Enhanced Performance of Laser-Induced Graphene Supercapacitors via Integration with Candle-Soot Nanoparticles.

Laser-induced graphene (LIG) has been emerging as a promising electrode material for supercapacitors due to its cost-effective and straightforward fabrication approach. However, LIG-based supercapacitors still face challenges with limited capacitance and stability. To overcome these limitations, in this work, we present a novel, cost-effective, and facile fabrication approach by integrating LIG materials with candle-soot nanoparticles. The composite electrode is fabricated by laser irradiation on a Kapton sheet to generate LIG material, followed by spray-coating with candle-soot nanoparticles and annealing. Materials characterization reveals that the annealing process enables a robust connection between the nanoparticles and the LIG materials and enhances nanoparticle graphitization. The prepared supercapacitor yields a maximum specific capacitance of 15.1 mF/cm2 at 0.1 mA/cm2, with a maximum energy density of 2.1 µWh/cm2 and a power density of 50 µW/cm2. Notably, the synergistic activity of candle soot and LIG surpasses the performances of previously reported LIG-based supercapacitors. Furthermore, the cyclic stability of the device demonstrates excellent capacitance retention of 80% and Coulombic efficiency of 100% over 10000 cycles.

The cellular response and molecular mechanism of superoxide dismutase interacting with superparamagnetic iron oxide nanoparticles.

This study explored the response of superoxide dismutase (SOD) under superparamagnetic iron oxide nanoparticles (SPIONs)-induced oxidative stress using combined cellular and molecular methods. Results found that SPIONs induced the inhibition of catalase activity, the U-inverted change of SOD activity and the accumulation of reactive oxygen species (ROS), leading to oxidative damage and cytotoxicity. The change of intracellular SOD activity was resulted from the increase of molecular activity induced by directly interacting with SPIONs and ROS-inhibition of activity. The increase of molecular activity could be attributed to the structural and conformational changes of SOD, which were caused by the direct interaction of SOD with SPIONs. The SOD-SPIONs interaction and its interacting mechanism were explored by multi-spectroscopy, isothermal titration calorimetry and zeta potential assays. SOD binds to SPIONs majorly via hydrophobic forces with the involvement of electrostatic forces. SPIONs approximately adsorb 11 units of SOD molecule with the binding affinity of 2.99 × 106 M-1. The binding sites on SOD were located around Tyr residues, whose hydrophilicity increased upon interacting with SPIONs. The binding to SPIONs loosened the peptide chains, changed the secondary structure and reduced the aggregation state of SOD.

Elaboration of Thermally Performing Polyurethane Foams, Based on Biopolyols, with Thermal Insulating Applications.

In this work, biobased rigid polyurethane foams (PUFs) were developed with the aim of achieving thermal and fireproofing properties that can compete with those of the commercially available products. First, the synthesis of a biopolyol from a wood residue by means of a scaled-up process with suitable yield and reaction conditions was carried out. This biopolyol was able to substitute completely the synthetic polyols that are typically employed within a polyurethane formulation. Different formulations were developed to assess the effect of two flame retardants, namely, polyhedral oligomeric silsesquioxane (POSS) and amino polyphosphate (APP), in terms of their thermal properties and degradation and their fireproofing mechanism. The structure and the thermal degradation of the different formulations was evaluated via Fourier Transformed Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Likewise, the performance of the different PUF formulations was studied and compared to that of an industrial PUF. From these results, it can be highlighted that the addition of the flame retardants into the formulation showed an improvement in the results of the UL-94 vertical burning test and the LOI. Moreover, the fireproofing performance of the biobased formulations was comparable to that of the industrial one. In addition to that, it can be remarked that the biobased formulations displayed an excellent performance as thermal insulators (0.02371-0.02149 W·m-1·K-1), which was even slightly higher than that of the industrial one.

Multifunctional polylactic acid sensing fabric based on biomass flame retardants for intelligent fire early-warning.

Today, building materials emit many hazardous gases in the event of a fire, causing great harm to human health and the environment. Therefore, it is of great significance to develop bio-based flame retardant materials and to realize preventive measures to reduce fires or their damage. In this work, we fabricated a novel multifunctional fire early-warning polylactic acid-based fabric (MFR-PBF) by coating MXene nanosheet, phytic acid @ furfurylamine (PA@FA) and ammonium polyphosphate (APP) via an eco-friendly layer-by-layer assembly method. MFR-PBF showed outstanding flame retardancy including a limiting oxygen index value of 35 % and better char formation capacity. More importantly, MFR-PBF exhibited sensitive fire early-warning capability (∼1 s) and excellent cyclic alarm stability (>15 cycles) due to the excellent semiconductor responsiveness (light and heat) and the significant catalytic char formation effect. Moreover, MFR-PBF is comfortable, flexible and strong enough to sew onto firefighter uniform to detect a variety of human motions, which can be monitored in the internet by using a LoRa emitter and a gateway. In addition, the controllable heating performance rendered MFR-PBF as a potential portable heater. This work provides new insights into the preparation and application of intelligent fire early-warning fabrics in the smart fire protection and Internet of Things.

