Limiting Oxygen Index Research Articles

Preparation of halogen-free flame retardant curing agent and its application in epoxy resin

9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-N-Aminoethylpiperazine (DOPO-AEP), a phosphorus and nitrogen intumescent flame retardant curing agent was prepared by using acetonitrile as solvent using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and N-aminoethylpiperazine (AEP) as raw materials. The structure of the flame retardant curing agent DOPO-AEP was analyzed Fourier Transform Infrared Spectrometer (FTIR), Nuclear Magnetic Resonance (NMR) and Electrospray Ionization Mass Spectrometry (ESI-MS), and the synthesis method of the target product was determined. In addition, the content of char residue was determined by thermogravimetric analyzer, and its thermal properties were comprehensively explored, and based on the obtained results, the curable epoxy resin was selected to prepare DOPO-AEP/EP flame retardant composites. According to the amount of DOPO-AEP added product, different proportions of DOPO-AEP/EP flame retardant composites were prepared, and the actual impact of flame retardant properties and mechanical properties of epoxy resin in different proportions was explored. When the content of DOPO-AEP is 35%, the limiting oxygen index of DOPO-AEP/EP reaches 29.9, which has a significant increase compared with the limiting oxygen index of pure epoxy resin of 19.8, but compared with the content of DOPO-AEP of 30%, the limiting oxygen index of DOPO-AEP/EP is 28.7, and there is no significant increase change. Comprehensive analysis shows that when the component content of DOPO-AEP is 30%, the flame retardant system has a tensile strength of 29.0 MPa, an impact strength of 4.5Kj/m2 and a flexural strength of 73.9 MPa, and its limiting oxygen index is as high as 28.7, and the comprehensive performance of the system is the best. By testing the surface morphology of the flame retardant composites after combustion by SEM, it was found that a dense char layer was formed on the surface of the epoxy resin cured char residue and foamed obviously, indicating that the flame retardant curing performance of DOPO-AEP was good.

Effect of diammonium hydrogen phosphate coated with silica on flame retardancy of epoxy resin.

Epoxy resin has become one of the most widely used polymers owing to their excellent comprehensive properties. However, the inherent inflammability of epoxy resin (EP) has seriously limited its application in a range of fields with high fire safety requirements. Herein, a novel shell-core hierarchy architecture (DAP@SiO2) was prepared, composed of diammonium hydrogen phosphate (DAP) and in situ grown silica, and its structure and morphology were characterized by electron microscopy and infrared spectroscopy. The results indicated that silica particles were uniformly coated onto the surface of DAP. The modified DAP was used to reinforce the epoxy resin. The thermal stability of the EP blends was studied with the use of thermogravimetric analysis. The diammonium phosphate in DAP@SiO2 flame retardant produces pyrolysis gases such as NH3 and N2 during decomposition, diluting the concentration of oxygen and flammable volatile products around the flame. Secondly, silica migrates to the surface of epoxy resin to form a shielding layer, forming compounds containing Si-O-Si and O-Si-C structures, which can be cross-linked with other condensed phase products, greatly improving the thermal stability of the carbon layer. Fire behavior was evaluated using the limiting oxygen index (LOI), vertical burning test, and the cone calorimetry, and the flame retardancy mode of action was explained. With 12% of DAP@SiO2 involved, the EP blend passes UL-94 V-0 level, and its limiting oxygen index (LOI) reaches 33.2%. The incorporation of DAP@SiO2 in an EP matrix showed a slight reduction in the heat release and smoke production. The flame retardant mode of the EP polymer shows that its flame retardant and smoke suppression characteristics are related to the interaction of flame retardants in the gas phase and condensed phase. The mechanical properties test results illustrated that the tensile strength, elastic modulus and impact strength of EP/3%DAP@SiO2 are improved compared with pure EP. This is due to the crosslinking reaction between a large number of amino groups on the surface of DAP@SiO2 and the epoxy group on the epoxy resin, which significantly enhances the interfacial compatibility between DAP@SiO2 and epoxy resin, making the combination of DAP@SiO2 and epoxy resin closer.

