Spatial inhomogeneity, interfaces and complex vitrification kinetics in a network forming nanocomposite.

A detailed calorimetric study on an epoxy-based nanocomposite system was performed employing bisphenol A diglycidyl ether (DGEBA) cured with diethylenetriamine (DETA) as the polymer matrix and a taurine-modified MgAL layered double hydroxide (T-LDH) as the nanofiller. The -NH2 group of taurine can react with DGEBA improving the interaction of the polymer with the filler. The combined X-ray scattering and electron microscopy data showed that the nanocomposite has a partially exfoliated morphology. Calorimetric studies were performed using conventional DSC, temperature modulated DSC (TMDSC) and fast scanning calorimetry (FSC) in the temperature modulated approach (TMFSC) to investigate the vitrification and molecular mobility dependent on the filler concentration. First, TMDSC and NMR were used to estimate the amount of the rigid amorphous fraction which consists of immobilized polymer segments at the nanoparticle surface. It was found to be 40 wt% for the highest filler concentration, indicating that the interface dominates the overall macroscopic properties and behavior of the material to a great extent. Second, the relaxation rates of the α-relaxation obtained by TMDSC and TMFSC were compared with the thermal and dielectric relaxation rates measured by static FSC. The investigation revealed that the system shows two distinct α-relaxation processes. Furthermore, two separate vitrification mechanisms were also found for a bulk network-former without geometrical confinement as also confirmed by NMR. This was discussed in terms of the intrinsic spatial heterogeneity on a molecular scale, which becomes more pronounced with increasing nanofiller content.

Highly efficient BiVO4single-crystal nanosheets with dual modification: phosphorus doping and selective Ag modification.

BiVO4, a visible-light response photocatalyst, has shown tremendous potential because of abundant raw material sources, good stability and low cost. There exist some limitations for further applicaitions due to poor capability to separate electron-hole pairs. In fact, a single-component modification strategy is barely adequate to obtain highly efficient photocatalytic performance. In this work, P substituted some of the V atoms from VO4oxoanions, namely P was doped into the V sites in the host lattice of BiVO4by a hydrothermal route. Meanwhile, Ag as an attractive and efficient electron-cocatalyst was selectively modified on the (010) facet of BiVO4nanosheets via facile photo-deposition. As a result, the obtained dually modified BiVO4sheets exhibited enhanced photocatalytic degradation property of methylene blue (MB). In detail, photocatalytic rate constant (k) was 2.285 min-1g-1, which was 2.78 times higher than pristine BiVO4nanosheets. Actually, P-doping favored the formation of O vacancies, led to more charge carriers, and facilitated photocatalytic reaction. On the other hand, metallic Ag loaded on (010) facet effectively transferred photogenerated electrons, which consequently helped electron-hole pairs separation. The present work may enlighten new thoughts for smart design and controllable synthesis of highly efficient photocatalytic materials.

Nanocarbon-Based Flame Retardant Polymer Nanocomposites.

In recent years, nanocarbon materials have attracted the interest of researchers due to their excellent properties. Nanocarbon-based flame retardant polymer composites have enhanced thermal stability and mechanical properties compared with traditional flame retardant composites. In this article, the unique structural features of nanocarbon-based materials and their use in flame retardant polymeric materials are initially introduced. Afterwards, the flame retardant mechanism of nanocarbon materials is described. The main discussions include material components such as graphene, carbon nanotubes, fullerene (in preparing resins), elastomers, plastics, foams, fabrics, and film-matrix materials. Furthermore, the flame retardant properties of carbon nanomaterials and their modified products are summarized. Carbon nanomaterials not only play the role of a flame retardant in composites, but also play an important role in many aspects such as mechanical reinforcement. Finally, the opportunities and challenges for future development of carbon nanomaterials in flame-retardant polymeric materials are briefly discussed.

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.

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.

Exploiting Waste towards More Sustainable Flame-Retardant Solutions for Polymers: A Review.

The development of sustainable flame retardants is gaining momentum due to their enhanced safety attributes and environmental compatibility. One effective strategy is to use waste materials as a primary source of chemical components, which can help mitigate environmental issues associated with traditional flame retardants. This paper reviews recent research in flame retardancy for waste flame retardants, categorizing them based on waste types like industrial, food, and plant waste. The paper focuses on recent advancements in this area, focusing on their impact on the thermal stability, flame retardancy, smoke suppression, and mechanical properties of polymeric materials. The study also provides a summary of functionalization methodologies used and key factors involved in modifying polymer systems. Finally, their major challenges and prospects for the future are identified.

