Construction of efficient and environmentally friendly bio-based flame retardant cotton fabric through layer by layer self-assembly of alkylammonium functional silsesquioxane/phosphorylated sodium alginate.

As an important source of green cleaning flame retardants, bio-based materials have been widely studied by researchers. However, the development of efficient biobased flame retardants and convenient finishing methods was of great significance for the functional finishing of materials. Herein, a convenient and efficient flame retardant cotton fabric was prepared via layer by layer self-assembly (LbL) by alternating precipitation of a novel bio-based flame retardant phosphorylated sodium alginate (PSA) and alkylammonium functionalized siloxane (A-POSS). The effect of coating number on flame retardancy and thermal properties of coated cotton fabric was systematically studied. Thermogravimetric analysis (TGA) results showed that residual char contents of AP/PS-15BL under air and N2 atmospheres increased by 252.0% and 225.2%, respectively, compared with control cotton. In vertical flammability tests, both the AP/PS-10BL and AP/PS-15BL showed self-extinguishing behavior and successfully passed the UL-94 V-0 rating. More importantly, the LOI value of AP/PS-15BL was significantly increased to 35.0% from 20.0% of pure cotton fabric. Additionally, coated samples showed good mechanical properties and washable resistance. In CONE test, the peak heat release rate (PHRR) and total heat release rate (THR) of AP/PS-15BL decreased by 89.3% and 49.3% respectively, compared with control cotton. Therefore, this green and convenient flame-retardant finishing method has great application potential in the multi-functional finishing of cotton fabrics.

Barrier function of graphene for suppressing the smoke toxicity of polymer/black phosphorous nanocomposites with mechanism change.

Recently, black phosphorous (BP) nanosheets as an emerging nanomaterial have presented significant fire safety improvement in polymer nanocomposites. However, as elemental phosphorus, fire safety improvement effect of BP nanosheets on polymer composites builds on the conversion of gaseous pyrolysis products into smoke particles, which inevitably promotes the formation and release of smoke particles. From the perspective of overall fire safety improvement, it is vital to simultaneously suppress the heat release and smoke production of polymer/BP composites. Herein, melamine-mediated graphene/black phosphorous nanohybrids (GNS/MA/BP) were fabricated through electrostatic-driving self-assembly process and introduced into polyether thermoplastic polyurethane (TPU). During combustion, the barrier function provided by thermally stable layered structure of graphene (GNS) enables more pyrolysis products of BP nanosheets to be kept within condensed phase and react with polymer matrix. Compared to pure TPU, the incorporated hierarchical nanostructure (GNS/MA/BP-2) decreases PHRR, THR, and total CO2 release of TPU composite by 54.7%, 23.5%, and 32.5%, respectively. Beside, in contrast to TPU-BP composite, the release rate of toxic smoke and CO gas of TPU-GNS/MA/BP-2 composite are reduced by 46.7% and 49.4%. With barrier function of graphene, the heat and smoke release behavior of polymer/BP nanocomposites is effectively suppressed.

Natural antioxidant functionalization for fabricating ambient-stable black phosphorus nanosheets toward enhancing flame retardancy and toxic gases suppression of polyurethane.

Herein, as a natural antioxidant, tannin (TA) is firstly used to functionalize black phosphorous (BP) nanosheets to improve the ambient stability and toxic suppression, thus decreasing the fire hazards of polymer materials. Compared to pure BP nanosheets, higher temperature for thermal oxidation decomposition is achieved for TA-BP nanosheets, directly confirming the ambient stability of TA-BP nanosheets. Meanwhile, from high resolution TEM and XPS results, TA-BP nanosheets after being exposed at air for 10 days present well-organized crystal structure and low POx bonds content. Cone calorimeter results illustrate that the incorporation of 2.0 wt% TA-BP nanosheets significantly decreases the peak value of heat release rate (-56.5 %), total heat release (-43.0 %), CO2 concentration (-57.3 %) of TPU composite. Meanwhile, with addition of low to 1.5 wt%, the release of highly-toxic CO gas is significantly suppressed, confirmed by lower peak value (0.52 mg/m3) and decreased total release amount (-55.1 %). The obviously enlarged tensile strength (36.7 MPa) and desirable elongation at break (622 %) are also observed. This strategy not only firstly adopts bio-based antioxidant to impart excellent environmental stability for BP nanosheets, but also promotes the promising potentials of BP nanosheets in the fire safety application of polymer composites.

Mimicking enzymatic systems: modulation of the performance of polymeric organocatalysts by ion-specific effects.

Like natural enzymatic systems, our study has demonstrated that the activity of the polymeric organocatalysts can be modulated by ion-specific effects via the combination of anion-specific salting-in/out effects and anion-specific polarization of hydrogen bonding induced stabilization of the transition state.