A rational design of functionalized black phosphorus cooperates with piperazine pyrophosphate to significantly suppress the fire hazards of polypropylene.

The flammability of polypropylene (PP) not only has negative effects on human health but also causes environmental pollution. Herein, from the molecular polarity point of view, rationally designed hyperbranched charring foaming agents (HCFA) modified black phosphorus nanosheets by in situ polymerization to solve the fire hazards of PP. Based on the UL-94 test V-0 rating, the conventional flame retardant of piperazine pyrophosphate (PAPP) is substituted partly by the BP@PPC. Surprisingly, compared with 27 wt% of PAPP/PP, composites consisting of only 2 wt% of BP@PPC and 20 wt% PAPP/PP also passes the V-0 rating. The results of the cone calorimeter test confirmed that adding BP@PPC decreases the total heat release (THR) and peak heat release (PHRR) by a large amount, which are decreased by 23.4%, 85.8% respectively compared with PP. Moreover, it is uncommon for the fire growth index of BP@PPC composites to be 66.7% lower than that of PAPP/PP composites. In addition, the incorporation of BP@PPC has almost no impact on the mechanical characteristics of PP composites. This study offers a reference for combining established flame retardants with novel compounds to modify the burning behaviors of PP.

Flame-retardant activity of ternary integrated modified boron nitride nanosheets to epoxy resin.

In order to improve the fire safety of epoxy resin, ZIF-8 nanoparticle in-situ decorated boron nitride nanosheet (BN-OH/ZIF-8) is fabricated via self-assembly method and then ternary integrated BN-OH/ZIF-8/PA hybrids are prepared through the chemical etching effect of phytic acid. FTIR, XRD, XPS, TEM and TGA measurements are used to characterize the structure and morphology of the nanohybrids. The researches show that BN-OH/ZIF-8/PA not only uniformly distributed in EP matrix, but also improve the thermal stability of EP. The peak heat release rate, peak smoke production rate, total smoke production values, the fire growth index and peak CO production rate obtained from cone test are significantly decreased, demonstrating the reduction of the fire hazards of EP composites containing BN-OH/ZIF-8/PA. The nano barrier effect and catalytic activity of BN-OH/ZIF-8/PA may be conducive to suppress the release of combustible volatile products and heat, facilitate the formation of graphitized carbon layer, and protect matrix from flame damage. The ternary integrated method developed in this study explores a new way to improve the flame retardant properties of EP, thereby promoting its application range.

Revealing and modeling of fire products in gas-phase for epoxy/black phosphorus-based nanocomposites.

This work aims at revealing and optimizing the mechanism, to promote the design of phosphorus-based flame retardants (PFRs) for controlling the spread of fire risk caused by the continuous spread of polymers. Herein, we synthesized about 10 nm TiO2 grown in situ on the surface of BP through a simple hydrothermal procedure to introduce it into epoxy (EP/BP-TiO2). In the first place, EP/BP-TiO22.0 nanocomposite achieves a reduction of 58.96% and 50.35% in PHRR and THR, respectively. Secondly, the pyrolysis of BP from Pn to P4, P3 and P2 is revealed. As a guide, P4 is established as a characteristic product of the analytical model for evaluating the effects in the gas phase for BP-based hybrids. Finally, this work clarifies the enhancement path for BP-TiO2 is optimized for the capturing of OH· and H· radicals by P4(POx). Crucially, this study reveals and controls the mechanism of the BP-based hybrids at the molecular level, which is expected to provide a promising analytical model for broad market PFRs design to address the risks and challenges of casualties and ecology caused by composites fire.

Novel CuCo2O4/graphitic carbon nitride nanohybrids: Highly effective catalysts for reducing CO generation and fire hazards of thermoplastic polyurethane nanocomposites.

