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Polyurea (PU) elastomers have become increasingly popular in recent years due to their exceptional blast mitigation, ballistic protection, and wear resistance properties. However, their applications as protective materials are often limited as a result of their high flammability. In this study, aromatic dianhydrides (ArDAs) were employed to capture the thermal decomposing products of PU during combustion and facilitate the generation of highly heat-resistant aromatic polyimides (i.e., end group capturing effect), thus enhancing the material's char-forming ability and improving its flame retardancy. The ArDAs were found to significantly reduce the peak heat release rate (PHRR), total heat release (THR), total smoke release (TSR), and total CO release (TCO) of PU, and meanwhile increased the amount of char residue. At 20 wt% content of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), PHRR, THR, TSR and TCO of PU were reduced by 70.6%, 32.5%, 44.7% and 58.8%, respectively, the char residue was increased by 405%, and the mechanical properties of PU were well maintained (88.5% tensile strength and 91.0% elongation at break of pure PU). These findings demonstrate that ArDAs could serve as a new kind of halogen/phosphorus-free flame retardant for PU elastomers. [Display omitted] • Novel halogen/phosphorus-free flame retardants were designed for PU elastomers. • The flame retardant mechanism is end group capturing by aromatic dianhydrides (ArDAs). • PHRR, THR, TSR and TCO were simultaneously reduced, and char residue was improved. • Both excellent flame retardant property and high mechanical property were achieved. [ABSTRACT FROM AUTHOR]

The aggregation and plasticizing of most 9,10-dihydro-9-oxa-10-phosphaphenanthrene −10-oxide (DOPO) derived additives often result in deteriorating the glass transition temperature and mechanical properties of epoxy resins (EP). To address this issue, an imide-DOPO derivative (BMP) with bulky aromatic structure was successfully synthesized. Benefitting from the space hindering and intermolecular interaction (π-π stacking) of BMP, it does not lead to the loss of glass transition temperature, and only a minor damage of tensile and impact strengths is caused. Additionally, with only 0.78 wt% loading of phosphorus (10 wt% BMP), the EP/BMP 10% achieves UL-94 V-0 and high LOI value of 35%. Simultaneously, both the heat release rate and total smoke production are markedly reduced. More excitingly, BMP exhibits aggregation-induced emission enhancement of fluorescence in the N, N -dimethylformamide/water mixed solution as well as epoxy resin. This work provides a new insight in simultaneously imparting flame retardancy and fluorescence to epoxy resins without losing glass transition temperature. [Display omitted] • Imide-DOPO derivative exhibits aggregation-induced emission enhancement. • Imide-DOPO derivative endows epoxy resin with excellent flame retardancy. • No loss of T g while the improvement of flame retardancy. • Fluorescence is imparted to the flame retardant epoxy resin. [ABSTRACT FROM AUTHOR]

Epoxy resins (EPs) are a kind of widely used engineering materials, because of their excellent mechanical, chemical and physical properties, but a severe problem they faced is their poor flame retardancy. Single molecule flame retardants have met the bottleneck after the massive researches of the past decade, so, with the development of the polymer technology, hyperbranched flame retardants have been researched and applied, owing to their better and more efficient flame retardancy. Herein, a facile thermal treating procedure was applied to the cured EP thermosets which contained a crosslinkable additive flame retardant to in-situ form a hyperbranched flame retardant. The single molecule flame retardants with N/P elements and crosslinkable nitrile groups were synthesized through an easy method, and physically mixed with EP matrix. After the curing reaction of EP matrix, the thermosets were further treated with a thermal treating procedure, while transferring the single molecule flame retardant into hyperbranched flame retardant, the semi-interpenetrating network was formed at the same time. The flame-retardant properties have been measured by limiting oxygen index (LOI) tests, UL-94 vertical burning tests and cone calorimeter tests, the results showed the flame retardants were extremely efficient and greatly elevated the flame retardancy of EPs, since the 0.5 wt% content could make modified EP samples pass the UL-94 V-0 rate, and with 20 wt% content the LOI value reached 49.5 % and the peak heat release rate reduced for 71.6 % compared with pure EPs. [ABSTRACT FROM AUTHOR]

In this manuscript, the Layer-by-Layer technique is used to modify the surface of flax fabrics using a quad-layer architecture (QL) prior to their assembly in polylactic acid biocomposites. The aim is to produce nanostructured interphases capable of conferring flame retardancy while maintaining mechanical properties. Only 2.5 QL significantly improve the flame retardancy and fire safety of the prepared composites as demonstrated by LOI values of 25.3%, considerably reduced flame spread rates and the substantial reduction in peak of heat release rate (−33%) and maximum average rate of heat emission (−30%) during cone calorimetry. Mechanical testing showed improved modulus and limited reductions in flexural strength. These results make the approach developed in this manuscript very attractive in the design of advanced biocomposites with optimized fire retardancy and mechanical properties. Image 1 • Layer-by-Layer nanostructured interphases are employed for biocomposites • Flame retardant confinement at the interphase avoids matrix degradation • Improved mechanical and flame retardant properties can be simultaneously achieved [ABSTRACT FROM AUTHOR]

