Phosphorus and nitrogen supramolecule for fabricating flame-retardant, transparent and robust polyvinyl alcohol film.

Supramolecular flame retardants have attracted increasing attention recently due to their simple and eco-friendly preparation process. In this study, a novel flame retardant HEPFR was prepared using supramolecular self-assembly technology between piperazine and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP). It was introduced into polyvinyl alcohol (PVA) matrix to form PVA/HEPFR composite film. Subsequently, the transparency, mechanical properties, thermal stability, and flame retardancy of PVA/HEPFR films were studied. Due to the hydrogen bonded cross-linked network structure between PVA and HEPFR, the mechanical properties of PVA/HEPFR films have been improved, while maintaining good transparency. With 10 wt% addition of HEPFR, PVA films can reach the VTM-0 level in UL-94 testing. And the limiting oxygen index can be increased from 18.5% of pure PVA to 26.5%. The peak heat release rate was reduced by 61.5%. The flame retardancy and thermal stability of PVA/HEPFR films have been greatly improved. This study provides a "one stone, three birds" strategy for preparing flame-retardant, transparent, and robust PVA film.

Overcoming the barrier: designing novel thermally robust shape memory vitrimers by establishing a new machine learning framework.

Shape memory vitrimers (SMVs) are an emerging class of advanced materials that have garnered significant interest from researchers in the past five to six years. These materials can return to their original shape when exposed to a stimulus, while also healing damage they have sustained. However, achieving both high healing/recycling efficiency and a high glass transition temperature (Tg) in SMVs has been challenging, due to the conflicting requirements between molecular chain mobility and the formation and reaction of dynamic covalent bond exchange. Based on the understanding of chemo-physical properties, this study first leverages machine learning (ML), involving supervised and unsupervised learning approaches, to navigate this complex design space of SMVs. Furthermore, we elaborated the basic mathematical frameworks of ML approaches and comprehensively compared their performances. Based on the best performing model, we designed four types of thermally robust shape memory vitrimers (TRSMVs), which boast high recycling efficiency, elevated Tg, and exemplary shape memory effects, overcoming conventional barriers. One of the discovered samples exhibited outstanding performance with a Tg of 233.5 °C, a recycling efficiency of 84.1%, and a recovery stress of 33 MPa in experiments. It aligns well with ML predictions, showcasing the potential of our ML framework in driving innovative materials design and advancing the field of smart polymers.

Eco-Friendly One-Pot Supramolecular-Assembly of P-N Flame Retardant for Fire-Safe Epoxy Resin.

Flame retardant treatment of epoxy resins (EP) to reduce their flammability for extending their range of applications attracts considerable attention. However, the synthesis process of conventional flame retardants is complicated and involves organic hazardous solvents. Meanwhile, how to ensure both the flame-retardant and mechanical properties is a long-standing and actual difficult problem. In this work, a supramolecular flame retardant (named ATPFR) is facilely created by one-pot reaction, using cheap and accessible raw materials in an ecologically benign aqueous solvent. ATPFR is applied to improve the fire safety of EP. With only 5 wt% ATPFR addition, EP can reach the limiting oxygen index of 28.5% and the UL-94 V-0 rating with a significant "blow-out effect." The cone calorimetry test reveals that the EP thermoset with 5 wt% ATPFR has a 75.8% reduction in the peak heat release rate (p-HRR) and a 67.3% reduction in the peak smoke production rate (p-SPR), respectively, compared with the pure EP. Additionally, EP composites with the small amount of ATPFR exhibit a slight decrease and maintain good mechanical properties. Therefore, the facile synthesis and application of this supramolecular flame retardant provide a reliable way for the construction of polymer materials with environment-friendly and effective flame-retardant system.

Synthesis and Applications of Supramolecular Flame Retardants: A Review.

The development of different efficient flame retardants (FRs) to improve the fire safety of polymers has been a hot research topic. As the concept of green sustainability has gradually been raised to the attention of the whole world, it has even dominated the research direction of all walks of life. Therefore, there is an urgent calling to explore the green and simple preparation methods of FRs. The development of supramolecular chemistry in the field of flame retardancy is expanding gradually. It is worth noting that the synthesis of supramolecular flame retardants (SFRs) based on non-covalent bonds is in line with the current concepts of environmental protection and multi-functionality. This paper introduces the types of SFRs with different dimensions. SFRs were applied to typical polymers to improve their flame retardancy. The influence on mechanical properties and other material properties under the premise of flame retardancy was also summarized.

