Construction of sustainable and highly efficient fire-protective nanocoatings based on polydopamine and phosphorylated cellulose for flexible polyurethane foam.

Layer-by-layer (LBL) self-assembly is an effective strategy for constructing fire-resistant coatings on flexible polyurethane foam (FPUF), while the efficiency of fire-resistant coatings remains limited. Therefore, this study proposes an in situ flame retardancy modification combined with LBL self-assembly technology to enhance the efficiency of flame retardant coatings for FPUF. Initially, polydopamine (PDA) and polyethyleneimine (PEI) were employed to modify the FPUF skeleton, thereby augmenting the adhesion on the surface of the skeleton network. Then, the self-assembly of MXene and phosphorylated cellulose nanofibers (PCNFs) via the LBL technique on the foam skeleton network formed a novel, sustainable, and efficient flame retardant system. The final fire-protective coatings comprising PDA/PEI and MXenes/PCNF effectively prevented the collapse of the foam structure and suppressed the melt dripping of the FPUF during combustion. The peak heat release rate, the peak CO production rate and peak CO2 production rate were reduced by 68.6 %, 61.1 %, and 68.4 % only by applying a 10-bilayer coating. In addition, the smoke release rate and total smoke production were reduced by 83.3 % and 57.7 %, respectively. This work offers a surface modification approach for constructing highly efficient flame retardant coatings for flammable polymeric materials.

Per- and polyfluoroalkyl substances and human health outcomes: An umbrella review of systematic reviews with meta-analyses of observational studies.

BACKGROUND: Although evidence on the association between per- and polyfluoroalkyl substances (PFASs) and human health outcomes has grown exponentially, specific health outcomes and their potential associations with PFASs have not been conclusively evaluated. METHODS: We conducted a comprehensive search through the databases of PubMed, Embase, and Web of Science from inception to February 29, 2024, to identify systematic reviews with meta-analyses of observational studies examining the associations between the PFASs and multiple health outcomes. The quality of included studies was evaluated using the A Measurement Tool to Assess Systematic Reviews (AMSTAR) tool, and credibility of evidence was assessed using the Grading of Recommendations, Assessment, Development, and Evaluations (GRADE) criteria. The protocol of this umbrella review (UR) had been registered in PROSPERO (CRD 42023480817). RESULTS: The UR identified 157 meta-analyses from 29 articles. Using the AMSTAR measurement tool, all articles were categorized as of moderate-to-high quality. Based on the GRADE assessment, significant associations between specific types of PFASs and low birth weight, tetanus vaccine response, and triglyceride levels showed high certainty of evidence. Moreover, moderate certainty of evidence with statistical significance was observed between PFASs and health outcomes including lower BMI z-score in infancy, poor sperm progressive motility, and decreased risk of preterm birth as well as preeclampsia. Fifty-two (33%) associations (e.g., PFASs and gestational hypertension, cardiovascular disease, etc) presented low certainty evidence. Additionally, eighty-five (55%) associations (e.g., PFASs with infertility, lipid metabolism, etc) presented very low certainty evidence. CONCLUSION: High certainty of evidence supported that certain PFASs were associated with the incidence of low birth weight, low efficiency of the tetanus vaccine, and low triglyceride levels.

ABO and Rhesus blood groups and multiple health outcomes: an umbrella review of systematic reviews with meta-analyses of observational studies.