Sustainably sourced and DOPO-derived triols as hardeners for epoxy thermosets: A promising solution to synchronously improve flame retardancy, mechanical strength and toughness

The flammability and brittleness of the diglycidyl ether of bisphenol A (DGEBA)-type epoxy resin greatly restrict its application in electronic appliances and structural materials. However, the synchronous improvement in the flame retardancy, mechanical strength, and toughness of DGEBA-type epoxy thermosets remains a significant challenge. To overcome this challenge, in this study, a sustainably sourced and DOPO-derived triol (DOPO-GL-DCDA) was synthesized from a bio-based material, glycerol 1, 3-diglycerolate diacrylate (GL-DCDA). A series of epoxy thermosets with different phosphorus contents were prepared by introducing DOPO-GL-DCDA into the DGEBA matrix. EP/DOPO-GL-DCDA demonstrated excellent flame retardancy and mechanical properties without compromising transparency. Specifically, EP/DOPO-GL-DCDA-1.0P exhibited a limit oxygen index (LOI) of 34.0 % and a UL-94 V-0 rating, and the total heat release (THR) and peak heat release rate (PHRR) of EP/DOPO-GL-DCDA-1.5P decreased by 36.6 % and 46.8 %, respectively, compared with those of pure EP. In addition, compared with those of pure EP, the tensile strength, impact strength, fracture toughness (KIC), and fracture energy (GIC) of EP/DOPO-GL-DCDA-1.5P increased by 62.8 %, 69.9 %, 62.9 %, and 99.0 %, respectively. Moreover, EP/DOPO-GL-DCDA had better dielectric properties than pure EP. Under the premise of maintaining transparency, this work provided a promising solution to synchronously improve the flame retardancy, mechanical strength, and toughness of epoxy thermosets.

Encapsulating montmorillonite and ammonium polyphosphate in one polyurea microcapsule to improve flame‐retardant and mechanical properties of polypropylene composites

AbstractAmmonium polyphosphate (APP) and montmorillonite (MMT) have been widely used in the flame‐retardant of polypropylene (PP), but the low synergistic flame‐retardant efficiency and their poor compatibility with PP matrix need to be greatly improved. In this work, APP and MMT were encapsulated in the one microcapsule (PU@A‐M) at the determined optimal ratio through the “bridging” reactions of diethylenetriamine (DETA) with APP and MMT. Compared with the PP/A + M composites with the physical mixture of APP and MMT, the limiting oxygen index, peak of heat release rate, total heat release, and total smoke production of PP/PU@A‐M were decreased by 5.7%, 48.8%, 3.1%, and 20%, respectively. The well‐dispersed PU@A‐M with charring‐forming agent (CFA) generated continuous and compact char layers with COP, COSi, and SiOP crosslinking structure. Furthermore, the tensile strength and elongation at break of PP/PU@A‐M were enhanced by 4.8% and 36.9%, respectively, as compared with PP/A + M because of good dispersibility and compatibility of PU@A‐M in PP matrix.

Fully biobased approach for sustainable flame retardancy, antibacterial and anti-UV modification of silk fabric

The versatile modification of silk fabric using a fully biobased approach is intriguing. In this study, phytic acid and vanillin, which are plant extracts, were utilized to synthesize reactive vanillin phytate ester for modifying silk fabric to achieve durable flame retardancy, antibacterial and anti-UV performance. The multifunctional properties, thermal resistance, smoke and heat suppression capacity, flame-retardant durability and mechanism of modified silk fabrics were investigated. The vanillin phytate ester imparted high antimicrobial and UV resistance to silk fabric, achieving a 97 % inhibition rate against Escherichia coli and reaching an “excellent” level of UV protection. The modified silk fabric also possessed the self-extinguishing capacity, with a limiting oxygen index value as high as 33.5 %. There was also a significant reduction of 71.7 % in peak heat release and 40 % in smoke release compared with those of the original silk. After undergoing 20 washing cycles, the modified silk fabrics also self-extinguished and passed the vertical burning test, and such good washing resistance was achieved by the Schiff base cross-linking of vanillin phytate ester on the silk fabric. An intumescent flame-retardant mechanism was also identified by char residue analyses, which was driven by the synergistic charring action of phosphate groups and aromatic structures.

