Dinghua Li

Ammonium polyphosphate (APP) is widely used in intumescent flame-retardant (IFR) systems because of its environmental friendliness, low cost, and high flame-retardant efficiency. However, its practical applications are limited by high hygroscopicity, poor compatibility with organic substrates, and the high loading required in single-component systems. To address these limitations, extensive studies have been conducted on APP modification and synergistic flame-retardant systems. This review systematically summarizes the modification strategies and flame-retardant mechanisms of APP. The synergistic flame-retardant effects and mechanisms of APP combined with silicon-, boron-, and metal-containing compounds are also discussed. In addition, the effects on the flame-retardant performance of different structural characteristics, such as nanostructures, layered structures, and ring structures, are reviewed. Finally, the current challenges and future perspectives of APP-based flame-retardant systems are highlighted. This review provides useful guidance for the design, optimization, and practical application of advanced APP-based intumescent flame-retardant materials.

The ladder phenyl/vinyl polysilsesquioxane (PhVPOSS) was used to improve the flame-retardancy performances of ethylene-vinyl acetate copolymer (EVA)/aluminum hydroxide (ATH) composites due to the reactivity of its vinyl groups. FTIR, XPS, ¹H NMR, and SEM-EDS data demonstrated the PhVPOSS grafting onto EVA molecular chains. The PhVPOSS improved the thermal stability of EVA/ATH composites, as shown by the thermogravimetric analysis (TGA). Furthermore, with the cone calorimeter (CONE) experiments, EVA/ATH/PhVPOSS showed better fire safety than the EVA/ATH composites, with the PHRR, PSPR, and PCOP reduced by 7.89%, 57.4%, and 90.9%, respectively. The mechanism investigations of flame retardancy revealed that the charring behaviors of the EVA/ATH/PhVPOSS composites were improved by the formation of Si-C bonds and Si-O bonds, and a more compact and denser char layer can contribute more to the barrier effect.

As synthetic fibers with superior performances, nylon 6 fibers are widely used in many fields. Due to the potential fire hazard caused by flammability, the study of the flame retardancy of nylon 6 fibers has been attracting more and more attention. The review has summarized the present research status of flame-retarded nylon 6 fibers from three aspects: intrinsic flame-retarded nylon 6, nylon 6 composites, and surface strategies of nylon 6 fibers/fabrics. The current main focus is still how to balance the application performances, flame retardancy, and production cost. Moreover, melt dripping during combustion remains a key challenge for nylon 6 fibers, and the further developing trend is to study novel flame retardants and new flame-retardancy technologies for nylon 6 fibers.

An eco-friendly clay-based synergistic flame-retardant coating was established on cotton fabrics via facile layer-by-layer assembly derived from polyethyleneimine (PEI), attapulgite clay (ATP), and phytic acid (PA). The fabricated flame-retardant (FR) cotton fabrics demonstrated improved thermal stability. Compared to untreated cotton fabrics, the limiting oxygen index of Cotton-8TL was improved to 27.0%. The peak heat release rates of the prepared FR cotton fabrics were lower than that of the pristine cotton fabrics, showing a maximum reduction of 41%. The deposition coating system improved the amount of char residue effectively. The intumescent flame-retardant mechanism was proposed through the analysis of char residue and the suppression properties of volatile gases. Furthermore, compared with those of the untreated cotton fabrics, the tensile strength and elongation at break of the FR cotton fabrics in the warp direction were improved by 20% and 47% remarkably, respectively. A feasible surface modification strategy was provided for the flame-retardant treatment of cotton fabrics with the improvement of mechanical properties.

