Effect of Hygrothermal Ageing on the Mechanical and Fire Properties of a Flame Retardant Flax Fiber/Epoxy Composite.

In engineering applications, natural fiber composites must comply with fire requirements including the use of flame retardant. Furthermore, biocomposites are known to be water sensitive. Whether flame retardants affect the water sensitivity and whether water absorption affects the fire behavior and the mechanical performance of biocomposites are the two main topics addressed in this work. In this study, a flax fiber/epoxy composite flame retardant with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or aluminum diethyl phosphinate (AlPi) was aged in humid atmosphere or by immersion in water. Water absorption kinetics revealed that DOPO induces an increase in equilibrium water content by approximately a factor of 2 due to its intrinsic hygroscopicity and/or its plasticizing effect on the epoxy matrix. In contrast, AlPi does not significantly change the water sensitivity of the biocomposite. Mechanical testing highlighted that, whatever the FR, the evolution of mechanical properties with ageing is governed by the moisture content. The drop of elastic modulus was attributed to a decrease in fiber rigidity due to plasticization, while the increase in tensile strength was assigned to an increase in fiber/matrix friction due to fiber swelling. As regards flame retardancy, only the highest water contents modified the fire behavior. For the AlPi containing biocomposite, the water release resulted in an increase by 50% of the time to ignition, while for the DOPO flame retardant biocomposite the water release was mainly postponed after ignition.

Graphene oxide incorporating carbon fibre-reinforced composites submitted to simultaneous impact and fire: Physicochemical characterisation and toxicology of the by-products.

The toxicological profile of particulates released from carbon fibre-reinforced composites (CFC) incorporating nanoadditives, under impact and fire conditions (e.g. aircraft crash), is unknown to date. Our aim was to investigate the effects of simultaneous impact and fire on the physicochemical features of the particles released from CFCs produced from a graphene oxide (GO)-reinforced epoxy resin and the consequences on its toxicological profile. CFC samples with (CFC + GO) or without GO (CFC) were subjected to simultaneous impact and fire through a specific setup. Soot and residues were characterised and their toxicity was compared to that of virgin GO. Virgin GO was not cytotoxic but induced pro-inflammatory and oxidative stress responses. The toxicity profile of CFC was similar for soot and residue: globally not cytotoxic, inducing a pro-inflammatory response and no oxidative stress. However, an increased cytotoxicity at the highest concentration was potentially caused by fibres of reduced diameters or fibril bundles, which were observed only in this condition. While the presence of GO in CFC did not alter the cytotoxicity profile, it seemed to drive the pro-inflammatory and oxidative stress response in soot. On the contrary, in CFC + GO residue the biological activity was decreased due to the physicochemical alterations of the materials.

New Biosourced Flame Retardant Agents Based on Gallic and Ellagic Acids for Epoxy Resins.

The aim of this work was an investigation of the ability of gallic (GA) and ellagic (EA) acids, which are phenolic compounds encountered in various plants, to act as flame retardants (FRs) for epoxy resins. In order to improve their fireproofing properties, GA and EA were treated with boric acid (to obtain gallic acid derivatives (GAD) and ellagic acid derivatives (EAD)) to introduce borate ester moieties. Thermogravimetric analysis (TGA) highlighted the good charring ability of GA and EA, which was enhanced by boration. The grafting of borate groups was also shown to increase the thermal stability of GA and EA that goes up respectively from 269 to 528 °C and from 496 to 628 °C. The phenolic-based components were then incorporated into an epoxy resin formulated from diglycidyl ether of bisphenol A (DGEBA) and isophorone diamine (IPDA) (72, 18, and 10 wt.% of DGEBA, IPDA, and GA or EA, respectively). According to differential scanning calorimetry (DSC), the glass transition temperature (Tg) of the thermosets was decreased. Its values ranged from 137 up to 108 °C after adding the phenolic-based components. A cone calorimeter was used to evaluate the burning behavior of the formulated thermosets. A significant reduction of the peak of heat release rate (pHRR) for combustion was detected. Indeed, with 10 wt.% of GA and EA, pHRR was reduced by 12 and 44%, respectively, compared to that for neat epoxy resin. GAD and EAD also induced the decrease of pHRR values by 65 and 33%, respectively. In addition, a barrier effect was observed for the resin containing GAD. These results show the important influence of the biobased phenolic compounds and their boron derivatives on the fire behavior of a partially biobased epoxy resin.

Lignin Nanoparticles as A Promising Way for Enhancing Lignin Flame Retardant Effect in Polylactide.