Bio-based flame retardant coatings for polyester/cotton fabrics with high physical properties using ammonium vinyl phosphonate-grafted chitosan complexes

Polyester/cotton (T/C) blended fabrics are widely utilized in textile due to the dimensional stability and high elasticity provided by polyester, combined with the comfort and moisture absorption offered by cotton. However, simultaneously enhancing the flame retardancy and maintaining the physical properties of T/C blended fabrics for clothing and furniture applications remains a big challenge. This study introduces a bio-based flame-retardant coating using polyelectrolyte complexes (PEC) composed of ammonium vinyl phosphonate-grafted chitosan (AMVP-g-CS). The protonation degree of the PEC coating is controlled by adjusting the pH to solidify and stabilize the complex structure, preparing bio-based PEC flame retardant T/C blended fabric. Flame retardant analysis reveals that the coated fabrics achieved a limiting oxygen index of 30.5 % and a char length of 11 mm, indicating significantly improved flame retardancy. The combustible volatile substances are significantly reduced for the coated fabrics, achieving a gas-phase flame retardant effect, and forming an expansive char layer with thermal insulation and oxygen blocking properties. Importantly, physical analysis proves that the PEC deposition improved mechanical properties, satisfactory whiteness index and hand feeling of the fabrics. This work opens up a pragmatic and industrially feasible strategy for the development of CSs in the field of flame retardant coating.

Enhancing Flame-Retardant Properties of Polyurethane Composites Using N-β-(Aminoethyl)-γ-aminopropyl Trimethoxysilane and Carbon Black Co-Modified Ammonium Polyphosphate

The search for a straightforward method to obtain efficient, affordable, and long-lasting flame retardants with both desirable flame-retardant and mechanical properties for polyurethane (PU) composites remains a significant challenge. In this study, the surface of ammonium polyphosphate (APP) was modified using N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane (KH792) via an ion-exchange reaction, and the modified APP was coated with nanoscale carbon black (CB) to obtain CBAPP. CBAPP demonstrated good compatibility within the PU matrix and notably increased the tensile strength of the PU composites. Furthermore, CBAPP significantly enhanced the flame-retardant properties of the PU composites. The CBAPP/PU composite with a CBAPP mass fraction of 20% achieved a limiting oxygen index of 41.5% and a UL-94 class of V-0. According to the results of this study, our modification approach can be applied to develop other high-performance flame-retardant polymer-based composites, representing a significant contribution to the field of fire safety materials.

Halogen-free epoxy flame retardant & promoter with diimidazole skeleton improves overall properties of epoxy resins

In order to solve the widespread problem in the field of flame retardancy epoxy(FREP), for the deterioration of the overall properties, we designed a novel structural flame retardant & promoter DOPO-CDI and synthesized it using a simple nucleophilic addition one-step method, which exhibits remarkable flame retardant and curing promotion, the flame retardant and promote mechanism of DOPO-CDI on neat EP is illustrated in Fig 0a, which obtained excellent overall properties shown in Fig 0b. Compared with neat epoxy, it has high flame retardancy, low additives results in an limiting oxygen index(LOI) of up to 37.5 % and a V-0 rating of UL-94, a lower curing exothermic peak temperature, a shorter curing time. And in terms of mechanical properties, the excellent strength of epoxy has been further enhanced, flexural strength and tensile strength are increased by 13.3 % and 21.6 % respectively. Moreover, the toughness of epoxy, which is generally lacking, has been greatly improved, in particular, compared with neat epoxy, the impact strength of epoxy with 3 wt% DOPO-CDI increased by 103.6 %. Unlike most FREP, glass transition temperature(Tg) of the epoxy with the introduction of DOPO-CDI raises to 165.6 °C, which is a significant improvement compared to that of the neat epoxy, in terms of combustion behavior, DOPO-CDI has a considerable inhibitory effect on the combustion exotherm and smoke emission. This work explores a way to balance processing, mechanical and thermal properties when preparing FREP, which has great potential for application.