ZIF-67 In Situ Grown on Attapulgite: A Flame Retardant Synergist for Ethylene Vinyl Acetate/Magnesium Hydroxide Composites.

ZIF-67@ATP was prepared by the in situ growth of the zeolite imidazole frame (ZIF-67) on the surface of attapulgite (ATP). The structure and surface morphology of ZIF-67@ATP were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Different mass fractions of ATP and ZIF-67@ATP were added to ethylene vinyl acetate (EVA)/magnesium hydroxide (MH) composites as flame retardant synergists. The flame retardancy of EVA composites was evaluated by the limiting oxygen index (LOI) test, UL-94 test and cone calorimeter test. Composites containing 3 wt% of ZIF-67@ATP reached an LOI value of 43% and a V-0 rating in the UL-94 test, and the ignition time of the composite increased from 38 s to 56 s. The tensile strength and impact strength of the composites did not change significantly, but the elongation at break increased greatly. Typically, for composites containing 4 wt% of ZIF-67@ATP, the elongation at break of the composites increased from 69.5% to 522.2% compared to the samples without the synergist. This study provides novel insights into the application of attapulgite in the field of flame retardant polymer materials.

Surface Modification of Ammonium Polyphosphate for Enhancing Flame-Retardant Properties of Thermoplastic Polyurethane.

Currently, the development of efficient and environmentally friendly flame-retardant thermoplastic polyurethane (TPU) composite materials has caused extensive research. Ammonium polyphosphate (APP) is used as a general intumescent flame retardant to improve the flame retardancy of TPU. In this paper, we developed a functionalized APP flame retardant (APP-Cu@PDA). Adding only 5 wt% of APP-Cu@PDA into TPU can significantly improve the flame-retardant's performance of the composite material, reflected by a high LOI value of 28% with a UL-94 test of V-0 rating. Compared with pure TPU, the peak heat release rate, total heat release, peak smoke release rate, and total smoke release were reduced by 82%, 25%, 50%, and 29%, respectively. The improvements on the flame-retardant properties of the TPU/5%APP-Cu@PDA composites were due to the following explanations: Cu2+-chelated PDA has a certain catalytic effect on the carbonization process, which can promote the formation of complete carbon layers and hinder the transfer of heat and oxygen. In addition, after adding 5% APP-Cu@PDA, the tensile strength and elongation at the break of TPU composites did not decrease significantly. In summary, we developed a new flame-retardant APP-Cu@PDA, which has better flame-retardant properties than many reported TPU composites, and its preparation process is simple and environmentally friendly. This process can be applied to the industrial production of flame retardants in the future.

Basalt Fiber Modified Ethylene Vinyl Acetate/Magnesium Hydroxide Composites with Balanced Flame Retardancy and Improved Mechanical Properties.

In this study, we selected basalt fiber (BF) as a functional filler to improve the mechanical properties of ethylene vinyl acetate (EVA)-based flame retardant materials. Firstly, BF was modified by grafting γ-aminopropyl triethoxysilane (KH550). Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscope (SEM), and energy dispersive X-ray spectroscopy (EDS) were used to comprehensively prove the successful modification of the BF surface. Subsequently, the modified BF was introduced into the EVA/magnesium hydroxide (MH) composites by melt blending. The limiting oxygen index (LOI), UL-94, cone calorimeter test, tensile test, and non-notched impact test were utilized to characterize both the flame retardant properties and mechanical properties of the EVA/MH composites. It was found that the mechanical properties were significantly enhanced without reducing the flame retardant properties of the EVA/MH composites. Notably, the surface treatment with silane is a simple and low-cost method for BF surface modification and the pathway designed in this study can be both practical and effective for polymer performance enhancement.

Bioinspired growth of iron derivatives on mesoporous silica: effect on thermal degradation and fire behavior of polystyrene.

Aiming to investigate the influence of pore property of mesoporous material on thermal degradation and fire behavior of polystyrene (PS), the ultrafine iron derivatives were uniformly grown on the interior wall of SBA-15 via the coordination-induced assembly by bioinspired polydopamine (PDA). The resultant SBA-15@PDA@Fe was verified by various characterizations with the dominant component of FeOOH. Compared with PS composites with SBA-15, PS composites with SBA-15@PDA@Fe revealed the notably divergent alteration in thermal and thermal-oxidation degradation behavior, which was determined by the changed pore property. The iron derivatives in SBA-15 mesopores possessed the stronger affinity to aerobic volatiles than anaerobic volatiles (via π-π coordination), which inhibited the release of oxidatively decomposed products and enhanced thermal-oxidation stability. In addition, SBA-15@PDA@Fe was capable to preferentially improve limiting oxygen index, accompanied by the decrease of smoke production through suppressing smoke precursors. The glass transition temperature (T g) of PS/SBA-15 was slightly increased via the bioinspired modification.