Novel spinel copper cobaltate (CuCo2O4)/graphitic carbon nitride (g-C3N4) (named C-CuCo2O4) nanohybrids with different weight ratios of g-C3N4 to CuCo2O4 were successfully synthesized via a facile hydrothermal method. Then the nanohybrids were added into the thermoplastic polyurethane (TPU) matrix to prepare TPU nanocomposites using a master batch-melt compounding approach. Morphological analysis indicated that CuCo2O4 nanoparticles were uniformly distributed on g-C3N4 nanosheets. Thermal analysis revealed that C-CuCo2O4-7 (proportion of g-C3N4 to CuCo2O4 of 93/7) was an optimal nanohybrid for the properties improvement of TPU. Incorporation of C-CuCo2O4-7 into TPU led to significant improvements in the onset decomposition temperature, temperature at maximal mass loss rate and char yields. The heat release rate and total heat release of TPU/C-CuCo2O4-7 decreased by 37% and 31.3%, respectively, compared with those of pure TPU. Furthermore, the amounts of pyrolysis gaseous products, including combustible volatiles and carbon monoxide (CO), were remarkably reduced, whereas, non-flammable gas (carbon dioxide) increased. Excellent dispersion of C-CuCo2O4-7 in TPU host was achieved, due to the synergistic effect between g-C3N4 and CuCo2O4. Enhancements in the thermal stability and flame retardancy were attributed to the explanations that g-C3N4 nanosheets showed the physical barrier effect and catalytic nitrogen monoxide (NO) decomposition, and that CuCo2O4 catalyzes the reaction of CO with NO and increased char residues.

Influence of g-C3N4 nanosheets on thermal stability and mechanical properties of biopolymer electrolyte nanocomposite films: a novel investigation.

A series of sodium alginate (SA) nanocomposite films with different loading levels of graphitic-like carbon nitride (g-C3N4) were fabricated via the casting technique. The structure and morphology of nanocomposite films were investigated by X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. Thermogravimetric analysis results suggested that thermal stability of all the nanocomposite films was enhanced significantly, including initial thermal degradation temperature increased by 29.1 °C and half thermal degradation temperature improved by 118.2 °C. Mechanical properties characterized by tensile testing and dynamic mechanical analysis measurements were also reinforced remarkably. With addition of 6.0 wt % g-C3N4, the tensile strength of SA nanocomposite films was dramatically enhanced by 103%, while the Young's modulus remarkably increased from 60 to 3540 MPa. Moreover, the storage modulus significantly improved by 34.5% was observed at loadings as low as 2.0 wt %. These enhancements were further investigated by means of differential scanning calorimetry and real time Fourier transform infrared spectra. A new perspective of balance was proposed to explain the improvement of those properties for the first time. At lower than 1.0 wt % loading, most of the g-C3N4 nanosheets were discrete in the SA matrix, resulting in improved thermal stability and mechanical properties; above 1.0 wt % and below 6.0 wt % content, the aggregation was present in SA host coupled with insufficient hydrogen bondings limiting the barrier for heat and leading to the earlier degradation and poor dispersion; at 6.0 wt % addition, the favorable balance was established with enhanced thermal and mechanical performances. However, the balance point of 2.0 wt % from dynamic mechanical analysis was due to combination of temperature and agglomeration. The work may contribute to a potential research approach for other nanocomposites.

The influence of titanate nanotube on the improved thermal properties and the smoke suppression in poly(methyl methacrylate).

The well-dispersed poly(methyl methacrylate)/titanate nanotube (PMMA/TNT) composites were synthesized by in situ polymerization of methyl methacrylate (MMA) in ethanol solution. Thermal stability and the glass transition temperature of the composites are significantly enhanced with a proper amount of TNTs. The comparison between PMMA/TNTs and PMMA/TiO(2) composites suggests the formation of network in PMMA/TNTs composite. The coaction of dehydration and the network is believed to be the crucial factor which improves the thermal properties. TG-FTIR analysis shows that the amount of organic volatiles of PMMA is significantly reduced and the non-flammable CO(2) is generated after incorporating TNTs. It implies the reduced toxicity of the volatiles. The possible mechanism of the smoke suppression is proposed as the dehydration and adsorption effect of TNTs.