Bio-based epoxy vitrimer with inherent excellent flame retardance and recyclability via molecular design.

The development of biobased fire-safe thermosets with recyclability heralds the switch for a transition towards a circular economy. In this framework, we introduced a novel high-performance bio-epoxy vitrimer (named GVD), which was fabricated by forming a crosslinking network between bio-epoxy glycerol triglycidyl ether (Gte), varying amounts of reactive flame-retardant agent 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) (0-7 wt%) and a vanillin-based hardener (VA) with imine bonds. For instance, the epoxy vitrimer GVD5, featuring a DOPO content of 5 wt%, achieved a V-0 rating in the vertical burning test (UL-94) and obtained a limiting oxygen index (LOI) value of 31 %, surpassing the performance of pristine epoxy. Furthermore, the peak heat release rate and total heat release of GVD5 were reduced by 38.2 % and 26.3 %, respectively, compared to pristine epoxy. The GVD vitrimers further demonstrated exceptional reprocessability and recyclability, attributed to the presence of dynamic imine bonds within the topological crosslinking network. Remarkably, the epoxy vitrimers maintained the mechanical properties of the parent epoxy. Therefore, this work provides a facile strategy for fabricating high-performance and multi-functional bio-epoxy thermosets.

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.

Cyclodextrin-based host-guest hierarchical fire retardants: Synthesis and novel strategy to endow polylactic acid fire retardancy and UV resistance.

ß-Cyclodextrin (ß-CD) with a cage-like supramolecular structure possesses the hydrophobic internal ring and external hydroxyl groups, which are beneficial for intramolecular interactions known as "host-guest" chemistry. This study presents a ß-CD-based three-functions-in-one and host-guest fire retardant (ßCD-MOF@Schiff base), which incorporates self-crosslinking Schiff base into its cavity and modification of its surface by metal-organic framework (MOF). With the presence of 5 wt% of ßCD-MOF@Schiff base, the LOI value of PLA composites increased to 29 % and showed 15 %, 17 % and 62 % reductions in peak heat release rate (pHRR), total heat release (THR), and the yield of hazard gas carbon monoxide, respectively. The mode action of FR on fire retardation of PLA showed that the FR promoted the char formation with higher thermal stability and graphitization, and modified the decomposition path of PLA. Additionally, the PLA composites exhibited enhanced UV resistance in the UVA and UVB areas with improved UV absorbance and the UPF values improving and doubling. This work develops a new approach to preparing biodegradable FR, which simultaneously endows fire safety and anti-UV properties for PLA.

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.

Recent Progress on Multifunctional Thermally Conductive Epoxy Composite.

In last years, the requirements for materials and devices have increased exponentially. Greater competitiveness; cost and weight reduction for structural materials; greater power density for electronic devices; higher design versatility; materials customizing and tailoring; lower energy consumption during the manufacturing, transport, and use; among others, are some of the most common market demands. A higher operational efficiency together with long service life claimed. Particularly, high thermally conductive in epoxy resins is an important requirement for numerous applications, including energy and electrical and electronic industry. Over time, these materials have evolved from traditional single-function to multifunctional materials to satisfy the increasing demands of applications. Considering the complex application contexts, this review aims to provide insight into the present state of the art and future challenges of thermally conductive epoxy composites with various functionalities. Firstly, the basic theory of thermally conductive epoxy composites is summarized. Secondly, the review provides a comprehensive description of five types of multifunctional thermally conductive epoxy composites, including their fabrication methods and specific behavior. Furthermore, the key technical problems are proposed, and the major challenges to developing multifunctional thermally conductive epoxy composites are presented. Ultimately, the purpose of this review is to provide guidance and inspiration for the development of multifunctional thermally conductive epoxy composites to meet the increasing demands of the next generation of materials.

Bio-based chitosan-based film as a bifunctional fire-warning and humidity sensor.