Synthesis of K-Carrageenan Flame-Retardant Microspheres and Its Application for Waterborne Epoxy Resin with Functionalized Graphene.

In this article, the intumescent flame-retardant microsphere (KC-IFR) was prepared by inverse emulsion polymerizations, with the use of k-carrageenan (KC) as carbon source, ammonium polyphosphate (APP) as acid source, and melamine (MEL) as gas source. Meanwhile, benzoic acid functionalized graphene (BFG) was synthetized as a synergist. A "four-source flame-retardant system" (KC-IFR/BFG) was constructed with KC-IFR and BFG. KC-IFR/BFG was blended with waterborne epoxy resin (EP) to prepare flame-retardant coatings. The effects of different ratios of KC-IFR and BFG on the flame-retardant properties of EP were investigated. The results showed that the limiting oxygen index (LOI) values increased from 19.7% for the waterborne epoxy resin to 28.7% for the EP1 with 20 wt% KC-IFR. The addition of BFG further improved the LOI values of the composites. The LOI value reached 29.8% for the EP5 sample with 18 wt% KC-IFR and 2 wt% BFG and meanwhile, UL-94 test reached the V-0 level. In addition, the peak heat release (pHRR) and smoke release rate (SPR) of EP5 decreased by 63.5% and 65.4% comparing with EP0, respectively. This indicated the good flame-retardant and smoke suppression property of EP composites coating.

Evolution of plastid genomes of Holcoglossum (Orchidaceae) with recent radiation.

BACKGROUND: The plastid is a semiautonomous organelle with its own genome. Plastid genomes have been widely used as models for studying phylogeny, speciation and adaptive evolution. However, most studies focus on comparisons of plastid genome evolution at high taxonomic levels, and comparative studies of the process of plastome evolution at the infrageneric or intraspecific level remain elusive. Holcoglossum is a small genus of Orchidaceae, consisting of approximately 20 species of recent radiation. This made it an ideal group to explore the plastome mutation mode at the infrageneric or intraspecific level. RESULTS: In this paper, we reported 15 complete plastid genomes from 12 species of Holcoglossum and 1 species of Vanda. The plastid genomes of Holcoglossum have a total length range between 145 kb and 148 kb, encoding a set of 102 genes. The whole set of ndh-gene families in Holcoglossum have been truncated or pseudogenized. Hairpin inversion in the coding region of the plastid gene ycf2 has been found. CONCLUSIONS: Using a comprehensive comparative plastome analysis, we found that all the indels between different individuals of the same species resulted from the copy number variation of the short repeat sequence, which may be caused by replication slippage. Annotation of tandem repeats shows that the variation introduced by tandem repeats is widespread in plastid genomes. The hairpin inversion found in the plastid gene ycf2 occurred randomly in the Orchidaceae.

Flame Retardant Polypropylene Composites with Low Densities.

Polypropylene (PP) is currently widely used in areas requiring lightweight materials because of its low density. Due to the intrinsic flammability, the application of PP is restricted in many conditions. Aluminum trihydroxide (ATH) is reported as a practical flame retardant for PP, but the addition of ATH often diminishes the lightweight advantage of PP. Therefore, in this work, glass bubbles (GB) and octacedylamine-modified zirconium phosphate (mZrP) are introduced into the PP/ATH composite in order to lower the material density and simultaneously maintain/enhance the flame retardancy. A series of PP composites have been prepared to explore the formulation which can endow the composite with balanced flame retardancy, good mechanical properties, and low density. The morphology, thermal stability, flame retardancy, and mechanical properties of the composites were characterized. The results indicated the addition of GB could reduce the density, but decreased the flame retardancy of PP composites at the same time. To overcome this defect, ATH and mZrP with synergetic effect of flame retardancy were added into the composite. The dosage of each additive was optimized for achieving a balance of flame retardancy, good mechanical properties, and density. With 47 wt % ATH, 10 wt % GB, and 3 wt % mZrP, the peak heat release rate (pHRR) and total smoke production (TSP) of the composite PP-4 were reduced by 91% and 78%, respectively. At the same time, increased impact strength was achieved compared with neat PP and the composite with ATH only. Maintaining the flame retardancy and mechanical properties, the density of composite PP-4 (1.27 g·cm-3) is lower than that with ATH only (PP-1, 1.46 g·cm-3). Through this research, we hope to provide an efficient approach to designing flame retardant polypropylene (PP) composites with low density.

A Geometry Effect of Carbon Nanomaterials on Flame Retardancy and Mechanical Properties of Ethylene-Vinyl Acetate/Magnesium Hydroxide Composites.

