Polystyrene (PS) is widely used in the plastics industry, but the application range of PS is limited due to its inherently high flammability. A variety of two-dimensional (2D) nanomaterials have been reported to impart excellent flame retardancy to polymeric materials. In this study, a 2D nanomaterial MXene–organic hybrid (O-Ti3C2) was applied to PS as a nanofiller. Firstly, the MXene nanosheets were prepared by acid etching, intercalation, and delamination of bulk MAX (Ti3AlC2) material. These exfoliated MXene nanosheets were then functionalized using a cationic surfactant to improve the dispersibility in DMF. Even with a small loading of functionalized O-Ti3C2 (e.g., 2 wt%), the resulting PS nanocomposite (PS/O-Ti3C2) showed good thermal stability and lower flammability evidenced by thermogravimetric analysis (TGA) and pyrolysis-combustion flow calorimetry (PCFC). The peak heat release rate (pHRR) was significantly reduced by 32% compared to the neat PS sample. In addition, we observed that the temperature at pHRR (TpHRR) shifted to a higher temperature by 22 °C. By comparing the TGA and PCFC results between the PS/MAX and different weight ratios of PS/O-Ti3C2 nanocomposites, the thermal stability and 2D thermal- and mass-transfer barrier effect of MXene–organic hybrid nanosheets were revealed to play essential roles in delaying the polymer degradation.
Metal–organic frameworks (MOFs) are emerging as novel flame retardants for polymers, which, typically, can improve their thermal stability and flame retardancy. However, there is a lack of specific studies on the thermal decomposition kinetics of MOF-based polymer composites, although it is known that they are important for the modeling of flaming ignition, burning, and flame spread over them. The thermal decomposition mechanisms of poly (methyl methacrylate) (PMMA) have been well investigated, which makes PMMA an ideal polymer to evaluate how fillers affect its decomposition process and kinetics. Thus, in this study, UiO-66, a common type of MOF, was embedded into PMMA to form a composite. Based on the results from the microscale combustion calorimeter, the values of the apparent activation energy of PMMA/UiO-66 composites were calculated and compared against those of neat PMMA. Furthermore, under cone calorimeter tests, UiO-66, at only 1.5 wt%, can reduce the maximum burning intensity and average mass loss rate of PMMA by 14.3% and 12.4%, respectively. By combining UiO-66 and SiO2 to form a composite, it can contribute to forming a more compact protective layer, which shows a synergistic effect on reducing the maximum burning intensity and average mass loss rate of PMMA by 22.0% and 14.7%, respectively.
Polyurethanes (PUs) are versatile and widespread, particularly as flexible and rigid foams. To avoid isocyanates and other toxic reagents required for synthesis, such as phosgene, alternative synthetic routes have been utilized to produce non-isocyanate polyurethanes (NIPUs). A thermally and flame-resistant rigid NIPU was produced from environmentally benign and bio-sourced ingredients, requiring no catalyst or solvents. A foamed structure was obtained by the addition of glutaraldehyde and four different carboxylic acids: malic acid, maleic acid, citric acid, and aconitic acid. The resulting morphology, thermal degradation, and flame resistance of each foam were compared. The properties vary with each carboxylic acid used, but in each case, peak thermal degradation and peak heat release are postponed by >100 °C compared to commercial rigid PU foam. Furthermore, in a butane torch test, NIPU foams exhibit an 80% higher remaining mass and a 75% reduction in afterburn time, compared to commercial polyurethane. This bio-based polyurethane eliminates the hazards of traditional PUs, while imparting inherent thermal stability and flame resistance uncharacteristic of conventional foams.
The intumescent flame retardant (IFR) technique is an alternative to halogen-based flame retardants for reducing fire hazards in polymers. However, IFR has drawbacks like unsatisfactory flame-retardant efficiency and high loading requirements. In this study, MIL-125 (Ti-based metal–organic framework) is added to ABS/IFR composites to improve flame retardancy and reduce smoke emissions. Thermogravimetric analysis (TGA) results indicate that combining ammonium polyphosphate (APP) and expandable graphite (EG) increases charred residue and slows mass loss compared with the original ABS resin. The ABS/IFR/MIL-125 system stabilizes the char layer, serving as a protective shield against combustible gases during combustion. Additionally, MIL-125 enhances performance in microscale combustion calorimetry (MCC) flammability testing. In fire tests (UL-94, limiting oxygen index (LOI), and cone calorimeter), the ABS/IFR/MIL-125 system achieves a UL-94 V0 rating and the highest LOI value of 31.5% ± 0.1%. Peak heat lease rate (PHRR) values in the cone calorimeter are reduced by 72% with 20 wt.% of additives, and smoke production decreases by 53% compared with neat ABS. These results demonstrate the efficient synergistic effects of MIL-125 and IFR additives in improving the formation and stability of the intumescent char layer, thereby protecting ABS from intense burning.
Graphitic carbon nitride is a semiconducting material of a graphite-like 2D layered structure. It is well known for its photocatalytic properties, which can be exploited for solar-light-driven water splitting and degradation of organic pollutants. Here, we report its capabilities of catalyzing the reduction of the azo bond by hydrazine to two amines under visible light. This photocatalytic reaction provides a novel, appealing way to reduce azo dye wastes as pollutants other than degradation. With this method, the azo dye wastes can be photochemically converted to amines, which can be used as precursors for new azo dyes.