New aircraft are being designed with increasing quantities of composite materials used in their construction. Different from the more traditional metals, composites have a higher propensity to burn. This presents a challenge to transportation safety analyses, as the aircraft structure now represents an additional fuel source involved in the fire scenario. Performance testing data for composites burning in a fire at the integral scales of an accident event are nearly non-existent. This report describes fire tests for relevant carbon fiber epoxy materials that were designed to explore the bulk decomposition behavior of said material in a severe fire. Together with TGA decomposition data, the material is found to decompose in three mostly distinctive and sequential phases, epoxy pyrolysis, char oxidation, and carbon fiber oxidation. Fires were not severe in their thermal intensity compared to liquid fuel fires. Peak thermal intensities of around 220 kW/m2 or 1100 °C are achieved at very low air flow rates. The burn tests were remarkable in their duration, lasting 4-8 hours for 25-40 kg of combustible material.
Composite materials behave differently from conventional fuel sources and have the potential to smolder and burn for extended time periods. As the amount of composite materials on modern aircraft continues to increase, understanding the response of composites in fire environments becomes increasingly important. An effort is ongoing to enhance the capability to simulate composite material response in fires including the decomposition of the composite and the interaction with a fire. To adequately model composite material in a fire, two physical model development tasks are necessary; first, the decomposition model for the composite material and second, the interaction with a fire. A porous media approach for the decomposition model including a time dependent formulation with the effects of heat, mass, species, and momentum transfer of the porous solid and gas phase is being implemented in an engineering code, ARIA. ARIA is a Sandia National Laboratories multiphysics code including a range of capabilities such as incompressible Navier-Stokes equations, energy transport equations, species transport equations, non-Newtonian fluid rheology, linear elastic solid mechanics, and electro-statics. To simulate the fire, FUEGO, also a Sandia National Laboratories code, is coupled to ARIA. FUEGO represents the turbulent, buoyantly driven incompressible flow, heat transfer, mass transfer, and combustion. FUEGO and ARIA are uniquely able to solve this problem because they were designed using a common architecture (SIERRA) that enhances multiphysics coupling and both codes are capable of massively parallel calculations, enhancing performance. The decomposition reaction model is developed from small scale experimental data including thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC) in both nitrogen and air for a range of heating rates and from available data in the literature. The response of the composite material subject to a radiant heat flux boundary condition is examined to study the propagation of decomposition fronts of the epoxy and carbon fiber and their dependence on the ambient conditions such as oxygen concentration, surface flow velocity, and radiant heat flux. In addition to the computational effort, small scaled experimental efforts to attain adequate data used to validate model predictions is ongoing. The goal of this paper is to demonstrate the progress of the capability for a typical composite material and emphasize the path forward.
Polymer foams are used as encapsulants to provide mechanical, electrical, and thermal isolation for engineered systems. In fire environments, the incident heat flux to a system or structure can cause foams to decompose. Commonly used foams, such as polyurethanes, often liquefy and flow during decomposition, and evolved gases can cause pressurization and ultimately failure of sealed containers. In systems safety and hazard analyses, numerical models are used to predict heat transfer to encapsulated objects or through structures. The thermo-mechanical response of systems involving coupled foam decomposition, liquefaction, and flow can be difficult to predict. Predicting pressurization of sealed systems is particularly challenging. To mitigate the issues caused by liquefaction and flow, hybrid polyurethane cyanate ester foams have been developed that have good adhesion and mechanical properties similar to currently used polyurethane and epoxy foams. The hybrid foam decomposes predictably during decomposition. It forms approximately 50 percent by weight char during decomposition in nitrogen. The foam does not liquefy. The charring nature of the hybrid foam has several advantages with respect to modeling heat transfer and pressurization. Those advantages are illustrated by results from recent radiant heat transfer experiments involving encapsulated objects, as well as results from numerical simulations of those experiments.
Thermal gravimetric analysis (TGA) combined with evolved gas analysis by Fourier transform infrared spectroscopy (FTIR) or mass spectrometry (MS) often is used to study thermal decomposition of organic polymers. Frequently, results are used to determine decomposition mechanisms and to develop rate expressions for a variety of applications, which include hazard analyses. Although some current TGA instruments operate with controlled heating rates as high as 500° C/min, most experiments are done at much lower heating rates of about 5° to 50° C/min to minimize temperature gradients in the sample. The intended applications, such as hazard analyses involving fire environments, for rate expressions developed from TGA experiments often involve heating rates much greater than 50° C/min. The heating rate can affect polymer decomposition by altering relative rates at which competing decomposition reactions occur. Analysis of the effect of heating rate on competing first-order decomposition reactions with Arrhenius rate constants indicated that relative to heating rates of 5° to 50° C/min, observable changes in decomposition behavior may occur when heating rates approach 1,000° C/min. Results from experiments with poly(methyl methacrylate) (PMMA) samples that were heated at 5° to 50° C/min during TGA-FTIR experiments and results from experiments with samples heated at rates on the order of 1,000° C/min during pyrolysis-GC-FTIR experiments supported the analyses.
