Composites on fire at reduced scale: evaluation, characterization and modeling

Composite materials are increasingly being used in the design of aircraft, train, ship and buildings. They are very often structural parts and they must meet the difficult challenge of having adequate structural fire protection. In fire scenarios of particular relevance according to the targeted applications, suitable strategies to control fire hazards are needed for composite structures. There are three main methods available to design composite structures with improved fire resistance behavior: (i) use “normal” structural materials and add surface protection, (ii) use fire retarded versions of “normal” structural materials, and (iii) use structural materials with inherently good fire retardant properties. The first approach is of interest since it does not modify the intrinsic properties of the structural composites and does not lead to processing problems (e.g. incorporation of fillers in the material). It can be achieved with intumescent coatings: when heating beyond a critical temperature, the intumescent material begins to swell and then to expand forming an insulative coating limiting heat and mass transfers. Intumescence will be used in this work On the other hand, the evaluation of fire resistance of intumescent coatings protecting structural composite requires large scale equipment. Due to the complexity of fire phenomenon, full-scale tests are still the main and the most credible tool for investigating fire-related issues but they are however very costly, and generally, the cost significantly increases with scale. For those reasons we have developed reliable, repeatable and fast small scale tests including: (i) a furnace delivering temperature/time curves such as ISO 834, UL-1709 and other curves depending on specific fire conditions (curves ‘on demand’), (ii) a jet fuel fire test (according to ISO 2685 or NextGen) devoted to evaluate the fire resistance of components, equipment and structure located in ‘fire zones’ in aircraft (e.g. compartments containing main engines and auxiliary power units) and (iii) a mini Steiner tunnel (according to ASTM E84). It then permits the ‘high throughput’ development of intumescent coatings protecting composites. Examples using the mini Steiner tunnel and the reduced jet fuel fire test will be presented in the talk. The first example deals with the fire protection carbon fiber reinforced polymer (CFRP) in aircraft structure. Intumescent silicone based-coatings (low and high intumescing coatings) are evaluated on CFRP using a bench mimicking a jet fuel fire occurring at high heat flux (200 kW/m²) (Figure 1). It is shown the development of large intumescence (high intumescing coating) associated with appropriate thermal properties of the coating (heat conductivity measured as low as 0.3 W/m.K) provides efficient protection for the CFRP at the jet fire test. On the other hand, the formation of cohesive ceramic (low intumescing coating) with low heat conductivity (constant heat conductivity as a function of temperature of 0.35 W/m.K) also provides protection but its efficiency is lower than that of intumescent char. It is evidenced that intumescent silicone-based coatings are materials of choice for protecting CFRP in the case of jet fuel fire. Figure 1 – Jet fuel fire at reduced scale on CFRP protected by an intumescent coating In the second example, different intumescent coatings protecting polyethylene terephthalate (PET) rigid foams used in roofing structure are evaluated using the mini Steiner tunnel. Results show good correlation between the two scales and the approach developed at the small scale permits the fast screening of intumescent paints to predict their fire behavior at the large scale. Finally, mechanistic aspects of intumescence based on our small scale tests will be investigated including the chemistry, the physic, the rheology and the modeling of the intumescenc

Innovative polyelectrolyte treatment to flame-retard wood

Fire protection has been a major challenge in wood construction for many years, mainly due to the high flame spread risk associated with wood flooring. Wood fire-retardancy is framed by two main axes: coating and bulk impregnation. There is a growing need for economically and environmentally friendly alternatives. The study of polyelectrolyte complexes (PECs) for wood substrates is in its infancy, but PECs’ versatility and eco-friendly character are already recognized for fabric fire-retardancy fabrics. In this study, a new approach to PEC characterization is proposed. First, PECs, which consist of polyethyleneimine and sodium phytate, were chemically and thermally characterized to select the most promising systems. Then, yellow birch (Betula alleghaniensis Britt.) was surface-impregnated under reduced pressure with the two PECs identified as the best options. Overall, wood fire-retardancy was improved with a low weight gain of 2 wt.% without increasing water uptake

Characterisation of the dispersion in polymer flame retarded nanocomposites

Flame retardant nanocomposites have attracted many research efforts because they combine the advantages of a conventional flame retardant polymer with that of polymer nanocomposite. However the properties obtained depend on the dispersion of the nanoparticles. In this study, three types of polymer flame retarded nanocomposites based on different matrices (polypropylene (PP), polybutadiene terephtalate (PBT) and polyamide 6 (PA6)) have been prepared by extrusion. In order to investigate the dispersion of nanoparticles in the polymer containing flame retardant, conventional methods used to characterise the morphology of composites have been applied to FR composites containing nanoclays. XRD, TEM and melt rheology give useful information to describe the dispersion of the nanofiller in the flame retarded nanocomposite. In the PA6-OP1311 (phosphorus based flame retardant) materials, the clay is well dispersed unlike in PBT and PP materials where microcomposites are obtained with some intercalation. The poor dispersion is also highlighted by NMR measurements but the presence of flame retardant particles interferes in the quantitative evaluation of nanoclay dispersion and underestimations are made