Early fire detection is an efficient method to mitigate disastrous fire loss. However, developing smart low-temperature fire-warning sensors that better diminish fire hazards, especially those caused by household appliances, is still challenging. Herein, a salts-modified chitosan (salts-modified CS) based sensor with integrated fire-warning and humidity-monitoring capability is proposed using an easy assembling method. This sensor can respond to temperatures as low as 50 °C and a flame within 2 s quickly and detect relative humidity (RH) range above 50 % at 50 °C and 75 °C sensitively. This system can be reusable for multiple ignitions and works in high-humidity environments (>50 %). Furthermore, the comparison between different salts-modified CS films is carried out to elucidate the mechanism of the formation of electric current under the joint driven by temperature and humidity. Moreover, real-time temperature and RH monitoring can be achieved with a wireless transmission section. This design shows a promising approach for multifunctional CS-based sensors and paves a path to developing a new generation of smart fire-warning detectors.

Highly efficient metal-organic framework based intumescent poly(L-lactic acid) towards fire safety, ignition delay and UV resistance.

Developing multifunctional biodegradable PLA with ignition delay, high efficient fire retardancy, and UV resistance properties is a challenging task owing to its high flammability, and mutually exclusive phenomenon between the latter two properties. In this work, we report a superior efficient synergistic action combining piperazine pyrophosphate (PAPP) and a Co based metal-organic framework (ZIF-67). Results illustrated that with merely 0.06 wt% ZIF-67, intumescent PLA containing 4.96 wt% PAPP reached UL-94 V0 rating. The PLA/4.9PAPP/0.1MOF sample possessed a limiting oxygen index (LOI) value at 33 %, exhibited a 28 % reduction in peak heat release rate (pHRR) and a 67 % increase in fire propagation index (FPI). Moreover, the presence MOF delayed the ignition time of PLA by 12 s due to the highly porous structure of MOF and its chemical heat-sink performance. Insightful reaction to fire mechanism in the condensed phase via TG-FTIR and Raman revealed that a crack free protective intumescent char layer with higher graphitization degree was formed, which effectively enhanced the barrier effect and minimize the heat and fuel transfer. In addition, the UV resistance of PLA composites is enhanced, remaining at and below 5 % transmittance in the UVA and UVB areas. This work provides a green production way of multifunctional degradable materials and broadens their application fields.

All-Fabric Triboelectric Nanogenerator (AF-TENG) Smart Face Mask: Remote Long-Rate Breathing Monitoring and Apnea Alarm.

Since the beginning of the COVID-19 pandemic, the use of face masks has become not only mandatory in several countries but also an acceptable approach for combating the pandemic. In the quest for designing an effective and useful face mask, triboelectric nanogenerators (TENGs) have been recently proposed. Novel functionalities are provided with the use of TENGs in face masks due to the induced triboelectrification generated by the exhaled and inhaled breath, allowing their use as an energy sensor. Nonetheless, within the face mask, the presence of nontextile plastics or other common triboelectric (TE) materials can be undesired. Herein, we propose the use of an all-fabric TENG (AF-TENG) with the use of high molecular weight polyethylene (UHMWPE) and cotton fabric as negative and positive triboelectric layers, respectively. With these materials, it is possible to detect the breathing of the patient, which in the case of not detecting a signal over a few minutes can trigger an alarm locally, providing valuable time. Also, in this article, we have sent breathing signals locally and remotely to distances up to 20 km via Wi-Fi and LoRa, the same as warning signals in the case of detecting anomalies. This work reveals the use of TENGs in smart face masks as an important tool to be used in difficult epidemiological periods to the general public, bringing much more comfort and relaxation to patients and elderly in today's society, and based on pristine eco-friendly materials.

Metal-organic framework-derived bird's nest-like capsules for phosphorous small molecules towards flame retardant polyurea composites.

The loading treatment of phosphorus flame retardants can mitigate their migration and plasticization effect. However, designing suitable carriers has remained a great challenge. Herein, two kinds of Co-based isomers, namely cobalt-cobalt layered double hydroxides (CoCo-LDH) and cobalt basic carbonate (CBC), were synthesized by employing ZIF-67 as a self-template, assemblied into two different nanostructures namely multi-yolk@shell CBC@CoCo-LDH (m-CBC@LDH) and solid CBC nanoparticles by facilely tuning the reaction time, which were employed as carriers, respectively. Subsequently, triphenyl phosphate (TPP)-loaded m-CBC@LDH (m-CBC-P@LDH) was prepared using TPP as the guest. The m-CBC@LDH with high specific surface area and hollow structure exhibited up to more than 30% of TPP loading. The peak of heat release rate and total heat release of polyurea composite blended with 5 wt% m-CBC-P@LDH reduced by 41.7% and 20.6% respectively, and the mechanical properties were less damaged. This work complements a feasible approach for preparation of metal-organic frameworks-derived flame retardant carriers.

