DOPO-Decorated Two-Dimensional MXene Nanosheets for Flame-Retardant, Ultraviolet-Protective, and Reinforced Polylactide Composites.

This study presents a novel and facile strategy for fabricating fire-resistant, ultraviolet (UV)-shielding, and tensile-enhanced polylactide (PLA) composites using two-dimensional (2D) MXene (Ti3C2) flakes chemically modified with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The thermal and burning performances of PLA composites were demonstrated by the limiting oxygen index, UL-94 test, and cone calorimetry. The UV-shielding and tensile performances were also examined. The results revealed that PLA/Ti3C2-DOPO (3 wt %) displayed a V-0 rating in the UL-94 test. The enhancement against fire hazard was reflected by the significant reduction in the peak heat release rate (33.7%), total heat release (47%), peak CO production (58.8%), and total smoke production (41.7%). The improved fire-safety performance of the composites is attributed to the interplay of catalytic, barrier, and condensed effects of the Ti3C2-DOPO nanosheets in the PLA matrix. PLA/Ti3C2-DOPO also showed an increase (∼9%) in tensile strength and an "Excellent" level (UPF 50+) in the UV-protection assessment. In all, this study introduces a novel chemical modification strategy for 2D MXene flakes to fabricate multifunctional PLA composites, which are promising candidates for next-generation sustainable and protective plastic products.

Controlled self-template synthesis of manganese-based cuprous oxide nanoplates towards improved fire safety properties of epoxy composites.

To date epoxy resins have been extensively used in the field of chemical engineering, aerospace and building materials. Nevertheless, the utilization of flammable epoxy resins has posed a huge threat to lives and properties, which restricted their applications. In this work, manganese-based cuprous oxides two-dimensional nanosheets (Mn@Cu2O-M) are rationally designed and successfully prepared to improve the toxic effluent elimination of epoxy resin. The fire safety properties of the prepared Mn@Cu2O-M based nanocomposites improved the heat release rate (<35 %) and total heat release (<40 %) compared to the control epoxy. Moreover, the production of smoke and toxic volatiles of the composites with Mn@Cu2O-M nanosheets is significantly reduced. The mechanism investigations indicate that the improved flame retardancy and toxic effluent elimination of epoxy composites are attributed to the physical barrier effect and catalytic carbonization awarded by Mn@Cu2O-M nanosheets during burning. This work provides a promising strategy to develop eco-friendly, efficient and fire-safe polymers by both physical barrier effect and catalytic carbonization.

Simultaneous fire safety enhancement and mechanical reinforcement of poly(lactic acid) biocomposites with hexaphenyl (nitrilotris(ethane-2,1-diyl))tris(phosphoramidate).

Poly(lactic acid) (PLA) is an important bioplastic polymer with wide engineering applications, but has relatively low tensile strength and high susceptibility to flames. This manuscript reports the synthesis of a new cyclo-phosphorus-nitrogen flame retardant (FR) - hexaphenyl (nitrilotris(ethane-2,1-diyl))tris(phosphoramidate) (HNETP) for concurrent FR and tensile strength enhancement. 1H, 13C Nuclear Magnetic Resonance and Fourier Transform Infra-red spectra showed that HNETP was successfully synthesized. The FR properties of PLA/HNETP composites were investigated, and the peak heat release rate (PHRR) reduced by ˜ 51.3%, total heat released (THR) ˜ 43.1%, and carbon monoxide (CO) production by ˜ 46.5% with 3 wt% HNETP loading. The fire performance index increased by ˜ 65.8%, while the fire growth index decreased by ˜ 56.7%. The tensile strength and the Young's Modulus improved to ˜ 67.4 and ˜ 87.8% respectively. A significant increase in limiting oxygen index (LOI) (32.5%) was attained with a V-0 rating in the vertical burning test. TG-IR study showed considerable reduction in pyrolysis gaseous products by the PLA/HNETP composites compared to PLA. Insignificant changes were observed in the glass transition and the melting temperature of PLA and PLA/HNETP biocomposites.

Electrochemically Exfoliated Functionalized Black Phosphorene and Its Polyurethane Acrylate Nanocomposites: Synthesis and Applications.