BACKGROUND: Numerous studies have been conducted to investigate the relationship between ABO and Rhesus (Rh) blood groups and various health outcomes. However, a comprehensive evaluation of the robustness of these associations is still lacking. METHODS: We searched PubMed, Web of Science, Embase, Scopus, Cochrane, and several regional databases from their inception until Feb 16, 2024, with the aim of identifying systematic reviews with meta-analyses of observational studies exploring associations between ABO and Rh blood groups and diverse health outcomes. For each association, we calculated the summary effect sizes, corresponding 95% confidence intervals, 95% prediction interval, heterogeneity, small-study effect, and evaluation of excess significance bias. The evidence was evaluated on a grading scale that ranged from convincing (Class I) to weak (Class IV). We assessed the certainty of evidence according to the Grading of Recommendations Assessment, Development, and Evaluation criteria (GRADE). We also evaluated the methodological quality of included studies using the A Measurement Tool to Assess Systematic Reviews (AMSTAR). AMSTAR contains 11 items, which were scored as high (8-11), moderate (4-7), and low (0-3) quality. We have gotten the registration for protocol on the PROSPERO database (CRD42023409547). RESULTS: The current umbrella review included 51 systematic reviews with meta-analysis articles with 270 associations. We re-calculated each association and found only one convincing evidence (Class I) for an association between blood group B and type 2 diabetes mellitus risk compared with the non-B blood group. It had a summary odds ratio of 1.28 (95% confidence interval: 1.17, 1.40), was supported by 6870 cases with small heterogeneity (I2 = 13%) and 95% prediction intervals excluding the null value, and without hints of small-study effects (P for Egger's test > 0.10, but the largest study effect was not more conservative than the summary effect size) or excess of significance (P < 0.10, but the value of observed less than expected). And the article was demonstrated with high methodological quality using AMSTAR (score = 9). According to AMSTAR, 18, 32, and 11 studies were categorized as high, moderate, and low quality, respectively. Nine statistically significant associations reached moderate quality based on GRADE. CONCLUSIONS: Our findings suggest a potential relationship between ABO and Rh blood groups and adverse health outcomes. Particularly the association between blood group B and type 2 diabetes mellitus risk.

Advances in Novel Flame-Retardant Technologies for Fire-Safe Polymeric Materials.

This Special Issue, titled "Advances in Novel Flame-Retardant Technologies for Fire-Safe Polymeric Materials", aims to detail the recent advances in the design and preparation of novel flame retardants for use in fire-safe polymeric materials [...].

Application of Silver-Loaded Halloysite Nanotubes in Flame Retardant and Smoke-Suppressive Coating for Polyester-Cotton Fabric.

Despite the wide applications in clothing, furniture, and transportation, the well-known "scaffolding effect" in polyester-cotton fabric has caused significant fire hazards compared to sole polyester or cotton fabrics. Therefore, it is of practical significance to endow polyester-cotton fabric with excellent fire safety. In this work, an organic-inorganic composite coating comprising nitrogen-phosphorus-silicon-containing flame retardant and silver nanoparticle-loaded halloysite nanotubes (Ag@HNTs) was designed and prepared to improve the fire safety of polyester-cotton fabrics. Microscale combustion colorimeter results indicated that the peak heat release rate of the modified polyester-cotton fabric with such a composite coating was reduced by 47%. Meanwhile, it could self-extinguish in 9 s after being ignited, and the limiting oxygen index was up to 25%, indicating excellent fire safety. In addition, the total smoke release of the coated polyester-cotton fabric was reduced by 21%, illustrating that the coating of Ag@HNTs could eliminate the smoke generated. The treated fabric also exhibited superior water resistance. Flame retardant mechanisms were well investigated using thermogravimetric analysis-infrared spectrometry analysis and chemiluminescence by studying the gaseous degradation products and hydroxyl radical in the gas phase. This work provides an effective approach to fabricating high-performance flame retardant and smoke-suppressive coatings for textiles.

Hindered phenolic antioxidant passivation of black phosphorus affords air stability and free radical quenching.

As an antioxidant, hindered phenol scavenges free radicals. Due to the oxidative degradation of black phosphorus (BP) in the presence of water and oxygen, free radical quenching of hindered phenol antioxidants can solve this issue and improve the environmental stability and flame retardant efficiency of BP. Herein, hydroxyl-modified BP (BP-OH) with active groups on the surface was obtained by hydroxylation, and then the hindered phenol antioxidant was grafted onto the surface of BP-OH through an isophorone diisocyanate bridging covalent reaction to obtain hindered phenol-modified BP (BP-HPL). The fire hazard of thermoplastic polyurethane (TPU) can be significantly reduced by introducing BP-HPL into TPU. Adding 2 wt% BP-HPL can reduce the heat release rate and total heat release values of TPU by 49.9% and 49.0%, respectively. In addition, the reductions in smoke volume and carbon monoxide production were also significant. Compared with BP-OH, the environmental stability of BP-HPL is significantly improved. This work provides a reference for the application of BP in the field of fire safety and simultaneously achieves the improvement of the environmental stability and flame retardant performance of BP.