Tailored Catalysis Inducing Exceptionally Fire-Safe and Mechanically Reinforced Epoxy at An Ultralow Loading.

An unconventional P/N/Si-free fire safety of epoxy at an ultralow loading with a significantly improved mechanical robustness and toughness via a mere nanocomposite technique is a great challenge. To achieve the goal, a proof of concept is proposed associated with a hierarchical manipulation of catalysis-tailored FexSy ultrathin nanosheets on organic-layered double hydroxide (LDH-DBS@FexSy) toward the formation of porous piling structure via a self-sacrificing conversion of metal-organic framework. A sufficient characterization certified the targeted architecture and composition. A P/N/Si-free ultralow loading of 2 wt % LDH-DBS@FexSy (i.e., 0.6 wt % FexSy) imparted epoxy with UL-94 V-0 rating, a 36.1% reduction of peak heat release rate, as well as a pronounced fire-protection feature. A systematic contrastive investigation evidenced a time-dependent fire-shielding effect induced by a featured catalysis-tailored ultrafast charring behavior at the interface of epoxy and LDH nanosheets. Intriguingly, the tensile strength, impact strength, and flexural strength were simultaneously enhanced by 62.2, 185.4, and 62.9%, respectively, with a 0.6 wt % incorporation of FexSy hierarchy on the basis of a "root-soil"-inspired interfacial "interlocking" structure. In perspective, an integrated manipulation of an interface catalysis-tailored ultrafast charring and hierarchical "interlocking" construction offer an effective balance of the fire safety, mechanical robustness, and toughness of polymers.

Method for Simultaneously improving the thermal stability and mechanical properties of poly(lactic acid): effect of high-energy electrons on the morphological, mechanical, and thermal properties of PLA/MMT nanocomposites.

Nanocomposites derived from poly(lactic acid) (PLA) and organically modified montmorillonite (oMMT) have been cross-linked by high-energy electrons in the presence of triallyl cyanurate (TAC). The morphology of untreated and cross-linked PLA/MMT nanocomposites was characterized by wide-angle X-ray scattering (WAXS) and transmission electron microscopy (TEM). This treatment can improve both the thermal stability and the glass-transition temperatures of the PLA nanocomposites (e.g., PLA-MMT-TAC 30kGy, 50kGy, and 70kGy) because of the formation of cross-linking structures in the nanocomposites that will considerably reduce the mobility of polymers. Interestingly, at relatively low irradiation doses (e.g., 30 and 50 kGy) a good balance between tensile strength and elongation at break for the PLA nanocomposites could be achieved. These mechanical properties are superior to those of pure PLA. Therefore, combining nanotechnology and electron beam cross-linking is a promising new method of simultaneously improving the mechanical properties (toughness and tensile strength) and thermal stability of PLA.

A novel thermotropic elastomer based on highly-filled LDH-SSB composites.

Elastomeric composites are prepared based on solution styrene butadiene elastomer and zinc-aluminium layered double hydroxides (LDH), using a conventional sulphur cure system. Up to 100 parts per hundred rubber of LDH are incorporated into the elastomer matrix. The composites exhibit an interesting phenomenon of thermoreversible transparency, i.e. the transparent sample becomes opaque at warm condition and restores the transparency at room temperature. The transparency is found to be increased as the amount of LDH was increased. The addition of LDH gradually improved the mechanical, dynamic mechanical performance and thermal stability of the base elastomer. These developped elastomers could be utilised as smart materials in different applications.

Toward a New Generation of Fire-Safe Energy Storage Devices: Recent Progress on Fire-Retardant Materials and Strategies for Energy Storage Devices.

Over the last few decades, tremendous progress has been achieved in the development of advanced materials for energy storage devices. These achievements have largely enabled the adoption and transition to key technologies such as mobile phones, electric vehicles, and internet of things. However, the recent surge in fire accidents and explosions emanating from energy storage devices have been closely associated with the highly flammable components that make up these devices which have often led to the loss of life and property. Therefore, replacing flammable materials with fire retardant materials has been recognized as the critical solution to the ever-growing fire problem in these devices. This review summarizes the progress achieved so far in the field of fire retardant materials for energy storage devices. Finally, a perspective on the current state of the art is provided, and a future outlook for these fire-retardant materials, strategies, and new characterization methods is discussed.

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.