Facile Ball Milling Preparation of Flame-Retardant Polymer Materials: An Overview.

To meet the growing needs of public safety and sustainable development, it is highly desirable to develop flame-retardant polymer materials using a facile and low-cost method. Although conventional solution chemical synthesis has proven to be an efficient way of developing flame retardants, it often requires organic solvents and a complicated separation process. In this review, we summarize the progress made in utilizing simple ball milling (an important type of mechanochemical approach) to fabricate flame retardants and flame-retardant polymer composites. To elaborate, we first present a basic introduction to ball milling, and its crushing, exfoliating, modifying, and reacting actions, as used in the development of high-performance flame retardants. Then, we report the mixing action of ball milling, as used in the preparation of flame-retardant polymer composites, especially in the formation of multifunctional segregated structures. Hopefully, this review will provide a reference for the study of developing flame-retardant polymer materials in a facile and feasible way.

Research Progress in Preparation, Properties and Applications of Biomimetic Organic-Inorganic Composites with "Brick-and-Mortar" Structure.

Inspired by nature, materials scientists have been exploring and designing various biomimetic materials. Among them, composite materials with brick-and-mortar-like structure synthesized from organic and inorganic materials (BMOIs) have attracted increasing attention from scholars. These materials have the advantages of high strength, excellent flame retardancy, and good designability, which can meet the requirements of various fields for materials and have extremely high research value. Despite the increasing interest in and applications of this type of structural material, there is still a dearth of comprehensive reviews, leaving the scientific community with a limited understanding of its properties and applications. In this paper, we review the preparation, interface interaction, and research progress of BMOIs, and propose possible future development directions for this class of materials.

Konjac Glucomannan Aerogels Modified by Hydrophilic Isocyanate and Expandable Graphite with Excellent Hydrolysis Resistance, Mechanical Strength, and Flame Retardancy.

At present, biomass foamlike materials are a hot research topic, but they need to be improved urgently due to their defects such as large size shrinkage rate, poor mechanical strength, and easy hydrolysis. In this study, the novel konjac glucomannan (KGM) composite aerogels modified with hydrophilic isocyanate and expandable graphite were prepared by a facile vacuum freeze-drying method. Compared with the unmodified KGM aerogel, the volume shrinkage of the KGM composite aerogel (KPU-EG) decreased from 36.36 ± 2.47% to 8.64 ± 1.46%. Additionally, the compressive strength increased by 450%, and the secondary repeated compressive strength increased by 1476%. After soaking in water for 28 days, mass retention after hydrolysis of the KPU-EG aerogel increased from 51.26 ± 2.33% to more than 85%. The UL-94 vertical combustion test showed that the KPU-EG aerogel can achieve a V-0 rating, and the limiting oxygen index (LOI) value of the modified aerogel can reach up to 67.3 ± 1.5%. To sum up, the cross-linking modification of hydrophilic isocyanate can significantly improve the mechanical properties, flame retardancy, and hydrolysis resistance of KGM aerogels. We believe that this work can provide excellent hydrolytic resistance and mechanical properties and has broad application prospects in practical packaging, heat insulation, sewage treatment, and other aspects.

Surface Flame-Retardant Systems of Rigid Polyurethane Foams: An Overview.

Rigid polyurethane foam (RPUF) is one of the best thermal insulation materials available, but its flammability makes it a potential fire hazard. Due to its porous nature, the large specific surface area is the key factor for easy ignition and rapid fires spread when exposed to heat sources. The burning process of RPUF mainly takes place on the surface. Therefore, if a flame-retardant coating can be formed on the surface of RPUF, it can effectively reduce or stop the flame propagation on the surface of RPUF, further improving the fire safety. Compared with the bulk flame retardant of RPUF, the flame-retardant coating on its surface has a higher efficiency in improving fire safety. This paper aims to review the preparations, properties, and working mechanisms of RPUF surface flame-retardant systems. Flame-retardant coatings are divided into non-intumescent flame-retardant coatings (NIFRCs) and intumescent flame-retardant coatings (IFRCs), depending on whether the flame-retardant coating expands when heated. After discussion, the development trends for surface flame-retardant systems are considered to be high-performance, biological, biomimetic, multifunctional flame-retardant coatings.