Fabrication of Laminated Electrospun Fire˗Resistant Phosphorylated Poly(Vinylalcohol) Membrane for Enhanced Firefighter Safety

AbstractThe current study focuses on the creation of breathable and fire˗retardant fibrous membranes using phosphorylated poly(vinylalcohol) (PPVA) via the electrospinning method, with a specific interest in their application for structural firefighter clothing. Poly(vinylalcohol) (PVA) was phosphorylated to enhance its inherent flame resistance. Optimization of reaction conditions, including time and temperature, was conducted to achieve a solution suitable for electrospinning. The flame resistance of PPVA was confirmed through vertical flammability tests, with thermogravimetric analysis indicating a significant increase in carbonaceous char formation during PPVA decomposition compared to unmodified PVA. The limiting oxygen index also exhibited a notable increase from PVA to PPVA. Furthermore, the study established optimal operating conditions for producing uniform fibers, considering parameters such as polymer concentration, feed rate, tip to collector distance, and applied potential difference. The PPVA membrane demonstrated superior water vapor transmission rates compared to PVA, indicating enhanced breathability. The entire fabrication process utilized an environmentally friendly water‐based solvent. Additionally, a moisture‐cum‐thermal barrier layer (MCTB) was developed by laminating the PPVA fibrous membranes with microporous polytetrafluoroethylene and further with needle punch‐spunlaced OPAN fabric. Experimental assessments of the MCTB layer revealed satisfactory breathability and thermal performance, surpassing the standard requirements of 35 cal/cm2 for structural firefighting configuration.

A DOPO-eugenol linear siloxane as a highly effective liquid flame retardant also imparting improved mechanical properties to an epoxy amine network

A liquid bio-derived eugenol-containing phosphorus silicone hybrid molecule (EGDS-DOPO) that endows excellent flame-retardancy and enhanced mechanical performance to an epoxy amine network at low levels of addition was successfully synthesized and characterised. The EGDS-DOPO significantly improved the flame retardancy requiring only 5 wt% of EGDS-DOPO to achieve a limiting oxygen index (LOI) of 34.9 % and a UL 94 V-0 rating. Cone calorimetry measurements reveal a reduction of the peak heat release rate, the total heat release, and total smoke production by 62.2 %, 34.0 % and 47.5 %, respectively when EGDS-DOPO concentration was 20 wt%, compared to the unmodified epoxy network. Viscosity remained low throughout cure, and despite some retardation of reactivity, the epoxy amine resin remains fast curing and suitable for liquid moulding composite fabrication technologies. Moreover, the modified EGDS-DOPO epoxy networks display a glass transition temperature (Tg) between 218.5 °C and 174.1 °C, a hydrophobic surface with water contact angle of 97.5°–106.6°, a low moisture ingress of 2.35 %–2.91 %, and improved overall mechanical properties in flexure (maximum 39.8 % increase in flexural strength and 27.0 % in flexural modulus), compression (maximum 24.5 % and 35.0 % increase in compressive strength and modulus, respectively), and fracture toughness (maximum 28.0 %).

Vanillin-derived co-curing agent for enhanced flame retardancy and mechanical properties in epoxy resin

Herein, we present the synthesis and characterization of a novel phosphorus-containing epoxy co-curing agent, ANVD, fabricated via a one-pot method utilizing vanillin, 1,5-diaminonaphthalene, and DOPO as raw materials. Structural analysis conducted through FTIR and NMR spectroscopy confirmed the composition of ANVD. Differential scanning calorimetry (DSC) results indicated ANVD has significant contribution to the curing crosslinking of DGEBA, resulting in a slightly decreased Tg value for EP/ANVD compared to EP/DOPO, albeit still notably higher. Thermogravimetric analysis (TGA) revealed a reduction in the T5% and Tmax values of EP/ANVD, yet ANVD’s superior char-forming ability increased char residue mass at elevated temperatures. Combustion tests showcased the outstanding flame retardancy of EP/ANVD, with EP/ANVD-5 exhibiting a limiting oxygen index (LOI) value of 33.2 % and achieving a V-0 rating in the UL-94 test. Furthermore, EP/ANVD-5 displayed a notable decrease of 38.6 % and 32.1 % in pHRR and av-HRR, respectively, compared to pure EP, surpassing EP/DOPO with equivalent phosphorus content. Analysis of decomposition products in both condensed and gas phases revealed ANVD’s role in forming dense and continuous expanded char layers during combustion, releasing phosphorus radicals and non-combustible gases, thus exhibiting dual-phase flame retardant effects. Additionally, EP/ANVD-3 exhibited enhanced mechanical properties, with tensile strength and modulus increasing from 68.5 MPa and 0.75 GPa to 76.5 MPa and 0.86 GPa, respectively, compared to pure EP. Overall, the introduction of the bio-based flame retardant ANVD presents promising opportunities for the utilization of bio-based materials in flame retardancy applications.