Construction of super-hydrophobic, highly effective flame retardant coating for cotton fabric with superior washability and abrasion resistance.

In order to meet the rapidly growing demand of multi-functional fabric, a super-hydrophobic flame retardant coating for cotton fabric with superior washability and abrasion resistance was prepared. Flame retardant finishing agent P, P-diphenyl-N-(3-(trithoxysilyl) propyl) phospinic amide (DPTES) and hydrophobic finishing agent polydimethylsiloxane @silicon dioxide (PDMS@SiO2) were fixed on the surface of cotton fabric by a simple sol-gel technology in combination with convenient brush-coating process. The coated cotton fabric was capable of self-extinguishing a flame, and the Limiting Oxygen Index (LOI) increased from 18.0% for the control cotton fabric to 26.0% for the treated one at weight gain of 30.3%. The water contact angle (WCA) of C3-PDMS-silica is around 154°, and the slip angle is 8°. In addition, the treated cotton fabric exhibits anti-washing and self-cleaning ability due to the superhydrophobic feature and superior friction resistance. The C3-PDMS-silica sample with excellent char-forming ability, as shown by thermogravimetric analysis (TGA), leading to outstanding flame retardancy. A composite char layer was constituted with char residues and ceramic layer during the combustion of inorganic silicon, which plays the role of heat insulation and flame retardant.

Facilely produced highly adhered, low thermal conductivity and non-combustible coatings for fire safety.

Fire resistant coatings have been proven as an efficient way to improve fire safety in three aspects: reducing the Heat Release Rate (HRR), delaying the ignition time and preventing heat transfer. Herein, a SiO2 based polymeric composite coating with a lower thermal conductivity and brilliant fire resistance was developed. Isocyanate and sodium silicate could form the final Si-O-Si network structure by polymerization. Compared to the wood without coating, the coated wood shows a significantly increase in limit oxygen index (LOI), has reached 48.0 vol% in the test. As for the cone calorimetry test, coated wood shows a 55.3% decrease in the first peak Heat Release Rate (pHRR) and the Total Heat Release (THR) obtains fire-resistant standard. After exposed to butane flame for 30 mins, the coated wood could still maintain its structural integrity with only 180℃ on the non-exposed side. The commercial standard test of the coating was also investigated. To better understand what role does the polyurea play in the system, a theoretical calculation was done during the research to discuss the interaction between the silica and polyurea. As a fast brush-formed coating, it exhibits a great potential in the field of fire-resistant materials, and may broaden the application prospects of wood.

Controllable magnetic field aligned sepiolite nanowires for high ionic conductivity and high safety PEO solid polymer electrolytes.

Poly (ethylene oxide) (PEO) polymer electrolyte, attracts great attention owing to its excellent flexibility, good processability and high safety compared with liquid electrolytes. However, its low ionic conductivity and weak ability to suppress the lithium dendrite severely restrict the further progress of PEO. Herein, we prepare a high ionic conductivity solid polymer electrolyte for all-solid-state lithium batteries by mixing PEO and magnetically aligned functionalized sepiolite (KFSEP) nanowires. The ionic conductivity of PEO/LiTFSI/10%⊥KFSEP solid polymer electrolyte is 2.0 × 10-5 S cm-1 at 20 °C (The ionic conductivity of PEO/LiTFSI solid polymer electrolyte is 4.0 × 10-7 S cm-1 at 20 °C). The experiments and simulation analysis indicate that the aligned nanowires provide a fast-moving channel for lithium ions. The capacity of Li/PEO/LiTFSI/10%⊥KFSEP/LFP cell is 130 mAh g-1 at 1.0 C under 60 °C after 450cycles. Furthermore, Li/PEO/LiTFSI/10%⊥KFSEP/LFP cell shows 150 mAh g-1 at 0.2 C under 25 °C. The Li/PEO/LiTFSI/10%⊥KFSEP/Li cell can work normally more than 600 h, indicating the high stability and lithium dendrite suppressing function of PEO/LiTFSI/10%⊥KFSEP. Overall, a high performance solid polymer electrolyte with higher safety is constructed by incorporating magnetically aligned sepiolite nanowires into PEO.