A novel approach simultaneously imparting well-hydrophobicity and photothermal conversion effect to polymer materials: solar-promoted absorption of organic solvents and oils.

In this work, a series of polymer materials including pomelo peel, cotton fabric, polyurethane foam, and so on, are treated by heated CH3SiCl3, presenting desirable photo-thermal conversion function and hydrophobicity. As a representative material, the surface element and skeleton morphology of pomelo peel foam treated by CH3SiCl3 are analyzed detailedly. It is found that well-hydrophobicity (water contact angle of ~147°) and photo-thermal conversion performance (~91.2 °C under one sun) are attributed to the surface carbonization reaction and formation of CH3-SiO2 nanoparticles. Meanwhile, the treatment of CH3SiCl3 significantly increases the BET surface area to 3.0635 m²/g from 0.0973 m²/g. Therefore, pomelo peel-derived carbon foam presents a desirable adsorption capacity of organic solvents and oils (up to 43.2 times its original weight) and excellent removal efficiency (>99.0%). In addition, the rapid photo-thermal response (achieve ~73 °C at 40 s) and high equilibrium temperature (~91.2 °C) are als° demonstrated in pomelo peel-derived carbon foam. As a result, the absorption rate of highly-viscous oils is effectively promoted by the higher fluidity and capillary action caused by the solar-promoted mechanism. This study offers a scalable, easily operated, and environmentally friendly approach to prepare hydrophobic and photo-thermal materials, thus demonstrating a huge potential in oil/water separation application.

A Thermoset Shape Memory Polymer-Based Syntactic Foam with Flame Retardancy and 3D Printability.

Here we report a thermoset shape memory polymer-based syntactic foam inherently integrated with flame retardancy, good mechanical properties, excellent shape memory effect, and 3D printability. The syntactic foam is fabricated by incorporating a high-temperature shape memory polymer (HTSMP) as the matrix, with 40 vol % hollow glass microspheres (HGM) K20, K15, and K1 as fillers. Compressive behavior, strain-controlled programming followed by free recovery, stress recovery, and flame retardancy of these three syntactic foams were studied. Dynamic mechanical analysis and thermal characterization validate their high glass transition temperature (T g = ∼250 °C) and excellent thermal stability. Our results suggest that the foam consisting of K20 HGM exhibits high compressive strength (81.8 MPa), high recovery stress (6.8 MPa), and excellent flame retardancy. Furthermore, this syntactic foam was used for three-dimensional (3D) printing by an extruder developed in our lab. Honeycomb, sinusoidal shapes, and free-standing helical spring were printed for demonstration. This high-temperature photopolymer-based syntactic foam integrated with high T g, flame retardancy, high recovery stress, and 3D printability can be beneficial in different sectors such as aerospace, construction, oil and gas, automotive, and electronic industries.

From Drug Molecules to Thermoset Shape Memory Polymers: A Machine Learning Approach.

Ultraviolet (UV)-curable thermoset shape memory polymers (TSMPs) with high recovery stress but mild glass transition temperature (Tg) are highly desired for 3D/4D printing lightweight load-bearing structures and devices. However, a bottleneck is that high recovery stress usually means high Tg. For a few TSMPs with high recovery stress, their Tg values are close to the decomposition temperature, and thus, the shape memory effect cannot be triggered safely and effectively. While machine learning (ML) has served as a useful tool to discover new materials and drugs, the grand challenge of using ML to discover new TSMPs persists in the very limited data available. Here, we report an enhanced ML approach by combining the transfer learning-variational autoencoder with a weighted-vector combination method. By learning a large data set with drug molecules in a pretraining process, we were able to effectively map the TSMPs to a hidden space that is much closer to a Gaussian distribution. Through this approach, we created a large compositional space and were able to discover five new types of UV-curable TSMPs with desired properties, one of which was validated by the experiments. Our contribution includes (1) representing the features of TSMPs by drug molecules to overcome the barrier of a limited training data set and (2) developing a ML framework that is able to overcome the barrier of mapping the molar ratio information. It is shown that this approach can effectively learn TSMP features by utilizing the relatedness between the data-scarce (and biased) TSMP target and data-abundant drug source, and the result is much more accurate and more robust than the benchmark set by the support vector machine method using direct label encoding and Morgan encoding. Therefore, it is believed that this framework is a state-of-the-art study in the TSMP field. This study opens new opportunities for discovering not only new TSMPs but also other thermoset polymers.