A versatile ionic liquid enables epoxy resin with excellent fire safety and mechanical properties but ultra-low loading

The emergence of ionic liquids provides an effective way to construct new advanced multifunctional epoxy resin (EP) composites with excellent fire retardancy and mechanical properties. In this study, 1-butyl-3-methylimidazolium dibutyl phosphate (BDBP) was synthesized via a facile strategy and then incorporated into the EP matrix. The results showed that ultra-low loading of BDBP (1 wt%) enabled EP composite to achieve a V-0 rating (3.2 mm) in the UL-94 test. When increasing the loading to 4 wt%, the limiting oxygen index (LOI) of EP/BDBP4 composites was improved to 31.9 %. Meanwhile, the peak heat release rate (PHRR), total heat release (THR), and total smoke production (TSP) significantly decreased by 48.1 %, 21.9 %, and 13.5 %, respectively, compared to neat EP. Moreover, the presence of BDBP increased the tensile strength of EP/BDBP2 by more than 7 %, while all EP/BDBP composites maintained high transparency. In summary, this work provides a feasible and low-cost idea for constructing multifunctional EP composites, paving the way for their applications in aerospace, wind turbines, and electronic and electrical fields.

The Effect of Di-Ammonium Phosphate (DAP) towards Flammability Properties of Polyester-Cotton Military Fabrics

Polyester-cotton fabric is one of the most common materials used in military fabrics. The study of the suitable fabric material is critical because military personnel must prepare themselves from inevitable events such as heat exposure. Therefore, the purpose of this study was to examine the flammability features of various cotton compositions in polyester-cotton military textiles with and without the presence of Di-ammonium Phosphate (DAP). We performed a full flammability test, including a cone calorimeter test and a limited oxygen index (LOI) test on three distinct types of polyester-cotton textiles treated with 10% di-ammonium phosphate (DAP). The result shows that, the higher the percentage of cotton, the lower the fire-retardant properties. Besides that, this study also found that the di-ammonium phosphate (DAP) improves the flammable properties of the military fabric.

Organic-inorganic hybrid-modified polyester/cotton fabric: Strategy for enhanced flame retardancy, chemical stability and amphiphobicity

As surface treatments for the application of functional components to substrates have gained increasing attention, there is a growing interest in endowing fabrics with multiple functionalities in addition to flame retardancy. This study describes the successful formation of a fluorination treatment of Al2O3 cross-linked onto the surface of a self-assembled PEI/PA coating for polyester/cotton (PC) fabrics. This coating approach aims to improve the flame retardancy, amphiphobicity, chemical stability, and self-cleaning properties of PC fabrics. The treated fabrics demonstrated exceptional fire resistance, with a significant reduction of 55.4 % in the peak heat release rate (pHRR) during combustion. Correspondingly, there was a decrease of 53.8 % in the peak release rate of CO2, while the limiting oxygen index increased from 17.9 % to 30.4 %. Additionally, the contact angles of water, glycol, and peanut oil droplets before and after treatment increased from 20.4°, 65.1°, and 34.6° to 146.0°, 143.1°, and 97.9°, respectively. The coating exhibits durable self-cleaning performance in both ambient and hot water and remains stable across a pH range of 1–14. This research offers a viable pathway for achieving flame retardancy on fabrics while enhancing their multifunctionality.