Owing to its mechanical performance, thermal stability, and size effects, single or few-layer black phosphorus (BP) has the potential to prepare the polymer nanocomposites as a candidate of nanoadditives, similar to graphene. The step to realize the scalable exfoliation of single or few-layer BP nanosheets is crucial to BP applications. Herein, we utilized a facile, green, and scalable electrochemical strategy for generating cobaltous phytate-functionalized BP nanosheets (BP-EC-Exf) wherein the BP crystal served as the cathode and phytic acid served as a modifier and an electrolyte simultaneously. Moreover, high-performance polyurethane acrylate/BP-EC-Exf (PUA/BP-EC) nanocomposites are easily prepared by a convenient UV-curable strategy for the first time. Significantly, the conclusion of introducing BP-EC-Exf into the PUA matrix resulted in enhancement in mechanical properties of PUA in terms of the tensile strength (increased by 59.8%) and tensile fracture strain (increased by 88.1%), in the distinct improvement in flame retardancy of PUA in terms of the decreased peak heat release rate (reduced by 44.5%) and total heat release (decreased by 34.5%), and in lower intensities of pyrolysis products including toxic CO. Moreover, it was confirmed by X-ray diffraction and Raman spectra that the air stability of PUA/BP-EC nanocomposites was maintained after exposure to environmental conditions for 4 months. The air-stable BP nanosheets, which were wrapped and embedded in the PUA matrix, can achieve the isolation and protection effect. This modified electrochemical method toward the simultaneous exfoliation and functionalization of BP nanosheets provides an efficient approach for fabricating BP-polymer-based nanocomposites.

Air-Stable Polyphosphazene-Functionalized Few-Layer Black Phosphorene for Flame Retardancy of Epoxy Resins.

Similar to graphene, few-layer black phosphorus (BP) features thermal stability, mechanical properties, and characteristic dimension effects, which has potential as a new member of nanofillers for fabricating polymer nanocomposites. Herein, a cross-linked polyphosphazene-functionalized BP (BP-PZN) is developed with abundant -NH2 groups via a one-pot polycondensation of 4,4'-diaminodiphenyl ether and hexachlorocyclotriphosphazene on the surface of BP nanosheets. Whereafter, the resulting BP-PZN is incorporated into epoxy resin (EP) to study the flame-retardant property and smoke suppression performance. Cone results show that the introduction of 2 wt% BP-PZN distinctly improves the flame-retardant property of EP, for instance, 59.4% decrease in peak heat release rate and 63.6% reduction in total heat release. The diffusion of pyrolysis products from EP during combustion is obviously suppressed after incorporating the BP-PZN nanosheets. Meanwhile, the EP/BP-PZN nanocomposites exhibit air stability after exposure to ambient conditions for four months. The air stability of the BP nanosheets in EP matrix is assigned to surface wrapping by PZN and embedded in the polymer matrix as dual protection. As a new member of the 2D nanomaterials, BP nanosheets have potential to be a new choice for fabricating high-performance nanocomposites.

Melamine-containing polyphosphazene wrapped ammonium polyphosphate: A novel multifunctional organic-inorganic hybrid flame retardant.

To achieve superior fire safety epoxy resins (EP), a novel multifunctional organic-inorganic hybrid, melamine-containing polyphosphazene wrapped ammonium polyphosphate (PZMA@APP) with rich amino groups was prepared and used as an efficient flame retardant. Thanks to the cross-linked polyphosphazene part, PZMA@APP exhibited high flame retardant efficiency and smoke suppression to the EP composites. Thermogravimetric analysis indicated that PZMA@APP significantly enhanced the thermal stability of EP composites. The obtained sample passed UL-94 V-0 rating with 10.0wt% addition of PZMA@APP. Notably, inclusion of incorporating PZMA@APP leads to significantly decrease on fire hazards of EP, for instance, bring about a 75.6% maximum decrease in peak heat release rate and 65.9% maximum reduction in total heat release, accompanied with lower smoke production rate and higher graphitized char layer. With regards to mechanical property, the glass transition temperature of EP/PZMA@APP10.0 was as high as 184.5°C. In particular, the addition of PZMA@APP did not worsen the mechanical properties, compared to pure APP. It was confirmed that the participation of melamine-containing polyphosphazene could significantly enhance the quality of char layer and thereby resulting the higher flame retardant efficiency of PZMA@APP.