Room-Temperature Self-Healable and Mechanically Robust Thermoset Polymers for Healing Delamination and Recycling Carbon Fibers.

The advocacy of carbon neutrality and circular economy encourages people to pursue self-healing and recycling of glassy thermoset polymers in a more realistic and energy-saving manner, the best being intrinsic healing under room temperature. However, the high mechanical robustness and healing ability are mutually exclusive because of their completely opposite requirements for the mobility of the polymer networks. Here, we report a dual-cross-linked network by slightly coupling the low-molecular-weight branched polyethylenimine with an ester-containing epoxy monomer in a nonstoichiometric proportion. The highly mobile and dense noncovalent hydrogen bonds at the chain branches and ends can not only complement the mechanical robustness (tensile strength of 61.6 MPa, elastic modulus of 1.6 GPa, and toughness of 19.2 MJ/m3) but also endow the glassy thermoset polymer (Tg > 40 °C) with intrinsic self-healing ability (healing efficiency > 84%) at 20 °C. Moreover, the resultant covalent adaptive network makes the thermoset polymer stable to high temperatures and solvents, yet it is readily dissolved in ethylene glycol through internal catalyzed transesterification. The application to room temperature delamination healing and carbon fiber recycling was demonstrated as a proof-of-concept.

Versatile Phosphate Diester-Based Flame Retardant Vitrimers via Catalyst-Free Mixed Transesterification.

We herein report a new vitrimer system integrated with UV curability, recyclability, and flame retardancy. Energy-efficiency, sustainability, and safety have been required features for next-generation polymer materials. Various attempts have been made to endow thermoset polymers with rapid prototyping capacity, recyclability, and flame retardancy. Thermoset vitrimers based on covalent adaptable networks (CANs) are recyclable and remoldable but are generally not UV curable or flame retardant. Here, we present a conceptually novel option to achieve fast exchange reactions in CANs via catalyst-free mixed transesterification of a UV curable phosphate diester-based acrylate cross-linker. In this system, the phosphate diesters serve as reversible covalent bonds, hydrogen bonding ligands, and flame-retardant structures, while acrylate groups serve as UV curable units as well as transesterification collaborators. After the facile UV curing, an intrinsic flame-retardant and mechanically strong dynamic network was achieved due to abundant hydrogen bonds between P-OH and C═O structures. Additionally, this highly cross-linked network exhibited an attractive recyclability even at temperatures lower than Tg. This phosphate diester-based mixed transesterification concept represents an efficient approach for developing multifunctional vitrimers and can also be generalized into other thermally cured polymer systems.

Multireusable Thermoset with Anomalous Flame-Triggered Shape Memory Effect.

While thermosets with high mechanical properties and shape memory capabilities have been developed in recent years, two main bottlenecks persist in their intrinsic nonreusability and flammability, especially for those shape memory thermosets used in recycling-required field with high glass transition temperatures ( Tg) and thus risky high temperatures to trigger shape recovery. Here, we report a new shape memory epoxy thermoset integrated with excellent fire retardancy, recyclability, high mechanical performance, and 100% shape recovery ratio. The shape memory effect of this new thermoset was directly triggered by high-temperature flame for the first time. Furthermore, the survival thermoset can be recycled by a simple solid-state recycling method and reused as reinforcing fillers for polyester. The highest recycling efficiency reached 85.4%, and the reinforced composite presented about four times higher storage modulus compared to that of neat sample. This work may open a door for application of thermoset shape memory polymers in many lightweight engineering structures and devices where fire hazard is a concern. The newly proposed concept of flame-triggered shape memory effect may also find applications in fire-protecting system.