Effect of natural agents on the mechanical and flame retardant properties of cotton fabrics – finishing technique

The current study carefully examines the antibacterial finished cotton fabric materials in terms of enhanced flame-retardant capability by eco-friendly herbal extracts to cotton fabrics while concurrently analysing their tensile strength qualities. Because active compounds have been incorporated into the fabric’s structure, the treated fabrics’ tensile strength has changed less over time than untreated fabrics. The plain weave cotton fabric with a specification of 140 g/m2 and a 15% finished concentration had a tensile strength of 238.92 kg/cm2, while cotton fabrics with specifications of 240 g/m2, terry weave with a 15% finished concentration, had a tensile strength of 294.43 kg/cm2. The finishing process has betterment in comparison to the untreated cotton fabrics had tensile strengths of of 140 g/m2 plain and 240 g/m2 terry weaves fabric which has 238.38 kg/cm2 and 288.47 kg/cm2, indicating that the ashwagandha-finished cotton fabrics performed better. The burning period increases from 35 sec for untreated 140 g/m2 plain cotton fabric, according to the flame reaction studies. According to tests on flame reaction, fabrics treated with a combination of banana peels and casein have a burning time rise from 35 s for untreated 140 g/m2 plain cotton fabric to 100 s, and up to 60 s for Ashwaganda and Ginger completed fabrics. The findings of the Limited Oxygen Index (LOI) test revealed that the completed fabrics made from a mixture of banana peels and casein had significantly higher LOI values of 23 than the other treated samples, which had an average LOI of 19 and 20, compared to the untreated cotton fabrics’ LOI of 18.

Integrated design of flame retardancy, smoke suppression and structure of carbon fiber reinforced vinyl ester resin composites through intercalation of nanofiber membranes

A novel flame-retardant method based on the intercalation of nanofiber flame-retardant membrane has been studied for composite laminates. Compared to traditional additive flame-retardant method, this method is more efficient, does not affect the composite forming process, and can improve the mechanical properties of composite. Nanofiber flame-retardant membranes (FPm) are prepared from polyether sulfone (PES) and pentaerythritol phosphate ester (PEPA) by electrospinning technique and inserted in the interlayer of carbon fiber reinforced vinyl ester resin (CF/VER) composites. The FPm can improve the flame-retardancy and smoke suppression of the CF/VER composites by promoting the charring of interlayer structure and form a barrier layer. The thickness of the FPm and the flame-retardant performance of the composites are positive correlation. At a FPm’s thickness of 50 μm, the limiting oxygen index (LOI) and UL-94 ratings of the CF/VER composites reached 33.5 % and V-1, respectively. The total heat release (THR) and total smoke release (TSP) are reduced by 26.4 % and 30.4 %, respectively. Due to the interlayer enhancement effect of FPm, the mechanical strength and interlaminar fracture toughness of CF/VER composites are also improved. Especially, when the thickness of FPm is 30 μm, the mode I interlaminar fracture toughness (GIC) of the CF/VER composite increased by 17.4 %. while the flexural strength, interlayer shear strength (ILSS), mode II interlaminar fracture toughness (GIIC) and storage modulus (E’) are all enhanced.

Improving flame resistance and shielding properties for cross-linked polyethylene (XLPE) using nanoclay filler

Polymers play an essential role in both industry and medical fields due to their diverse and adaptable properties. In this work, prepared crosslinking polyethylene (XLPE) samples with hydrophilic bentonite nanoclay fillers (H2Al2O6Si) at concentrations of 0, 1, 2.5, 4, and 5 wt% enhance their flame-retardant and radiation shielding efficiency. The research investigated flame retardancy and thermal stability parameters. The XLPE/H2Al2O6Si nanocomposite polymer sheets were exposed to a collimated beam of fast neutrons using an Am/Be neutron source (5 Ci) and to gamma radiation using a 137Cs point source (5 μCi) to assess their radiation shielding properties. The study found that uniform dispersion of nanoclay particles enhanced the thermal properties of the composite, forming a char layer that acted as a barrier, slowing thermal decomposition and reducing the heat release rate. Limiting oxygen index (LOI) increased from 28% to 34%, and burning rate improved with higher nanoclay concentrations. Additionally, absorption and optical band gap calculations decreased with increasing filler concentrations. Radiation attenuation capabilities increased by approximately 40% for neutrons and 30% for gamma radiation compared to pure XLPE. The study concluded that incorporating nanoclay fillers into XLPE enhances its shielding capabilities and improves flame resistance properties, making the prepared samples suitable for various industrial applications.

