Bio-based P-N flame retardant with ZIF-67 in-situ growth on flexible polyurethane foam with excellent fire safety performance.

The wide application of flexible polyurethane foam (FPUF) poses a giant challenge to human society in terms of fire prevention and environmental pollution. To solve this problem, the lignocellulose-based P-N flame retardant (LFPN) has been developed using mechanochemical methods. It was found that FPUF treated using LFPN exhibited good flame retardancy, but suffered from high smoke generation and toxicity. The hollow dodecahedral ZIF-67 has been used for smoke suppression catalysis, but the agglomeration phenomenon makes it inefficient. Hence, in this study, the adhesive properties of polydopamine (PDA) were utilized to assist the in-situ growth of ZIF-67. The results showed that the total smoke release rate of the treated FPUF was reduced by 40.5%. The toxic gases, such as carbon monoxide (CO), hydrogen cyanide, etc., also showed the same decreasing trend. What's more, the catalytic effect of ZIF-67 itself and the synergistic effect with LFPN gave FPUF great flame retardant and smoke inhibition properties. This novel FPUF provides a new reference for achieving smoke suppression and toxicity reduction.

A biomimetic design for efficient petrochemical spill disposal: CoFe-PBA modified superhydrophobic melamine sponge with mechanical/chemical durability and low fire risk.

Due to frequent petrochemical spills, environmental pollution and the threat of secondary marine fires have arisen, necessitating an urgent need for petrochemical spill treatment strategies with high-performance oil-water separation capabilities. To address the challenges of poor durability, instability in hydrophobic conditions, and difficulty in absorbing high-viscosity crude oil associated with hydrophobic absorbent materials, the authors of this study took inspiration from the unique micro and nanostructures of springtails' water-repellent skin. We engineered a superhydrophobic melamine sponge using interfacial assembly techniques designated as Si@PBA@PDA@MS. This material demonstrated improved mechanical and chemical durability, enhanced photothermal performance, and reduced fire risk. The metal-organic framework (MOF)-derived cobalt-iron Prussian blue analog (CoFe-PBA) was firmly anchored to the sponge framework by the chelation of cobalt ions using polydopamine (PDA). The results demonstrated that Si@PBA@PDA@MS demonstrated excellent superhydrophobicity (WCA=163.5°) and oil absorption capacity (53.4-97.5 g/g), maintaining high durability even after 20 cycles of absorption-squeezing. Additionally, it could still exhibit excellent mechanical properties, hydrophobic stability, and absorption performance across a wide temperature range (0-100 °C), pH range (1-14), and high compression strength (ε = 80%), with excellent mechanical/chemical durability. Furthermore, Si@PBA@PDA@MS demonstrated remarkable photothermal performance and low fire risk, offering efficient, safe, and sustainable practical value for effective petrochemical spill treatment.

A High-Efficient DOPO-Based Flame Retardant as a Co-Curing Agent for Simultaneously Enhancing the Fire Safety and Mechanical Properties of Epoxy Resin.

Simultaneously enhancing the fire safety and mechanical properties of epoxy resin (EP) remains a persistent challenge. Herein, a high-efficient phosphaphenanthrene-based flame retardant (FNP) is synthesized using 3,5-diamino-1,2,4-triazole, 4-formylbenzoic acid, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Due to the presence of active amine groups, FNP is employed as a co-curing agent for fabricating EP composites with outstanding fire safety and mechanical properties. EP containing 8 wt% FNP (EP/8FNP) achieves a vertical burning (UL-94) V-0 rating with a limiting oxygen index of 31%. Meanwhile, FNP declines the peak heat release rate, total heat release, and total smoke release of EP/8FNP by 41.1%, 31.8%, and 16.0%, respectively, compared to those of unmodified EP. The increased fire safety of EP/FNP composites is because FNP promotes the formation of an intumescent, compact, and cross-linking char layer for EP/FNP composites, and releases P-containing substances and noncombustible gases in the gas phase during combustion. In addition, EP/8FNP exhibits 20.3% and 5.4% increase in the flexural strength and modulus compared with those of pure EP. Furthermore, FNP enhances the glass transition temperature of EP/FNP composites from 141.6 °C for pure EP to 147.3 °C for EP/8FNP. Therefore, this work is conducive to the future development of fabricating fire-safe EP composites with enhanced mechanical properties.

Organic Phosphoric Acid Doped Polyaniline-Coupled g-C3 N4 for Enhancing Fire Safety of Intumescent Flame-Retardant Epoxy Resin.