Mussel-inspired functionalization of electrochemically exfoliated graphene: Based on self-polymerization of dopamine and its suppression effect on the fire hazards and smoke toxicity of thermoplastic polyurethane.

The suppression effect of graphene in the fire hazards and smoke toxicity of polymer composites has been seriously limited by both mass production and weak interfacial interaction. Though the electrochemical preparation provides an available approach for mass production, exfoliated graphene could not strongly bond with polar polymer chains. Herein, mussel-inspired functionalization of electrochemically exfoliated graphene was successfully processed and added into polar thermoplastic polyurethane matrix (TPU). As confirmed by SEM patterns of fracture surface, functionalized graphene possessing abundant hydroxyl could constitute a forceful chains interaction with TPU. By the incorporation of 2.0 wt % f-GNS, peak heat release rate (pHRR), total heat release (THR), specific extinction area (SEA), as well as smoke produce rate (SPR) of TPU composites were approximately decreased by 59.4%, 27.1%, 31.9%, and 26.7%, respectively. A probable mechanism of fire retardant was hypothesized: well-dispersed f-GNS constituted tortuous path and hindered the exchange process of degradation product with barrier function. Large quantities of degradation product gathered round f-GNS and reacted with flame retardant to produce the cross-linked and high-degree graphited residual char. The simple functionalization for electrochemically exfoliated graphene impels the application of graphene in the fields of flame retardant composites.

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

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

Novel Melamine/o-Phthalaldehyde Covalent Organic Frameworks Nanosheets: Enhancement Flame Retardant and Mechanical Performances of Thermoplastic Polyurethanes.

Covalent organic frameworks (COFs) nanosheets prepared from condensation reaction between melamine and o-phthalaldehyde are first prepared through ball milling and then incorporated into thermoplastic polyurethanes (TPU) by solution mixing. Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectrometer are applied to characterize COFs nanosheets. It is observed apparently from TEM image that COFs nanosheets are obtained. Successful preparation of COFs nanosheets is proved further by vanishment of typical diffraction peak of COFs at around 23.5° in COFs nanosheets XRD pattern, appearance of quadrant and semicircle stretching of the s-triazine ring at 1568 and 1469 cm-1 in FTIR spectra and N═C bond at 389.5 eV in N1s high-resolution XPS spectra of COFs nanosheets. The thermal property, combustion behavior and mechanical performance of TPU naoncomposites are also investigated. Incorporation of COFs nanosheets into TPU contributes to char forming of TPU under nitrogen atmosphere and 14.3% decrease of peak heat release rate of TPU. Besides, the elongation at break, Young's modulus, and fracture strength of TPU nanocomposites increase sharply compared with that of neat one.

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

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

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

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

Studies on Synthesis of Electrochemically Exfoliated Functionalized Graphene and Polylactic Acid/Ferric Phytate Functionalized Graphene Nanocomposites as New Fire Hazard Suppression Materials.

Practical application of functionalized graphene in polymeric nanocomposites is hampered by the lack of cost-effective and eco-friendly methods for its production. Here, we reported a facile and green electrochemical approach for preparing ferric phytate functionalized graphene (f-GNS) by simultaneously utilizing biobased phytic acid as electrolyte and modifier for the first time. Due to the presence of phytic acid, electrochemical exfoliation leads to low oxidized graphene sheets (a C/O ratio of 14.8) that are tens of micrometers large. Successful functionalization of graphene was confirmed by the appearance of phosphorus and iron peaks in the X-ray photoelectron spectrum. Further, high-performance polylactic acid/f-GNS nanocomposites are readily fabricated by a convenient masterbatch strategy. Notably, inclusion of well-dispersed f-GNS resulted in dramatic suppression on fire hazards of polylactic acid in terms of reduced peak heat-release rate (decreased by 40%), low CO yield, and formation of a high graphitized protective char layer. Moreover, obviously improvements in crystallization rate and thermal conductivities of polylactic acid nanocomposites were observed, highlighting its promising potential in practical application. This novel strategy toward the simultaneous exfoliation and functionalization for graphene demonstrates a simple yet very effective approach for fabricating graphene-based flame retardants.