Intumescent Flame Retardant Mechanism of Lignosulfonate as a Char Forming Agent in Rigid Polyurethane Foam

Intumescent flame retardants (IFR) have been widely used to improve flame retardancy of rigid polyurethane (RPU) foams and the most commonly used char forming agent is pentaerythritol (PER). Lignosulfonate (LS) is a natural macromolecule with substantial aromatic structures and abundant hydroxyl groups, and carbon content higher than PER. The flame retardancy and its mechanism of LS as char forming agent instead of PER in IFR formulation were investigated by scanning electron microscopy, thermogravimetric analysis, limiting oxygen index testing and cone calorimeter test. The results showed LS as a char forming agent did not increase the density of RPU/LS foams. LOI value and char residue of RPU/LS foam were higher than RPU/PER and the mass loss of RPU/LS foam decreased 18%, suggesting enhanced thermal stability. CCT results showed LS as a char forming agent in IFR formulation effectively enhanced the flame retardancy of RPU foams with respect to PER. The flame retardancy mechanism showed RPU/LS foam presented a continuous and relatively compact char layer, acting as the effect of the flame retardant and heat insulation between gaseous and condensed phases. The efficiency of different LS ratio in IFR formulation as char forming agent was different, and the best flame retardancy and thermal stability was obtained at RPU/LS1.

Research on the Flame Retardancy Properties and Mechanism of Modified Asphalt with Halloysite Nanotubes and Conventional Flame Retardant

The inflammability of asphalt road will promote fire spread in the tunnel and produce lots of toxic smoke. To improve the fire resistance of asphalt pavement, mineral powder flame retardants are generally replaced by flame retardants in equal amounts. In this study, the effects of the synergistic flame retardancy system of halloysite nanotubes (HNTs) and conventional flame retardants (CFR) on the flame retardancy performance and mechanism of asphalt were investigated. Firstly, the flame retardancy properties of the HNTs and CFR composite modified asphalt were investigated based on the Cleveland open cup method (COC), Limiting oxygen index meter (LOI), and Cone calorimeter tests (CCTs). Then, the flame retardancy mechanism of the modified asphalt was studied based on Thermogravimetric analyzer (TGA), Fourier-transform infrared (FTIR), and Scanning electron microscopy (SEM). The results show that adding HNTs could improve the flame retardancy of the CFR modified asphalt binder. When 1 wt % HNTs and 8 wt % CFR were used, the limiting oxygen index of asphalt increased by 40.1%, the ignition temperature increased by 40 °C, while the heat release rate, total heat release, the smoke production rate, total smoke release, and other parameters decreased with varying degrees. Based on TG, FTIR, and SEM, the targeted flame retardancy mechanism and synergistic effect of HNTs/CFR flame retardancy system were revealed and summarized as three stages: (1) Stage 1, aluminum hydroxide (ATH) absorbs heat through thermal decomposition and inhibits the decomposition of lightweight components in asphalt; (2) Stage 2, aluminum diethyl phosphate (ADP) decomposes and produces organic phosphoric acid, which catalyzes crosslinking and ring thickening of asphalt and the quenching effect of phosphorus free radicals to block the combustion; and (3) Stage 3, HNTs plays an important role in increasing the integrity and density of the barrier layer. In addition, the Al2O3 produced by the decomposition of ATH, the carbon layer formed by the ADP catalyzed pitch, and HNTs play a significant synergistic effect in the formation of the barrier layer. Thus, the combination of HNTs and CFR has been proved to be a prospective flame retardancy system for asphalt.

Excellent Fireproof Characteristics and High Thermal Stability of Rice Husk-Filled Polyurethane with Halogen-Free Flame Retardant

The thermal stabilities, flame retardancies, and physico-mechanical properties of rice husk-reinforced polyurethane (PU–RH) foams with and without flame retardants (FRs) were evaluated. Their flammability performances were studied by UL94, LOI, and cone calorimetry tests. The obtained results combined with FTIR, TGA, SEM, and XPS characterizations were used to evaluate the fire behaviors of the PU–RH samples. The PU–RH samples with a quite low loading (7 wt%) of aluminum diethylphosphinate (OP) and 32 wt% loading of aluminum hydroxide (ATH) had high thermal stabilities, excellent flame retardancies, UL94 V-0 ratings, and LOIs of 22%–23%. PU–RH did not pass the UL94 HB standard test and completely burned to the holder clamp with a low LOI (19%). The cone calorimetry results indicated that the fireproof characteristics of the PU foam composites were considerably improved by the addition of the FRs. The proposed flame retardancy mechanism and cone calorimetry results are consistent. The comprehensive FTIR spectroscopy, TG, SEM, and XPS analyses revealed that the addition of ATH generated white solid particles, which dispersed and covered the residue surface. The pyrolysis products of OP would self-condense or react with other volatiles generated by the decomposition of PU–RH to form stable, continuous, and thick phosphorus/aluminum-rich residual chars inhibiting the transfer of heat and oxygen. The PU–RH samples with and without the FRs exhibited the normal isothermal sorption hysteresis effect at relative humidities higher than 20%. At lower values, during the desorption, this effect was not observed, probably because of the biodegradation of organic components in the RH. The findings of this study not only contribute to the improvement in combustibility of PU–RH composites and reduce the smoke or toxic fume generation, but also solve the problem of RHs, which are abundant waste resources of agriculture materials leading to the waste disposal management problems.

Flame Retardant Effect of Isocyanate Trimer on Polyisocyanurate Foam

The effect of Isocyanate trimer on the flame retardancy mechanism of polyisocyanurate (PIR) foam was studied through 3 aspects including the mechanism of thermal decomposition stage in condensed phase, the barrier mechanism of carbon layer formation on the surface in condensed phase and the mechanism in gaseous phase by using infrared spectroscopy, scanning electron microscopy, thermal analysis, cone calorimeter, high temperature pyrolysis gas chromatography mass spectrometry. The results show that the trimer can improve the thermal stability of the PIR foam and is not easily decomposed in the combustion. The trimer can increase the carbon content of the PIR foam to 29.9% than that of the polyurethane (PU) foam. The carbon layer formed is denser, and it can retards heat and oxygen and thus improve the flame retardant properties; trimer can reduce the release of flammable polyol gas, decompose into more carbon dioxide which is inert gas and it has certain flame retardant effect in the gaseous phase.

Flame retardancy mechanism of poly(butylene terephthalate)/aluminum diethylphosphinate composites with an epoxy-functional polysiloxane

The manuscript presents an outstanding synergistic effect of aluminum diethylphosphinate (AlPi) and epoxy-functional polysiloxane (EPM) for preparing flame-retardant poly(butylene terephthalate) (PBT).