Two kinds of polyaniline coupled graphitized carbon nitride nanosheets doped with different organic phosphoric acids (CP@PA, with phytic acid; CP@NP, with amino trimethyl phosphonic acid) are developed by in-situ polymerization. According to the analysis of the section morphology and element distribution of epoxy resin (EP) composites, although CP@PA and CP@NP show completely different morphology, they can significantly enhance the dispersion of graphitized carbon nitride nanosheets in EP. Moreover, the different oxidation states of phosphorus contained in the CP@PA and CP@NP lead to varying effects on the fire safety of EP. The flame retardancy Index (FRI) is a dimensionless index to evaluate the performance of flame retardants. When used as a flame retardant, CP@NP (FRI = 3.22) is better than CP@PA (FRI = 1.29) in flame retardant, especially in suppressing thermal hazards. As a synergist of intumescent flame retardants (IFR), CP@PA (FRI = 26.12) is most effective in improving the comprehensive fire safety property of EP and achieves an "Excellent" rating. Therefore, two different flame-retardant mechanisms of CP@PA and CP@NP are summarized by analyzing the combustion behavior and changes of condensed phase. In summary, this research may be helpful to the design of nano synergies for IFR systems.

MOF-derived LDH modified flame-retardant polyurethane sponge for high-performance oil-water separation: Interface engineering design based on bioinspiration.

Frequent petrochemical spill accidents and secondary fire hazards have threatened the ecological environment and environmental safety. The traditional purification technology has the problems of high energy consumption and secondary pollution, which also brings new challenges to spill disposal. Herein, we demonstrate a biomimetic structure-based flame-retardant polyurethane (PU) sponge (FPUF@MOF-LDH@HDTMS) for continuous oil-water separation. Inspired by desert beetle and lotus leaf, the biomimetic micro-nano composite structure was constructed by in-situ growth of metal-organic framework-derived layered double hydroxide (MOF-LDH) on the surface of the PU sponge. After grafting MOF-LDH with hexadecyltrimethoxysilane, FPUF@MOF-LDH@HDTMS showed excellent superhydrophobic/superoleophilic performance (water contact angle=153° and oil contact angle=0°). FPUF@MOF-LDH@HDTMS can easily and quickly adsorb oily liquids suspended/settled in the water thanks to the unique bionic structure. FPUF@MOF-LDH@HDTMS has excellent oil/organic solvents absorption capacity; even after 20 cycles of use still maintains high adsorption capacity. More importantly, the continuous oil-water separation through FPUF@MOF-LDH@HTMS has achieved a separation efficiency of up to 99.1%. In addition, the bionic superhydrophobic sponge has excellent flame retardancy, which reduces the possibility of secondary fire caused by PU sponges. Thus, the biomimetic micro-nano composite structure provides a new design strategy for the more high-performance oil-water separation sponges.

Co-curing preparation of flame retardant and smoke-suppressive epoxy resin with a novel phosphorus-containing ionic liquid.

Phosphorus-containing ionic liquid derivatives have been proven to be effective flame retardants for epoxy resin (EP). Flame retardants can accelerate the curing process and improve flame retardancy and smoke suppression of EP composites, which is challenging. In this paper, a novel phosphorus-containing ionic liquid (TPP-PF6) was synthesized and used both as a co-curing agent with 4,4'-diaminodiphenylmethane (DDM) and as a highly effective flame retardant for EP. It has been found that TPP-PF6 was conducive to improve the char formation of EP to inhibit the smoke release at high temperatures. For EP/TPP-PF6 composites, the flame-retardant performance was enhanced rapidly with the increase of TPP-PF6. With only 2 wt% of TPP-PF6, EP/2.0TPP-PF6 reached a UL-94 V-0 rating and a limiting oxygen index of 30.3%. The peak heat release rate, total heat release, and total smoke production values of EP/2.0TPP-PF6 were reduced by 36.32%, 45.81%, and 15.1% compared with those of pure EP, respectively. The thermal degradation products and flame retardant mechanism in gas and condensed phases were studied. It was found that TPP-PF6 had flame retardant effect in the barrier effect of the condensed phase and the quenching effect of the gas phase. This work explores the high-efficiency flame retardant and smoke-suppressive structures with co-curing properties for EP, thus promoting the wide application of EP materials.

Effect of Functionalized Carbon Microspheres Combined with Ammonium Polyphosphate on Fire Safety Performance of Thermoplastic Polyurethane.

In this article, carbon microspheres (CMSs) synthesized by the hydrothermal method and CMSs-Fe (with Fe3+ adsorbed on the surface of CMSs) were combined with ammonium polyphosphate (APP) to achieve the fire safety improvement of thermoplastic polyurethane (TPU). The fire safety performance of TPU composites was investigated by the cone calorimeter test, microscale combustion calorimeter test, thermogravimetric analysis/infrared spectrometry, Raman spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy. The results showed that CMSs and CMSs-Fe can improve the fire safety performance of TPU/APP composites and the effect of CMSs-Fe was better than that of CMSs. The peak heat release rate of the sample containing 0.25 wt % CMSs and 7.75 wt % APP was 16.7% lower than that of the sample containing 8.00 wt % APP, and the content of toxic gases was also reduced in the fire smoke. Also, total heat release and total smoke release of the sample containing CMSs-Fe were 54.7% and 11.6%, respectively, lower than those of the sample containing 0.25% CMSs. It confirmed the contribution of CMSs to the flame retardant system, and the performance of CMSs is improved by adsorbing Fe3+.