A facile technique to extract the cross-sectional structure of brittle porous chars from Intumescent coatings

Intumescent coatings are part of passive fire protection systems. In case of fire, they expand under thermal stimuli and reduce heat transfer rates. Their expansion mechanisms are more or less recognized, but the fire testing data shall be interpreted as function of coating morphology. Expansion ratios are examined together with the inner structures of specimens submitted to fire. Bare cutting techniques damage the highly porous and fibrous specimens because they become very crumbly due to charring. So far, absorption contrasted X-ray computed microtomography (CT) was used as a non-destructive technique. Nevertheless, access to X-ray platforms can be relatively expensive and scarce for regular use. Also, it has some drawbacks for carbon rich specimens strongly adhering on steel substrates because it leads sometimes to noisy images and lost data due to resolution limits on specimens reaching ten of centimeters. Therefore, we propose an inexpensive and more accessible experimental approach to observe those specimens with minimized structural damage under visible lighting. To that end, charred specimens were casted into pigmented epoxy resin. After surface treatments, color contrasted cross-sections could be observed under optical digital microscopy thanks to high level of interconnectivity of pores. Subsequent image treatments confirmed that the structural integrity was kept when compared to previous CT data. The proposed method is practical, cheaper and more accessible for the quantitative assessment of inner structure of charred brittle specimens

Intumescent Polymer Metal Laminates for Fire Protection

Intumescent paints are applied on materials to protect them against fire, but the development of novel chemistries has reached some limits. Recently, the concept of “Polymer Metal Laminates,” consisting of alternating thin aluminum foils and thin epoxy resin layers has been proven efficient against fire, due to the delamination between layers during burning. In this paper, both concepts were considered to design “Intumescent Polymer Metal Laminates” (IPML), i.e., successive thin layers of aluminum foils and intumescent coatings. Three different intumescent coatings were selected to prepare ten-plies IPML glued onto steel substrates. The IPMLs were characterized using optical microscopy, and their efficiency towards fire was evaluated using a burn-through test. Thermal profiles obtained were compared to those obtained for a monolayer of intumescent paint. For two of three coatings, the use of IPML revealed a clear improvement at the beginning of the test, with the slopes of the curves being dramatically decreased. Characterizations (expansion measurements, microscopic analyses, in situ temperature, and thermal measurements) were carried out on the different samples. It is suggested that the polymer metal laminates (PML) design, delays the carbonization of the residue. This work highlighted that design is as important as the chemistry of the formulation, to obtain an effective fire barrier

Additive manufacturing of fire‐retardant ethylene‐vinyl acetate

International audienceThermocompression (with also extrusion and injection molding) is a classical polymer shaping manufacturing, but it does not easily allow designing sophisticated shapes without using a complex mold, on the contrary to 3D printing (or polymer additive manufacturing), which is a very flexible technique. Among all 3D printing techniques, fused deposition modeling is of high potential for product manufacturing, with the capability to compete with conventional polymer processing techniques. This is a quite low cost 3D printing technique, but the range of filaments commercially available is limited. However, in some specific 3D printing processes, no filaments are necessary. Polymers pellets feed directly the printing nozzle allowing to investigate many polymeric matrices with no commercial limitation. This is of high interest for the design of flame-retarded materials, but literature is scarce in that field. In this paper, a comparison between thermocompression and 3D printing processes was performed on both neat ethylene-vinyl acetate (EVA) copolymer and EVA flame retarded with aluminum triHydroxyde (ATH) containing different loadings (30 or 65 wt%) and with expandable graphite (EG), ie, EVA/ATH (30 wt%), EVA/ATH (65 wt%), and EVA/EG (10 wt%), respectively. Morphological comparisons, using microscopic and electronic microprobe analyses, revealed that 3D printed plates have lower apparent density and higher porosity than thermocompressed plate. The fire-retardant properties of thermocompressed and 3D printed plates were then evaluated using mass loss calorimeter test at 50 kW/m2. Results highlight that 3D printing can be used to produce flame-retardant systems. This work is a pioneer study exploring the feasibility of using polymer additive manufacturing technology for designing efficient flame-retarded materials