Constructing 3D Polyphosphazene Nanotube@Mesoporous Silica@Bimetallic Phosphide Ternary Nanostructures via Layer-by-Layer Method: Synthesis and Applications.

A novel ternary nanostructure polyphosphazene nanotube (PZS)@ mesoporous silica (M-SiO2)@bimetallic phosphide (CoCuP) was facilely fabricated, using PZS as the template, where large amount of cetyltrimethylammonium bromide molecules were anchored to PZS via a similar layer-by-layer assembly strategy, and then uniform M-SiO2 shells can be formed successfully by Hyeon's coating method. Subsequently, the three-dimensional (3D) nanostructure on the basis of bimetallic phosphide (CoCuP) interconnected with PZS@M-SiO2 was synthesized via a convenient, mild hydrothermal route. It is noted that incorporating well-designed PZS@M-SiO2@CoCuP led to significant decrease on fire hazard of thermoplastic polyurethane (TPU), that is, 58.2% and 19.4% reductions in peak heat release rate and total heat release, respectively, as well as lower toxic hydrogen cyanide and carbon monoxide yield accompanied by higher graphitized char layer. In the case of TPU/PZS@M-SiO2@CoCuP system, the storage modulus at -97 °C was dramatically improved by 62.6%, and glass transition temperature was shifted to higher value, compared to those of pure TPU. The enhanced fire safety and mechanical property for TPU composites can be ascribed to tripartite cooperative effect from respective parts (CoCuP and M-SiO2) plus the PZS.

Graphitic carbon nitride/phosphorus-rich aluminum phosphinates hybrids as smoke suppressants and flame retardants for polystyrene.

Graphitic carbon nitride/organic aluminum hypophosphites (g-C3N4/OAHPi) hybrids, i.e., CPDCPAHPi and CBPODAHPi, were synthesized by esterification and salification reactions, and then incorporated into polystyrene (PS) to prepare composites through a melt blending method. Structure and morphology characterizations demonstrated the successful synthesis of PDCPAHPi, BPODAHPi and their hybrids. The g-C3N4 protected OAHPi from external heat and thus improved the thermal stability of OAHPi. Combining g-C3N4 with OAHPi contributed to reduction in peak of heat release rate, total heat release and smoke production rate of PS matrix. Reduced smoke released has also been demonstrated by smoke density chamber testing. Additionally, introduction of the hybrids led to decreased release of flammable aromatic compounds. These properties improvement could be attributed to gas phase action and physical barrier effect in condensed phase: phosphorus-containing low-energy radicals generated from OAHPi effectively captured high-energy free-radicals evolved from PS; g-C3N4 nanosheets retarded the permeation of heat and the escape of volatile degradation products. Therefore, g-C3N4/OAHPi hybrids will provide a potential strategy to reduce the fire hazards of PS.

Flame-retardant-wrapped polyphosphazene nanotubes: A novel strategy for enhancing the flame retardancy and smoke toxicity suppression of epoxy resins.

The structure of polyphosphazene nanotubes (PZS) is similar to that of carbon nanotubes (CNTs) before modification. For applications of CNTs in polymer composites, surface wrapping is an economically attractive route to achieve functionalized nanotubes. Based on this idea, functionalized polyphosphazene nanotubes (FR@PZS) wrapped with a cross-linked DOPO-based flame retardant (FR) were synthesized via one-step strategy and well characterized. Then, the obtained FR@PZS was introduced into epoxy resin (EP) to investigate flame retardancy and smoke toxicity suppression performance. Thermogravimetric analysis indicated that FR@PZS significantly enhanced the thermal stability of EP composites. Cone calorimeter results revealed that incorporation of FR@PZS obviously improved flame retardant performance of EP, for example, 46.0% decrease in peak heat release rate and 27.1% reduction in total heat release were observed in the case of epoxy composite with 3wt% FR@PZS. The evolution of toxic CO and other volatile products from the EP decomposition was significantly suppressed after the introduction of FR@PZS, Therefore, the smoke toxicity associates with burning EP was reduced. The presence of both PZS and a DOPO-based flame retardant was probably responsible for this substantial diminishment of fire hazard.