A recycled environmental friendly flame retardant by modifying para-aramid fiber with phosphorus acid for thermoplastic polyurethane elastomer.

The application of fibers is more and more extensive, and the pollution caused by abandoned fibers is getting more serious, which has aroused wide attention. So it is necessary to find a way to solve the problem. In this paper, the para-aramid fiber (AF) was recycled and modified by phosphoric acid, and then was applied as environmental friendly flame retardant for thermoplastic polyurethane elastomer (TPU). The flame retardant properties of TPU were tested using cone calorimeter test (CCT) and thermogravimetric/Fourier transform infrared spectroscopy (TG-IR). The CCT test showed that AF-P had better flame retardant effect on TPU than pure AF. Remarkably, the pHRR value for the sample with 1.00wt% content of AF-P was decreased by 48.1%; AF-P had improved the char forming progress and the residual mass was 30.6%, which was much more than pure TPU. TG test showed that AF-P could improve the thermal stability of TPU at high temperature. The TG-IR test revealed that AF-P had reduced the release of CO2 at the beginning. Based on the above results, it will make a great influence on the study of reuse of fibers and environmental friendly flame retardant of polymer.

Fire hazard reduction of hollow glass microspheres in thermoplastic polyurethane composites.

Nowadays, reducing the fire hazard of thermoplastic polyurethane (TPU) is an important research direction in the fields of fire safety materials. In this article, hollow glass microsphere (HGM) was used to reduce the fire hazard of TPU in combustion process. The fire characteristics including smoke and heat production of TPU composites were evaluated using smoke density test (SDT) and cone calorimeter test (CCT). And the thermal decomposition and flammable properties were further studied using thermogravimetric analysis/infrared spectrometry (TG-IR) and limiting oxygen index (LOI), etc. The SDT results showed that the luminous flux (LF) of TPU4 containing 2.00wt% HGM was up to 24% at the end of test without flame, which is much higher than that of TPU0 (5%). And, the CCT results indicated that 2.00wt% HGM could make the total smoke release (TSR) decrease from 1019m2/m2 (TPU0) to 757m2/m2 (TPU4), reduced by 26%. The TG-IR results confirmed that HGM could improve the thermal stability of composites and reduce the production of some toxic gases. The above results illustrated HGM had a good prospect in reducing the fire hazard for TPU.

Fire safety improvement of para-aramid fiber in thermoplastic polyurethane elastomer.

This article mainly studied fire safety effects of para-aramid fiber (AF) in thermoplastic polyurethane (TPU). The TPU/AF composites were prepared by molten blending method, and then the fire safety effects of all TPU composites were tested using cone calorimeter test (CCT), microscale combustion colorimeter test (MCC), smoke density test (SDT), and thermogravimetric/fourier transform infrared spectroscopy (TG-IR). The CCT test showed that AF could improve the fire safety of TPU. Remarkably, the peak value of heat release rate (pHRR) and the peak value of smoke production rate (pSPR) for the sample with 1.0wt% content of AF were decreased by 52.0% and 40.5% compared with pure TPU, respectively. The MCC test showed that the HRR value of AF-2 decreased by 27.6% compared with pure TPU. TG test showed that AF promoted the char formation in the degradation process of TPU; as a result the residual carbon was increased. The TG-IR test revealed that AF had increased the thermal stability of TPU at the beginning and reduced the release of CO2 with the decomposition going on. Through the analysis of the results of this experiment, it will make a great influence on the study of the para-aramid fiber in the aspect of fire safety of polymer.

Smoke suppression properties of ferrite yellow on flame retardant thermoplastic polyurethane based on ammonium polyphosphate.

This article mainly studies smoke suppression properties and synergistic flame retardant effect of ferrite yellow (FeOOH) on flame retardant thermoplastic polyurethane (TPU) composites using ammonium polyphosphate (APP) as a flame retardant agent. Smoke suppression properties and synergistic flame retardant effect of FeOOH on flame retardant TPU composites were intensively investigated by smoke density test (SDT), cone calorimeter test (CCT), scanning electron microscopy (SEM), and thermal-gravimetric analysis (TGA). Remarkably, the SDT results show that FeOOH can effectively decrease the amount of smoke production with or without flame. On the other hand, the CCT data reveal that the addition of FeOOH can apparently reduce heat release rate (HRR), total heat release (THR), and total smoke release (TSR), etc. Here, FeOOH is considered to be an effective smoke suppression agent and a good synergism with APP in flame retardant TPU composites, which can greatly improve the structure of char residue realized by TGA and SEM results.