Developing superior properties of epoxy resin composites with high fire resistance, light smoke, and low toxicity has been the focus of the research in the flame-retardant field. In particular, it is essential to decrease the emissions of toxic gases and smoke particles generated during the thermal decomposition of epoxy resin (EP) to satisfy the industrial requirements for environmental protection and safety. Consequently, the PZS@ZIF-67 composite was designed and synthesized by employing the hydroxyl group-containing polyphosphazene (poly(cyclotriphosphazene-co-4,4′-dihydroxydiphenylsulfone), PZS) as both the interfacial compatibility and an in situ template and the ZIF-67 nanocrystal as a nanoscale coating and flame-retardant cooperative. ZIF-67 nanocrystal with multidimensional nanostructures was uniformly wrapped on the surface of PZS microspheres. Subsequently, the acquired PZS@ZIF-67 composite was incorporated into the epoxy resin to prepare composite samples for the study of their fire safety, toxicity suppression, and mechanical performance. Herein, the EP/5% PZS@ZIF-67 passed the V-0 rating in a UL-94 test with a 31.9% limit oxygen index value. More precisely, it is endowed with a decline of 51.08%, 28.26%, and 37.87% of the peak heat release rate, the total heat release, and the total smoke production, respectively. In addition, the unique structure of PZS@ZIF-67 microsphere presented a slight impact on the mechanical properties of EP composites at low loading. The PZS@ZIF-67 possible flame-retardant mechanism was speculated based on the analysis of the condensed phase and the gas phase of EP composites.

A new strategy for the preparation of an integrated three-source intumescent flame retardant (IFR) has been developed to improve the flame-retardant and smoke suppression performance of epoxy resin (EP) with a synergistic flame retardant effect. Herein, the synthesis of a macromolecular spirocyclic phosphorus/nitrogen-containing IFR poly sulfonamide spirocyclic pentaerythritol bisphosphonate (SAPC) is reported via a two-step method that uses pentaerythritol, phosphorus oxychloride and sulfonamide (SAA) as raw materials. Subsequently, the SAPC was incorporated into EP to prepare the composite to investigate its thermal stability, flame retardancy, and smoke suppression performance. Herein, a differential scanning calorimetry (DSC) analysis showed that the addition of SAPC increased the glass transition temperature (T_g) of the composite. Cone test results indicated that the incorporation of 8 wt % SAPC significantly improved the flame-retardant performance for the composite, with a 43.45% decrease in peak of heat release rate, a 28.55% reduction in total heat release, and a 30.04% decrease in total smoke release. Additionally, the composite received the V-0 rating in a UL-94 vertical burning test, accompanied by the “blowout” phenomenon. After the addition of SAPC, the amount of flammable gas products from the EP composite decomposition was obviously suppressed, and the amount of non-flammable as was increased. All of this suggests a good dilution role of SAPC. There are enough reasons to believe that the enhanced flame-retardant and toxicity suppression performance for the EP composite can be attributed to the good coordination of carbonization agent, acid source, and blowing agent in the SAPC structure.

Fire-protection coatings with a self-monitoring ability play a critical role in safety and security. An intelligent fire-protection coating can protect humans from personal and property damage. In this work, we report the fabrication of a low-cost and facile intelligent fire coating based on a composite of ammonium polyphosphate and epoxy (APP/EP). The composite was processed using laser scribing, which led to a laser-induced graphene (LIG) layer on the APP/EP surface via a photothermal effect. The C–O, C=O, P–O, and N−C bonds in the flame-retardant APP/EP composite were broken during the laser scribing, while the remaining carbon atoms recombined to generate the graphene layer. A proof-of-concept was achieved by demonstrating the use of LIG in supercapacitors, as a temperature sensor, and as a hazard detection device based on the shape memory effect of the APP/EP composite. The intelligent flame protection coating had a high flame retardancy, which increased the time to ignition (TTI) from 21 s to 57 s, and the limiting oxygen index (LOI) value increased to 37%. The total amount of heat and smoke released during combustion was effectively suppressed by ≈ 71.1% and ≈ 74.1%, respectively. The maximum mass-specific supercapacitance could reach 245.6 F·g⁻¹. The additional LIG layer enables applications of the device as a LIG-APP/EP temperature sensor and allows for monitoring of the deformation according to its shape memory effect. The direct laser scribing of graphene from APP/EP in an air atmosphere provides a convenient and practical approach for the fabrication of flame-retardant electronics.