This study was aimed at investigating the effects of carbon nanomaterials with different geometries on improving the flame retardancy of magnesium hydroxide⁻filled ethylene-vinyl acetate (EM). The thermal stability and flame retardancy were studied by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 test, and cone calorimeter test (CCT). The in situ temperature monitoring system and interrupted combustion offered direct evidence to link flame retardancy and composite structure. Results demonstrated that carbon nanomaterials enhanced the thermal stability and fire safety of EM. The geometry of carbon nanomaterials played a key role in synergistic flame retardancy of EM, with the flame-retardant order of carbon nanotube > nanoscale carbon black > graphene. Based on an online temperature monitoring system and interrupted combustion test, one-dimensional carbon nanotube was more inclined to form the network structure synergistically with magnesium hydroxide in ethylene-vinyl acetate, which facilitated the generation of more continuous char structure during combustion. In parallel, the mechanical property was characterized by a tensile test and dynamic mechanical analysis (DMA). The incorporation of carbon nanomaterials presented a limited effect on the mechanical properties of the EM system.

Interfacial engineering of renewable metal organic framework derived honeycomb-like nanoporous aluminum hydroxide with tunable porosity.

Novel honeycomb-like mesoporous aluminum hydroxide (pATH) was synthesized via a facile one-step reaction by employing ZIF-8 as a template. This self-decomposing template was removed automatically under acidic conditions without the need for any tedious or hazardous procedures. Meanwhile, the pore size of pATH was easily modulated by tuning the dimensions of the ZIF-8 polyhedrons. Of paramount importance was the fact that the dissolved ZIF-8 in solution was regenerated upon deprotonation of the ligand under mild alkali conditions, and was reused in the preparation of pATH, thus forming a delicate synthesis cycle. The renewable template conferred cost-effective and sustainable features to the as-synthesized product. As a proof-of-concept application, the fascinating nanoporous structure enabled pATH to load more phosphorous-containing flame retardant and endowed better interaction with epoxy resin over that of commercial aluminum hydroxide. The limiting oxygen index, UL-94 vertical burning test and cone calorimeter test showed that the results of epoxy with the modified pATH rivalled those of epoxy with two times the loading amount of the commercial counterpart, while the former presented better mechanical properties. The proposed "amorphous replica method" used in this work will advance the potential for launching a vast area of research and technology development for the preparation of porous metal hydroxides for use in practical applications.

A new approach to reducing the flammability of layered double hydroxide (LDH)-based polymer composites: preparation and characterization of dye structure-intercalated LDH and its effect on the flammability of polypropylene-grafted maleic anhydride/d-LDH composites.

Dye structure-intercalated layered double hydroxide (d-LDH) was synthesized using a one-step method, and its intercalated behaviors have been characterized by Fourier transform infrared spectroscopy (FTIR), wide angle X-ray scattering (WAXS), scanning electron microscopy, thermogravimetric analysis (TGA), etc. As a novel functional potential fire-retarding nanofiller, it was used to prepare a polypropylene-grafted maleic anhydride (PP-g-MA)/d-LDH composite by refluxing the mixture of d-LDH and PP-g-MA in xylene, aiming to investigate its effect on the flammability of the PP-g-MA composite. The morphological properties, thermal stability, and flame retardant properties of the PP-g-MA/d-LDH composite were determined by FTIR, WAXS, transmission electron microscopy, TGA, and microscale combustion calorimetry. Compared with NO3-LDH (unmodified LDH) and LDH intercalated by sodium dodecylbenzenesulfonate (conventional organo-modified LDH), d-LDH can significantly decrease the heat release rate and the total heat release of the PP-g-MA composite, offering a new approach to imparting low flammability to LDH-based polymer composites.

Synthesis of organo cobalt-aluminum layered double hydroxide via a novel single-step self-assembling method and its use as flame retardant nanofiller in PP.

Synthesis of polypropylene/organo-layered double hydroxide (PP/OLDH) has been carried out based on self-assembled organocobalt-aluminum LDH (O-CoAl-LDH). The novel method of synthesizing self-assembled CoAl-LDH and its characterization have also been reported in details. This method is proven to be very efficient way of producing OLDH in a single step with homogeneous composition and structure. As flame-retardant nanofiller, O-CoAl-LDH shows significant decrease in heat release rate (HRR), the total heat release (THR) and the heat release capacity (HRC) of the PP composites, though the thermal stability of the compounds decreases slightly compared to the base polymer. Morphological analyses show that the LDH particles are dispersed in PP matrix in a partially exfoliated form. The activation energy calculation based on the Kissinger method reveals that O-CoAl-LDH has a positive effect on the activation energy of thermal decomposition of PP. However, in the presence of this filler, decomposition of the composites starts at an earlier stage than that of pure PP.