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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Recent Advances on Early-Stage Fire-Warning Systems: Mechanism, Performance, and Perspective.

Early-stage fire-warning systems (EFWSs) have attracted significant attention owing to their superiority in detecting fire situations occurring in the pre-combustion process. Substantial progress on EFWSs has been achieved recently, and they have presented a considerable possibility for more evacuation time to control constant unintentional fire hazards in our daily life. This review mainly makes a comprehensive summary of the current EFWSs, including the working mechanisms and their performance. According to the different working mechanisms, fire alarms can be classified into graphene oxide-based fire alarms, semiconductor-based fire alarms, thermoelectric-based fire alarms, and fire alarms on other working mechanisms. Finally, the challenge and prospect for EFWSs are briefly provided by comparing the art of state of fire alarms. This work can propose a more comprehensive understanding of EFWSs and a guideline for the cutting-edge development direction of EFWSs for readers.

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.

Synergistic Effect of Cerium Oxide for Improving the Fire-Retardant, Mechanical and Ultraviolet-Blocking Properties of EVA/Magnesium Hydroxide Composites.

Rare earth oxide particles have received important attention in recent years, and due to the wide diversity of promising applications, the need for this kind of material is predicted to expand as the requirements to use the current resources become more demanding. In this work, cerium oxide (CeO2) was introduced into ethylene-vinyl acetate (EVA)/magnesium hydroxide (MDH) composites for enhancing the flame retardancy, mechanical properties and anti-ultraviolet aging performance. The target EVA/MDH/CeO2 composites were prepared by extrusion and injection molding, and the effects of the addition of the CeO2 were explored by thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD), limiting oxygen index (LOI), UL-94, cone calorimetry test, and anti-ultraviolet aging test. Typically, the incorporation of the CeO2 allows a significant increase of the elongation at break and Young's modulus compared with EVA/MDH by 52.25% and 6.85%, respectively. The pHRR remarkably decreased from 490.6 kW/m2 for EVA/MDH to 354.4 kW/m2 for EVA/MDH/CeO2 composite. It was found that the CeO2 presents excellent synergism with MDH in the composites for the anti-UV properties in terms of mechanical properties preservation. Notably, the combination of CeO2 with MDH is a novel and simple method to improve the filler-polymer interaction and dispersion, which resulted in the improvement of the mechanical properties, flame retardancy and the anti-ultraviolet aging performance of the composites.

Sodium alginate and Chitosan aided design of form-stable Polyrotaxane based phase change materials with ultra-high latent heat.

We prepared a series of highly porous Polyrotaxane/sodium alginate, and Polyrotaxane/Chitosan foam alloys according to a sustainable pathway by using water as the only solvent. The foam alloys were further used as supporter materials for poly (ethylene glycol) (PEG) encapsulation, to fabricate shape-stable bio-based phase change materials (PCMs). The pore morphology and the internal interface between PEG and foam alloys were characterized by scanning electron microscope (SEM). Due to the good compatibility between foam alloys and PEG, the PCM performed perfect anti-leakage properties. The introduction of sodium alginate or Chitosan ensures the shape stability of the PCMs during the phase transition. The PCMs performed good cycle stability and showed ultra-high latent heat (171.6 J g-1-189.5 J g-1). Finally, we compared the typical indicators of this work with those reported in the literature, and the comparison highlighted that the present PCMs have the significant advantages: high melting enthalpy, convenient preparation and outstanding sustainability. Notably, the work provided a sustainable idea for the design of anti-leakage and shape-stable PEG-based PCMs.

Development of multifunctional highly-efficient bio-based fire-retardant poly(lactic acid) composites for simultaneously improving thermal, crystallization and fire safety properties.

Currently, it is still a huge challenge to prepare high performance eco-friendly poly(lactic acid) (PLA) with high thermal stability, good processability, excellent crystallization behavior, good transparency and highly-efficient fire safety. In this paper, a novel bio-based nucleation agent N-(furan-2-ylmethyl)-P,P-diphenylphosphinic amide (FPPA) was prepared and used for the fabrication of fire safety PLA/FPPA composites. The chemical structure of FPPA was measured by FTIR, NMR and MS. Further, the crystallization behavior, thermal stability, fire safety and mechanical properties of PLA/FPPA composites were performed by TGA, DSC, polarization microscope, LOI, UL94, cone calorimeter, DMA and, SEM, Raman, GC-MS, and TGA-FTIR. The results showed that the multifunctional FPPA not only had a high thermal stability and was a good nucleation agent for PLA. Moreover, only loading of 3 wt% FPPA increased the LOI of PLA from 19.0 to 33.8 % with UL-94 V-0 classification. Furthermore, the heat release rate and total heat release values of PLA/3%FPPA composite reduced by 6.3 % and 15.3 % in cone-calorimeter test. Such high fire safety was mainly attributed to specific fire safety radicals due to thermal degradation of FPPA to interrupt composites burning in gas phase. Besides, transparency and mechanical properties were almost not changed because of low loading of FPPA in PLA. This multifunctional bio-based fire-retardant for PLA with good comprehensive performance promises broad application in engineering electronics, automobiles, 3D printing and construction 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.

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 Functionalization of Black Phosphorus via Amine Compounds and Its Impacts on the Flame Retardancy and Thermal Decomposition Behaviors of Epoxy Resin.

Recently, lots of effort has been placed into stabilizing black phosphorus (BP) in the air to improve its compatibility with polymers. Herein, BP was chemically functionalized by aliphatic amine (DETA), aromatic amine (PPDA) and cyclamine (Pid) via a nucleophilic substitution reaction, aiming to develop an intensively reactive BP flame retardant for epoxy resin (EP). The -NH2 group on BP-DETA, BP-PPDA and BP-Pid reacted with the epoxide group at different temperatures. The lowest temperature was about 150 °C for BP-DETA. The impacts of three BP-NH2 were compared on the flame retardancy and thermal decomposition of EP. At 5 wt% loading, EP/BP-NH2 all passed UL 94 V 0 rating. The limiting oxygen index (LOI) of EP/BP-PPDA was as high as 32.3%. The heat release rate (HRR) of EP/BP-DETA greatly decreased by 46% and char residue increased by 73.8%, whereas HRR of EP/BP-Pid decreased by 11.5% and char residue increased by 50.8%, compared with EP. Average effective heat of combustion (av-EHC) of EP/BP-Pid was lower than that of EP/BP-DETA and EP/BP-PPDA. In view of the flame-retardant mechanism, BP nanosheets functionalized with aliphatic amine and aromatic amine played a dominant role in the condensed phase, while BP functionalized with cyclamine was more effective in the gas phase.