A bio-flame retardant filler was synthesized via the self-polymerization of dopamine hydrochloride in alkaline condition, yielding nano-sized polydopamine (nano-PDA) particles ranging between 50 and 100 nm in diameters. Adding a small amount (2 wt%) of the nano-PDA particles into an epoxy can remarkably reduce the value of peak heat release rate by 53.6%, exceeding the performance aluminum trihydroxide (ATH) particles at 10 wt%. The significant improvement in flame retardancy at a relatively low loading of PDA has been found to originate from several key mechanisms including radical scavenging, higher char yield, and production of CO 2. Furthermore, the addition of nano-PDA in the epoxy resin increased the tensile strength by ~6%. In contrast, the addition of common flame retardant, such as ATH, to achieve the same increase in flame retardancy of epoxy would reduce the tensile strength by 22%. This improvement in mechanical properties is attributed to the better bonding between PDA particles with epoxy than ATH with epoxy. [ABSTRACT FROM AUTHOR]

This work reports our recent effort on the preparation of α-Phenyl-N-(2-propyl-2-hydroxymethyl-1, 3-dihydroxy)-imine-Nickel (Ⅱ) (Ni-MOF) containing polyhydroxy groups and its application in improving the fire performance of PLA composites in combination with ammonium polyphosphate (APP). The flame retardant evaluation revealed that the presence of 1.7% Ni-MOF and 3.3% APP in PLA increased the LOI value to 31.0%, upgraded the UL-94 level to V-0, decreased the peak heat release rate (pHRR), total heat release (THR) and total smoking production (TSP) by 27%, 19% and 50%, respectively, and substantially delayed the time to ignition (TTI) from 67 to 97 s. It was proposed that the flame retardants take effect in both vapor and condensed phases, and Ni-MOF nanosheets can synergistically improve the flame resistance of PLA with APP. The incorporation of Ni-MOF effectively inhibited the deterioration of mechanical properties for PLA composites caused by the presence of APP. • The Ni-MOF nanosheets containing polyhydroxy groups was prepared. • APP and Ni-MOF nanosheets significantly improved the fire safety of PLA composite. • The possible synergistic flame-retardant mechanism of Ni-MOF and APP was proposed. • Ni-MOF effectively improved the mechanical properties of PLA composites. [ABSTRACT FROM AUTHOR]

The SiO 2 @metal organic framework (Universitetet i Oslo-66, UiO-66) core–shell microspheres were constructed through covalent linkage between amine groups in UiO-66-NH 2 and epoxy groups on the surface of silica. The morphology and size of the SiO 2 @UiO-66 core–shell microspheres could be simply controlled by tuning the ratio between UiO-66-NH 2 and epoxy terminated silica (E-SiO 2). As observed by TEM, the SiO 2 @UiO-66 hybrids showed better dispersion state within epoxy matrix compared to either E-SiO 2 or UiO-66-NH 2. The incorporation of SiO 2 @UiO-66 hybrids slightly promoted the thermal degradation of the resultant epoxy composites but improved residual yield. The dynamic mechanical analysis results indicated that the SiO 2 @UiO-66 hybrids slightly increased the glass transition temperature and the modulus. The SiO 2 @UiO-66 hybrids exhibited higher efficiency in reducing the heat release rate and the smoke production rate compared to either E-SiO 2 or UiO-66-NH 2. The influence of the component ratio in SiO 2 @UiO-66 on flame retardancy of the epoxy composites was also studied by cone calorimeter. Specifically, the SiO 2 @UiO-66 hybrid with medium ratio (SiO 2 @UiO-66-2) exhibited maximum reduction in peak heat release rate (−31%), total heat release (−23%) and total smoke production (−16%). The char residues were investigated by the Fourier transform infrared spectra, scanning electron microscopy and X-ray photoelectron spectroscopy, which demonstrated that the enhanced flame retardancy of EP/SiO 2 @UiO-66-2 was attributable to the continual morphology and high thermal resistance originated from the presence of the silicon and zirconium complex. These favorable characteristics including high flame retardant efficiency and good smoke suppression make SiO 2 @UiO-66 hybrids promising for flame retardant polymers application. • The SiO 2 @UiO-66 hybrids showed core–shell microsphere structure. • The addition of 3 wt% SiO 2 @UiO-66-2 caused 31% reduction in peak heat release rate. • The addition of 3 wt% SiO 2 @UiO-66-2 led to 16% reduction in total smoke production. [ABSTRACT FROM AUTHOR]