The present study investigates the effect of using lignin at nanoscale as new flame-retardant additive for polylactide (PLA). Lignin nanoparticles (LNP) were prepared from Kraft lignin microparticles (LMP) through a dissolution-precipitation process. Both micro and nano lignins were functionalized using diethyl chlorophosphate (LMP-diEtP and LNP-diEtP, respectively) and diethyl (2-(triethoxysilyl)ethyl) phosphonate (LMP-SiP and LNP-SiP, respectively) to enhance their flame-retardant effect in PLA. From the use of inductively coupled plasma (ICP) spectrometry, it can be considered that a large amount of phosphorus has been grafted onto the nanoparticles. It has been previously shown that blending lignin with PLA induces degradation of the polymer matrix. However, phosphorylated lignin nanoparticles seem to limit PLA degradation during melt processing and the nanocomposites were shown to be relatively thermally stable. Cone calorimeter tests revealed that the incorporation of untreated lignin, whatever its particle size, induced an increase in pHRR. Using phosphorylated lignin nanoparticles, especially those treated with diethyl (2-(triethoxysilyl)ethyl) phosphonate allows this negative effect to be overcome. Moreover, the pHRR is significantly reduced, even when only 5 wt% LNP-SiP is used.

Fire behavior of halogen-free flame retardant electrical cables with the cone calorimeter.

Fires involving electrical cables are one of the main hazards in Nuclear Power Plants (NPPs). Cables are complex assemblies including several polymeric parts (insulation, bedding, sheath) constituting fuel sources. This study provides an in-depth characterization of the fire behavior of two halogen-free flame retardant cables used in NPPs using the cone calorimeter. The influence of two key parameters, namely the external heat flux and the spacing between cables, on the cable fire characteristics is especially investigated. The prominent role of the outer sheath material on the ignition and the burning at early times was highlighted. A parameter of utmost importance called transition heat flux, was identified and depends on the composition and the structure of the cable. Below this heat flux, the decomposition is limited and concerns only the sheath. Above it, fire hazard is greatly enhanced because most often non-flame retarded insulation part contributes to heat release. The influence of spacing appears complex, and depends on the considered fire property.

Some Key Factors Influencing the Flame Retardancy of EDA-DOPO Containing Flexible Polyurethane Foams.

The role of various additives (emulsifier, anti-dripping agent) and formulation procedures (pre-dispersion of solid additives in polyol via milling) which influence the flame retardancy of 6,6'-[ethan-1,2-diylbis(azandiyl)]bis(6H-dibenzo[c,e][1,2]oxaphosphin-6-oxid) (EDA-DOPO) containing flexible polyurethane foams has been investigated in this work. For comparison, the flame retardancy of two additional structurally-analogous bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-based compounds, i.e., ethanolamine-DOPO (ETA-DOPO) and ethylene glycol-DOPO (EG-DOPO) were also evaluated together with EDA-DOPO in flexible PU foams of various formulations. The flame retardancy of these three bridged-DOPO compounds depends on the type of PU formulation. For certain PU formulations containing EDA-DOPO, lower fire performance was observed. Addition of emulsifier and polytetrafluoroethylene (PTFE) to these PU formulations influenced positively the flame retardancy of EDA-DOPO/PU foams. In addition, dispersion of EDA-DOPO and PTFE via milling in polyol improved the flame retardancy of the PU foams. Mechanistic studies performed using a microscale combustion calorimeter (MCC) and its coupling to FTIR showed no difference in the combustion efficiency of the bridged-DOPO compounds in PU foams. From MCC experiments it can be concluded that these bridged-DOPO compounds and their decomposition products may work primarily in the gas phase as flame inhibitors. The physiochemical behavior of additives in PU formulation responsible for the improvement in the flame retardancy of PU foams was further investigated by studying the dripping behavior of the PU foams in the UL 94 HB test. A high-speed camera was used to study the dripping behavior in the UL 94 HB test and results indicate a considerable reduction of the total number of melt drips and flaming drips for the flame retardant formulations. This reduction in melt drips and flaming drips during the UL 94 HB tests help PU foams achieve higher fire classification.

Controlled Emissivity Coatings to Delay Ignition of Polyethylene.

Semi-opaque to opaque films containing small amounts of various aluminium particles to decrease emissivity were easily prepared and coated onto low-density polyethylene (LDPE) sheets. The thermal-radiative properties (reflectivity, transmissivity and absorptivity) of the films were measured and related to the aluminum particles' content, size and nature. Time-to-ignition of samples was assessed using a cone calorimeter at different heat flux values (35, 50 and 75 kW/m²). The coatings allowed significant ignition delay and, in some cases, changed the material behaviour from thermally thin to thick behaviour. These effects are related both to their emissivity and transmissivity. A lower emissivity, which decreases during the degradation, and a lower transmissivity are the key points to ensure an optimal reaction-to-fire.