Anisotropic, low-tortuosity and ultra-thick red P@C-Wood electrodes for sodium-ion batteries.

Red phosphorus (P) is considered to be the most suitable electrode for sodium-ion batteries due to its low cost, earth abundance and high theoretical capacity. Numerous studies have focused on improving the low conductivity and the extremely large volume change of red P during the cycling process. However, these strategies heavily decrease the P mass loading in the electrode. Herein, inspired by natural wood, we successfully develop an ultra-thick bulk red Phosphorus@Carbon-Wood (red P@C-Wood) electrode via the vaporization-condensation process. The sodium-ion batteries assembled with the fabricated red P@C-Wood electrode provide a high areal capacity of 18 mA h cm-2 (≈5 times those of other reported electrodes) and the P mass loading of up to 8.4 mg cm-2 (≥2 times those of other reported electrodes). The combination of red phosphorus and carbonized wood provides a new strategy for people to improve the areal energy density of lithium and sodium batteries.

Self-assembly followed by radical polymerization of ionic liquid for interfacial engineering of black phosphorus nanosheets: Enhancing flame retardancy, toxic gas suppression and mechanical performance of polyurethane.

As one of emerging layered nanomaterials, the potential of black phosphorous nanosheets (BP) for fabricating high performance polymer composites was seriously confined by incompatible interface. Herein, interfacial engineering between BP nanosheets and polyurethane (PU) matrix was rationally designed, where employing polymerized ionic liquid as linking bridge between robust BP nanosheets and soft TPU. The ionic liquid (IL) was firstly confined onto the surface of BP nanosheets with the combination of electrostatic-driving self-assembly process and in situ radical polymerization was then performed. The successful preparation of IL-functionalized BP (IL-BP) nanosheets was confirmed by a series of analytic methods, incluing TEM, XPS, FTIR, and so on. The resultant IL-BP nanosheets imparted well mechanical performance and flame retardancy to TPU composites. Compared to the mechanical enhancement reported by other literatures, the break strength of TPU/IL-BP-1.0 was significantly increased by 50%, attributing to strong interfacial regulation of polymerized IL and mechanically robust BP nanosheets, generated by the similar polarity. Meanwhile, significant decreases of 38.2% and 19.7% in peak values of heat release rate and total heat release were achieved for TPU/IL-BP-2.0. With the investigation of combustion residue and pyrolysis products, it was found that a mass of pyrolysis products reacted with IL-BP nanosheets to form mechanically robust protective char and solid products, being no longer used as fuel to support combustion. Meanwhile, the maximum concentration of CO2 and highly toxic CO of TPU/IL-BP-2.0 were effectively decreased by 36.9% and 26.5%, compared to the pure TPU. Such a design route effectively regulates the interfacial interaction between BP nanosheets and polymer matrix and offers a practical route for preparing high performance materials.

Design of Hierarchical NiCo-LDH@PZS Hollow Dodecahedron Architecture and Application in High-Performance Epoxy Resin with Excellent Fire Safety.