Effect of different IFS (MWCNTs, BN, and ZnO) on flame retardant, thermal and mechanical properties of PA6/aluminum diisobutyl phosphinate composites

AbstractIn this paper, the effects of the synergistic flame retardation of aluminum diisobutyl phosphinate acid (APBA) with three inorganic fillers of different dimensions (multi‐walled carbon nanotubes [MWCNTs] [1‐dimensional], hexagonal boron nitride [BN] [2‐dimensional], and zinc oxide [ZnO] [3‐dimensional]), respectively, on the properties of nylon 6 (polyamide 6 [PA6]) materials were investigated. It was shown that under the same additive amount, with the increase of spatial dimension of inorganic fillers, the thermal stability and residual carbon capacity were improved. Which would catalyze the formation of more and denser carbon layers in the matrix material, effectively blocked the transfer of oxygen and heat, enhanced the cohesive‐phase flame retardancy of synergistic flame‐retardant PA6 composites, and exerted a better synergistic flame‐retardant effect with APBA. So that the flame‐retardant properties of PA6 composites were gradually improved, and the mechanical properties were also gradually increased. The comprehensive performance of three types of inorganic fillers gradually improves in the order of MWCNTs < BN < ZnO. When the addition amount of ZnO was 2 wt%, the vertical combustion grade (UL‐94) of PA6 composite was V‐0, and the limiting oxygen index (LOI) was as high as 36.5%. The tensile strain increased by 19.11% and impact strength increased by 20.26% compared with PA6, and PA6/APBA‐Zn can be used as a flame retardant PA6 composite material with balanced overall performance.Highlights Diisobutylaluminium hypophosphite and inorganic fillers have efficient synergistic flame retardant effects in PA6. With the increase of spatial dimension of inorganic fillers, the better the synergistic flame retardant effect in PA6. The flame retardant can degrade to release the phosphorous free radicals. Inorganic fillers can cross‐link with the PA6 substrate and promote the charring.

Construction of a durable, halogen-free, and phosphorus-free flame retardant cotton fabric system with hydrophobic properties by phase separation and interface polymerization

Inspired by the synthesis of polyurethane, a multifunctional fabric with hydrophobic and long-lasting flame retardancy was prepared through the phase separation and interfacial reaction process between PEI (polyethyleneimine)/BX (borax) aqueous solution and isocyanate terminated polydimethylsiloxane (PDMS-NCO) in tetrahydrofuran solution. The limit oxygen index of the treated fabric increased from 18.0 % to 33.7 %, and the total heat release decreased by 34.2 %. The enhancement of flame retardant performance and thermal stability is attributed to the enhanced char-forming capacity. After 50 cycles of water washing, the cotton fabric can still pass the vertical flammability test because of the curing effect of PDMS-NCO on functional additives. Furthermore, SEM analysis revealed that the formation of nano-rough structures on the fibers was promoted by phase separation, thus leading an increased water contact angle of sample to 139°. The materials utilized in this modified process do not contain elements such as F, Cl, Br, and P, indicating its potential as an environmentally friendly methodology for fabric functionalization.

Stereolithographic 3D Printing of Intrinsically Flame‐Retardant Shape‐Memory Polymers

AbstractThis study presents a novel approach to fabricate 3D‐printed phosphorous‐based acrylate monomers using stereolithographic 3D printing technology, aiming to create demonstrators with exceptional shape‐memory characteristics and robust flame retardant properties. The synthesized materials combine the advantages of 3D printing precision with the intrinsic flame retardancy of phosphorous‐based monomers, offering a versatile solution for applications requiring both shape memory functionality and fire resistance. The limiting oxygen index (LOI) value of the intrinsically flame‐retardant shape‐memory polymer (IFR‐SMP) can reach 34%, and the vertical combustion rating after UL 94 can obtain V‐0. The mechanism of the IFR‐SMP flame retardant mainly includes terminating a free‐radical chain reaction and gas phase dilution, which indicates that the gas‐phase mechanism plays an important role in the flame retardancy. This work advances the frontiers of 3D printing technology by demonstrating the synergistic potential of shape memory and flame retardancy within a single material system, providing a pathway toward the development of innovative and resilient materials for the future.