The effects of hydrogen bonding between solvents (ethanol, ethanol–acetone and ethanol–ethyl acetate) and ammonium dinitramide (ADN) crystal faces on the morphology of ADN are studied experimentally and by molecular dynamics (MD) simulation. Scanning electron microscopy shows that ADN recrystallized from ethanol, ethanol–acetone and ethanol–ethyl acetate takes the form of a slice, a sheet aggregate and a sphere, respectively. The MD results show that the order of the standard deviation (E _dev) of the hydrogen-bonding energy (E _b) in the three solvent systems is as follows: ethanol > ethanol–acetone > ethanol–ethyl acetate. The larger the E _dev, the larger the difference of each crystal plane size. The radial distribution function reveals that the carbonyl group of ethyl acetate promotes hydrogen-bond formation between O atoms in the nitro groups of ADN and H atoms in ethanol; meanwhile the O atom in the C—O bond of ethyl acetate forms a hydrogen bond with an H atom in ADN. Therefore, the E _dev of each crystal face is further lowered, and finally a spherical ADN is obtained.

Based on the molecular dynamics method, the tris-(1-chloropropan-2yl) phosphate (TCPP)/montmorillonite (MMT) molecular model was established to study the binding energy and microstructure changes in TCPP and MMT. The theoretical simulation results showed that TCPP can enter the MMT layer and increase the layer spacing. From this, an organic intercalated Ca-montmorillonite TCPP-CaMMT was prepared by a very simple direct mixing method using flame retardant TCPP as a modifier. Polypropylene (PP) composites were prepared by TCPP, CaMMT, and TCPP-CaMMT. The microstructures of TCPP-CaMMT nanocompounds and PP composites were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM). The results showed that TCPP-CaMMT nanocompounds could be exfoliated into nanosheets in PP. The flame retardancy and mechanical properties of PP/TCPP-CaMMT samples were studied by limited oxygen index (LOI) measurements and tensile tests. The PP/TCPP-CaMMT composites showed better LOI, tensile strength, and elongation at break than the machine-mixed PP/TCPP + CaMMT.

A novel composite and functional micro-nanometer particle is designed by the hydrolysis of aluminium isopropoxide on the surface of ammonium polyphosphate (APP) to prepare surface nanostructured ammonium polyphosphate (NSAPP). NSAPP is characterised by XPS, XRF, SEM, water solubility tests, and TGA. Results indicate that nanosized aluminium hydroxide is deposited on the surface of NSAPP, which enhanced its water resistance and thermostability. Then, APP and NSAPP coupled with dipentaerythritol (DPER) is used for the flame retardant of polypropylene (PP). The limiting oxygen index (LOI) value of the PP/DPER/NSAPP composite is higher than that of PP/DPER/APP. Besides, the UL 94 vertical burning test of PP/DPER/NSAPP composites can reach the V-0 rating easily. According to the study of the combustion behaviour of FR-PP composites, NSAPP contributes to form a dense and multi-layered char in the combustion process. Thus, such an intumescent char with a ceramic-like, continuous, and dense structure over the PP matrix protects the underlying matrix and enhances the thermal stability of the condensed phase, thereby improving the flame retardant performance of FR-PP.

The choice of charring agent is one of the major issues for solvent‐free fireproof coatings. The effects of processing method and charring agent on the thermal insulation and fire resistance of the coatings were investigated in simulated fire scenarios. Dipentaerythritol (DPER), triazine agent (CFA), and pentaerythritol phosphate (PEPA) were compared as charring agent, and the thermal, combustion, fire resistance, and charring behaviors in different fire scenario were characterized for the fireproof coatings. Compared with high‐speed dispersing equipment, kneading processing equipment is favorable for improving the thermal stability and fire resistance of the coatings, because the stronger shearing force has promoted mixing and dispersion of the ingredients in solvent‐free fireproof coatings. As for charring agents, it is found that the fireproof coatings containing CFA or PEPA show better thermal and flame‐retardant performances. More residue was observed under nitrogen atmosphere in thermogravimetric analysis, less heat and smoke were released in cone calorimetry test. However, during the high temperature fire resistance test, their char layers were prone to delaminate while DPER‐containing coatings produced intact and stronger char layer with better heat insulation. For practical applications, the coating formulations need to be optimized to achieve both fire resistance and flame retardancy.