To provide input to numerical models for hazard and vulnerability analyses, thermal decomposition of eight polymers has been examined in both nitrogen and air atmospheres. Experiments have been done with poly(methyl methacrylate), poly(diallyl phthalate), Norwegian spruce, polyvinyl chloride), polycarbonate, poly(phenylene sulphide), and two polyurethanes. Polymers that formed a substantial amount of carbonaceous char during decomposition in a nitrogen atmosphere were completely consumed in an air atmosphere. However, in the case of polyurethanes, complete consumption did not occur until temperatures of 700° C or higher. Furthermore, to varying degrees, the presence of oxygen appeared to alter the decomposition processes in all of the materials studied.
Organic polymer materials are used frequently in structures and transportation systems. Polymer materials may provide fuel for a fire or be damaged catastrophically due to an incident heat flux. Modeling the response of such structures and systems in fire environments has important applications in safety and vulnerability analyses. The decomposition chemistry of the organic polymer materials is an important factor in many analyses. To provide input to numerical models for hazard and vulnerability analyses, the thermal decomposition chemistry of organic polymers is being experimentally investigated using TGA-FTIR, GC-FTIR, infrared microprobe (IRMP), and DSC Both TGA-FTIR and DSC experiments are done with unconfined and partially confined samples. Unconfined samples are used to examine initial decomposition reactions. Partially confined samples are used to examine reversible and secondary reactions. This paper discusses phenomena pertinent to using the aforementioned techniques to develop rate expressions for polymer decomposition reactions, and a specific example illustrating development of rate expressions for decomposition of PMMA is given.
A Chemical-structure-based PolyUrethane Foam (CPUF) decomposition model has been developed to predict the fire-induced response of rigid, closed-cell polyurethane foam-filled systems. The model, developed for the B-61 and W-80 fireset foam, is based on a cascade of bondbreaking reactions that produce CO2. Percolation theory is used to dynamically quantify polymer fragment populations of the thermally degrading foam. The partition between condensed-phase polymer fragments and gas-phase polymer fragments (i.e. vapor-liquid split) was determined using a vapor-liquid equilibrium model. The CPUF decomposition model was implemented into the finite element (FE) heat conduction codes COYOTE and CALORE, which support chemical kinetics and enclosure radiation. Elements were removed from the computational domain when the calculated solid mass fractions within the individual finite element decrease below a set criterion. Element removal, referred to as ?element death,? creates a radiation enclosure (assumed to be non-participating) as well as a decomposition front, which separates the condensed-phase encapsulant from the gas-filled enclosure. All of the chemistry parameters as well as thermophysical properties for the CPUF model were obtained from small-scale laboratory experiments. The CPUF model was evaluated by comparing predictions to measurements. The validation experiments included several thermogravimetric experiments at pressures ranging from ambient pressure to 30 bars. Larger, component-scale experiments were also used to validate the foam response model. The effects of heat flux, bulk density, orientation, embedded components, confinement and pressure were measured and compared to model predictions. Uncertainties in the model results were evaluated using a mean value approach. The measured mass loss in the TGA experiments and the measured location of the decomposition front were within the 95% prediction limit determined using the CPUF model for all of the experiments where the decomposition gases were vented sufficiently. The CPUF model results were not as good for the partially confined radiant heat experiments where the vent area was regulated to maintain pressure. Liquefaction and flow effects, which are not considered in the CPUF model, become important when the decomposition gases are confined.
Preliminary thermal decomposition experiments with Ablefoam and EF-AR20 foam (Ablefoam replacement) were done to determine the important chemical and associated physical phenomena that should be investigated to develop the foam decomposition chemistry sub-models that are required in numerical simulations of the fire-induced response of foam-filled engineered systems for nuclear safety applications. Although the two epoxy foams are physically and chemically similar, the thermal decomposition of each foam involves different chemical mechanisms, and the associated physical behavior of the foams, particularly ''foaming'' and ''liquefaction,'' have significant implications for modeling. A simplified decomposition chemistry sub-model is suggested that, subject to certain caveats, may be appropriate for ''scoping-type'' calculations.
The decomposition of unconfined rigid polyurethane foam has been modeled by a kinetic bond-breaking scheme describing degradation of a primary polymer and formation of a thermally stable secondary polymer. The bond-breaking scheme is resolved using percolation theory to describe evolving polymer fragments. The polymer fragments vaporize according to individual vapor pressures. Kinetic parameters for the model were obtained from thermal gravimetric analysis (TGA). The chemical structure of the foam was determined from the preparation techniques and ingredients used to synthesize the foam. Scale-up effects were investigated by simulating the response of an incident heat flux of 25 W/cm2 on a partially confined 8.8-cm diameter by 15-cm long right circular cylinder of foam that contained an encapsulated component. Predictions of internal foam and component temperatures, as well as regression of the foam surface, were in agreement with measurements using thermocouples and X-ray imaging.
The decomposition of unconfined rigid polyurethane foam has been modeled by a kinetic bond-breaking scheme describing degradation of a primary polymer and formation of a thermally stable secondary polymer. The bond-breaking scheme is resolved using percolation theory to describe evolving polymer fragments. The polymer fragments vaporize according to individual vapor pressures. Kinetic parameters for the model were obtained from Thermal Gravimetric Analysis (TGA). The chemical structure of the foam was determined from the preparation techniques and ingredients used to synthesize the foam. Scale-up effects were investigated by simulating the response of an incident heat flux of 25 W/cm{sup 2} on a partially confined 8.8-cm diameter by 15-cm long right circular cylinder of foam which contained an encapsulated component. Predictions of center, midradial, and component temperatures, as well as regression of the foam surface, were in agreement with measurements using thermocouples and X-ray imaging.