A 3D Nanostructure Based on Transition-Metal Phosphide Decorated Heteroatom-Doped Mesoporous Nanospheres Interconnected with Graphene: Synthesis and Applications.

A novel three-dimensional nanostructure based on cobalt phosphide nanoparticles (Co2P NPs) and heteroatom-doped mesoporous carbon spheres interconnected with graphene (3D PZM@Co2P@RGO) was facilely synthesized for the first time, and it was used for enhancing the flame retardancy and toxicity suppression of epoxy resins (EP) via a synergistic effect. Herein, the cross-linked polyphosphazene hollow spheres (PZM) were used as templates for the fabrication of 3D architecture. The 3D architecture based on Co2P-decorated heteroatom-doped carbon sphere and reduced graphene oxide was prepared via a carbonization procedure followed by a hydrothermal self-assembly strategy. The as-prepared material exhibits excellent catalytic activity with regard to the combustion process. Notably, inclusion of incorporating PZM@Co2P@RGO resulted in a dramatic reduction of the fire hazards of EP, such as a 47.9% maximum decrease in peak heat release rate and a 29.2% maximum decrease in total heat release, lower toxic CO yield, and formation of high-graphitized protective char layer. In addition, the mechanism for flame retardancy and toxicity suppression was proposed. It is reasonable to know that the improved flame-retardant performance for EP nanocomposites is attributed to tripartite cooperative effect from respective components (Co2P NPs and RGO) plus the heteroatom-doped carbon spheres.

Functionalized Carbon Nanotubes with Phosphorus- and Nitrogen-Containing Agents: Effective Reinforcer for Thermal, Mechanical, and Flame-Retardant Properties of Polystyrene Nanocomposites.

Aminated multiwalled carbon nanotubes (A-MWCNT) were reacted with diphenylphosphinic chloride (DPP-Cl) to prepare the functionalized MWCNT (DPPA-MWCNT). A-MWCNT and DPPA-MWCNT were respectively mixed with polystyrene (PS) to obtain composites through the melt compounding method. SEM observations demonstrated that the DPPA-MWCNT nanofillers were more uniformly distributed within the PS matrix than A-MWCNT. PS/DPPA-MWCNT showed improved thermal stability, glass transition temperature, and tensile strength in comparison with PS/A-MWCNT, resulting from good dispersion and interfacial interactions between DPPA-MWCNT and PS matrix. The incorporation of DPPA-MWCNT to PS significantly reduced peak heat release rate, smoke production rate, and carbon monoxide and carbon dioxide release in cone calorimeter tests. The enhanced fire-retardant properties should be ascribed to the barrier effect of carbon nanotubes, which could provide enough time for DPPA-MWCNT and its functionalized groups to trap the degrading polymer radicals to catalyze char formation. The char layer served as an efficient insulating barrier to reduce the exposure of polymer matrix to an external heat source as well as retarding the flammable gases from feeding the flame.

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.

A hybrid neural network model for noisy data regression.

A hybrid neural network model, based on the fusion of fuzzy adaptive resonance theory (FA ART) and the general regression neural network (GRNN), is proposed in this paper. Both FA and the GRNN are incremental learning systems and are very fast in network training. The proposed hybrid model, denoted as GRNNFA, is able to retain these advantages and, at the same time, to reduce the computational requirements in calculating and storing information of the kernels. A clustering version of the GRNN is designed with data compression by FA for noise removal. An adaptive gradient-based kernel width optimization algorithm has also been devised. Convergence of the gradient descent algorithm can be accelerated by the geometric incremental growth of the updating factor. A series of experiments with four benchmark datasets have been conducted to assess and compare effectiveness of GRNNFA with other approaches. The GRNNFA model is also employed in a novel application task for predicting the evacuation time of patrons at typical karaoke centers in Hong Kong in the event of fire. The results positively demonstrate the applicability of GRNNFA in noisy data regression problems.