Developing advanced performance epoxy (EP) resin with low flammability and light smoke has been an increasing focus of its research. Especially, it is crucial to reduce the emission of smoke and toxic gases generated during the burning of EP, so that it meets the green and safe industrial requirement. Therefore, a 3D NiCo-LDH@PZS hollow dodecahedral structure was designed and synthesized by using the ZIF-67 as both the precursor and an in situ sacrificial template and the amino group-containing polyphosphazene (PZS) as interfacial compatibilizer and flame retardant cooperative. The release behaviors of heat, smoke, and poisonous gases were carefully investigated. More precisely, the EP/NiCo-LDH@PZS4.0 is endowed with a decrease of 30.9% and 11.2% of the peak heat release rate and the total heat release, respectively. The emissions of smoke and poisonous gases including nitric oxides, aromatic compounds, carbonyl compounds, oxycarbide, and hydrocarbons are much less as well. Especially, the maximum release concentrations of HCN of EP/NiCo-LDH4.0 are reduced by 87.8%. With regard to styrene, methane, and ethane, the maximum release concentrations of EP/NiCo-LDH@PZS4.0 are reduced by 85.9%, 90.6%, and 93.1%, respectively. The total yield of CO and CO2 and the consumption of O2 of EP/NiCo-LDH@PZS4.0 are also reduced by 64.5%, 32.4%, and 33.6%. The fractional effective dose, an index of toxicity smoke, of EP/NiCo-LDH@PZS4.0 is reduced by 20.4%. The DMA tests were performed to study the mechanical properties of EP composites, and the storage modulus and Tg of EP composites are increased with the incorporation of NiCo-LDH@PZS. The possible mechanism of flame retardant was proposed based on the analysis of the condensed and gas phases of EP composites.

Bi2Se3 decorated recyclable liquid-exfoliated MoS2 nanosheets: Towards suppress smoke emission and improve mechanical properties of epoxy resin.

Bimetallic compounds have been proved superior suppression effect on smoke emission during combustion of polymers. In this work, MoS2/Bi2Se3 (MB) hybrids were prepared by a facile wet chemical method and showed superior performance on smoke suppression of EP matrix during combustion. N-vinyl pyrrolidone (NVP) was employed to exfoliate molybdenum disulfide (MoS2) nanosheets in a recyclable method, which showed high efficiency and was recyclable. Exfoliated MoS2 exhibited large surface area and used as carriers to synthesize MB hybrids. Considering the catalytic effect of bismuth and molybdenum, the hybrids had a great influence on the smoke emission behaviors of EP composites. The smoke production was obviously suppressed during the flaming combustion (more than 22% and 23% decrease obtained from cone calorimeter and steady state tube furnace, respectively) or smolder processes (more than 23% decrease obtained from smoke chamber) at only 1 wt% content of MB hybrids. What's more, due to superior dispersion state, the addition of MB hybrids also enhanced the mechanical properties of EP matrix, including wear resistance and tensile property. This work provided a safe and green exfoliation method of MoS2 to prepare polymers/MoS2 composites and also constructed a novel binary hybrids for enhancing combination performances of polymers.

Bioinspired polymeric woods.

Woods provide bioinspiration for engineering materials due to their superior mechanical performance. We demonstrate a novel strategy for large-scale fabrication of a family of bioinspired polymeric woods with similar polyphenol matrix materials, wood-like cellular microstructures, and outstanding comprehensive performance by a self-assembly and thermocuring process of traditional resins. In contrast to natural woods, polymeric woods demonstrate comparable mechanical properties (a compressive yield strength of up to 45 MPa), preferable corrosion resistance to acid with no decrease in mechanical properties, and much better thermal insulation (as low as ~21 mW m-1 K-1) and fire retardancy. These bioinspired polymeric woods even stand out from other engineering materials such as cellular ceramic materials and aerogel-like materials in terms of specific strength and thermal insulation properties. The present strategy provides a new possibility for mass production of a series of high-performance biomimetic engineering materials with hierarchical cellular microstructures and remarkable multifunctionality.

Manganese phytate dotted polyaniline shell enwrapped carbon nanotube: Towards the reinforcements in fire safety and mechanical property of polymer.