Preparation and Characterisation of UV-Curable Flame Retardant Wood Coating Containing a Phosphorus Acrylate Monomer

The application of a flame retardant coating is an effective solution to enhance the fire retardancy of wood flooring. However, finding the right balance between reducing the flame propagation and good overall coating properties while conserving wood appearance is complex. In order to answer this complex problem, transparent ultraviolet (UV)-curable flame retardant wood coatings were prepared from an acrylate oligomer, an acrylate monomer, and the addition of the tri(acryloyloxyethyl) phosphate (TAEP), a phosphorus-based monomer, at different concentrations in the formulation. The coatings’ photopolymerisation, optical transparency, hardness, water sorption and thermal stability were assessed. The fire behaviour and the adhesion of the coatings applied on the yellow birch panels were evaluated, respectively, using the cone calorimeter and pull-off tests. Scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) analyses were performed on the collected burnt residues to obtain a better understanding of the flame retardancy mechanism. Our study reveals that phosphorus monomer addition improved the coating adhesion and the fire performance of the coated wood without impacting the photopolymerisation. The conversion percentage remained close to 70% with the TAEP addition. The pull-off strength reached 1.12 MPa for the coating with the highest P-monomer content, a value significantly different from the non-flame retarded coating. For the same coating formulation, the peak of heat release rate decreased by 13% and the mass percentage of the residues increased by 37% compared to the reference. However, the flame-retarded coatings displayed a higher hygroscopy. The action in the condensed phase of the phosphorus flame retardant is highlighted in this study

A Facile Technique to Extract the Cross-Sectional Structure of Brittle Porous Chars from Intumescent Coatings

Intumescent coatings are part of passive fire protection systems. In case of fire, they expand under thermal stimuli and reduce heat transfer rates. Their expansion mechanisms are more or less recognized, but the fire testing data shall be interpreted as function of coating morphology. Expansion ratios are examined together with the inner structures of specimens submitted to fire. Bare cutting techniques damage the highly porous and fibrous specimens because they become very crumbly due to charring. So far, absorption contrasted X-ray computed microtomography (CT) was used as a non-destructive technique. Nevertheless, access to X-ray platforms can be relatively expensive and scarce for regular use. Also, it has some drawbacks for carbon rich specimens strongly adhering on steel substrates because it leads sometimes to noisy images and lost data due to resolution limits on specimens reaching ten of centimeters. Therefore, we propose an inexpensive and more accessible experimental approach to observe those specimens with minimized structural damage under visible lighting. To that end, charred specimens were casted into pigmented epoxy resin. After surface treatments, color contrasted cross-sections could be observed under optical digital microscopy thanks to high level of interconnectivity of pores. Subsequent image treatments confirmed that the structural integrity was kept when compared to previous CT data. The proposed method is practical, cheaper and more accessible for the quantitative assessment of inner structure of charred brittle specimens

Intumescent ethylene-vinyl acetate copolymer: Reaction to fire and mechanistic aspects

The concept of intumescence was applied to flame retard ethylene vinyl acetate copolymer (EVA). The paper examines two types of intumescence based on expandable graphite (EG, physical expansion) and on modified ammonium polyphosphate (AP760, chemical expansion). The incorporation of expandable graphite (EG) at relatively low loading (10 wt%) in EVA permits the reduction up to 65% of peak of heat release rate (pHRR) measured by cone calorimetry. The mode of action occurs via the formation of an expanded carbonaceous layer acting mainly as heat barrier limiting heat and mass transfer as evidenced by the temperature measurement as a function of time during cone calorimetry. The incorporation of small amount of ZnCO3 in EVA-AP760 enhances strongly the performance: pHRR was not reduced using the sole AP760 while it is decreased by 54% when only 2 wt% of AP760 is substituted by ZnCO3. A strong synergistic effect was therefore observed. Solid state NMR of 31P and 13C on cone residues prepared at different characteristic times evidenced the mechanism involved is the reinforcement of the protective char by the formation of phosphate glass limiting the creation of cracks and increasing the char strength

An efficient bi-layer intumescent paint metal laminate fire barrier for various substrates: Extension to other application

Different types of passive fireproofing materials exist such as intumescent paints. Our approach was to modify the design the material instead of changing the formulations. By combining two concepts namely intumescence and delamination, and adjustable design, new effective fire barrier was developed to protect composites. It was evaluated using a burn-through fire scenario (heat flux of 116 kW/m2 and temperature of flame of 1100 °C). The fire barrier revealed to provide fire protection to the composite and stabilized the temperature at the backside of the composite plate under 200 °C. Characterisations (cross-section observations, expansion measurements, etc.) were carried out on the samples and a mechanism of action was proposed