High fire hazard of epoxy resin (EP) has been an unavoidable obstruction on its wide application. Here, a manganese phytate dotted polyaniline shell enwrapped carbon nanotube (MPCNT) is facilely constructed and employed as flame retardant for EP. By adding 4.0 wt% MPCNT, the peak heat release rate, total heat release values, peak CO yields and total CO yields are decreased by 27.2, 12.3, 44.8, and 23.3%, respectively. The decreased absorbance intensity of toxic aromatic volatiles is also observed. Then, a tripartite cooperative flame retardant mechanism (a continuous barrier network, catalytic charring function of phytate, and catalytic activity of MnP/C system) is proposed. Furthermore, the storage modulus of EP composites with 2.0 and 4.0 wt% MPCNT are increased by 23.0 and 25.8% at 40 °C, respectively. Thus, the simultaneous reinforcements in fire safety and mechanical performance of EP are successfully achieved. This work may represent a significant step forward in the facile construction of functionalized carbon materials for achieving their whole potentials in polymer-matrix composite.

Fire-Retardant and Thermally Insulating Phenolic-Silica Aerogels.

Energy efficient buildings require materials with a low thermal conductivity and a high fire resistance. Traditional organic insulation materials are limited by their poor fire resistance and inorganic insulation materials are either brittle or display a high thermal conductivity. Herein we report a mechanically resilient organic/inorganic composite aerogel with a thermal conductivity significantly lower than expanded polystyrene and excellent fire resistance. Co-polymerization and nanoscale phase separation of the phenol-formaldehyde-resin (PFR) and silica generate a binary network with domain sizes below 20 nm. The PFR/SiO2 aerogel can resist a high-temperature flame without disintegration and prevents the temperature on the non-exposed side from increasing above the temperature critical for the collapse of reinforced concrete structures.

Hierarchical Polyphosphazene@Molybdenum Disulfide Hybrid Structure for Enhancing the Flame Retardancy and Mechanical Property of Epoxy Resins.

A novel polyphosphazene (PZS) microsphere@molybdenum disulfide nanoflower (MoS2) hierarchical hybrid architecture was first synthesized and applied for enhancing the mechanical performance and flame retardancy of epoxy (EP) resin via a cooperative effect. Herein, using PZS microsphere as the template, a layer of MoS2 nanoflowers were anchored to PZS spheres via a hydrothermal strategy. The well-designed PZS@MoS2 exhibits excellent fire retardancy and a reinforcing effect. The obtained PZS@MoS2 significantly enhanced the flame-retardant performance of EP composites, which can be proved by thermogravimetric and cone calorimeter results. For instance, the incorporation of 3 wt % PZS@MoS2 brought about a 41.3% maximum reduction in the peak heat-release rate and decreased by 30.3% maximum in the total heat release, accompanying the higher graphitized char layer. With regard to mechanical property, the storage modulus of EP/PZS@MoS23.0 in the glassy state was dramatically increased to 22.4 GPa in comparison with that of pure EP (11.15 GPa). It is sensible to know that the improved flame-retardant performance for EP composites is primarily assigned to a physical barrier effect of the MoS2 nanoflowers and the polyphosphazene structure has an positive impact on promoting char formation in the condensed phase.

Space-Confined Growth of Defect-Rich Molybdenum Disulfide Nanosheets Within Graphene: Application in The Removal of Smoke Particles and Toxic Volatiles.

In this work, molybdenum disulfide/reduced graphene oxide (MoS2/RGO) hybrids are synthesized by a spatially confined reaction to insert the growth of defect-rich MoS2 nanosheets within graphene to enable incorporation into the polymer matrix for the application in the removal of smoke particles and toxic volatiles. The steady-state tube furnace result demonstrates that MoS2/RGO hybrid could considerably reduce the yield of CO and smoke particles. The TG-IR coupling technique was utilized to identify species of toxic volatiles including aromatic compounds, CO, and hydrocarbons and to investigate the removal effect of MoS2/RGO hybrids on reducing toxic volatiles. The removal of smoke particles and toxic volatiles was attributed to the adsorption capacity derived from edges sites of MoS2 and the honeycomb lattice of graphene, as well as the inhibition of nanobarrier resulting from two-dimensional structure. The work will offer a strategy for fabricating graphene-based hybrids by the space-confined synthesis and exploiting the application of space-confined graphene-based hybrid.

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.