Remarkable effects of silicone rubber on flame retardant property and mechanical properties of crosslinked high-density polyethylene/bio-based magnesium phosphate flame retardant (MHPA) composite

In this paper, a new bio-based flame retardant MHPA was prepared by the reaction of magnesium hydroxide (MH) and phytic acid (PA). Then the crosslinked high-density polyethylene (HDPE) flame-retardant composite was prepared by adding it and silicone rubber (SR) into HDPE and using electron beam irradiation. The test results of limiting oxygen index (LOI) and cone calorimeter test (CCT) show that the combination of MHPA and SR can increase the flame retardancy and smoke suppression performance of HDPE. The LOI of HDPE composite with 10 parts of SR is 28.3%, and its pHRR, THR and TSP values are reduced to 454.1 kW/m², 99.7 MJ/m² and 8.3 m², respectively, which is because MHPA and SR jointly promote the formation of continuous and high-density carbon slag in the combustion process of HDPE and inhibit the penetration of flame. In addition, the HDPE composite with 10 parts of SR has significant tensile strength, elongation breaking strength and tear strength, because SR can produce continuous stable structure with HDPE after irradiation and crosslinking. Therefore, this study verified that MHPA and SR together can effectively improve the flame retardancy, smoke suppression and mechanical properties of HDPE composite.     

Synergistic flame retardant effects of activated carbon and molybdenum oxide in poly(vinyl chloride)

The synergistic effects of activated carbon (AC) and molybdenum oxide (MoO₃) in improving the flame retardancy of poly(vinyl chloride) (PVC) were investigated. The effects of AC, MoO₃ and their mixture with a mass ratio of 1:1 on the flame retardancy and smoke suppression properties of PVC were studied using the limiting oxygen index and cone calorimeter tests. It was found that the flame retardancy of the relatively cheaper AC was slightly weaker than that of MoO₃. In addition, the incorporation of AC and MoO₃ greatly reduced the total heat release and improved smoke suppressant property of PVC composites. When the total content of AC and MoO₃ was 10 phr, PVC/AC/MoO₃ had the lowest peak heat release rate and peak smoke production rate values of 173.80 kW m^?2 and 0.1472 m² s^?1, which represented reductions of 47.3 and 59.9%, respectively, compared with those of PVC. Furthermore, thermogravimetric analysis and gel content tests were used to analyze the flame retardant mechanism of AC and MoO₃, with results showing that AC could promote early crosslinking in PVC. Char residue left after heating at 500 °C was analyzed using scanning electron microscopy and Raman spectroscopy, and the results showed that MoO₃ produced the most compact char, with the smallest and most organized carbonaceous microstructures. © 2017 Society of Chemical Industry     

Preparation and smoke suppression mechanism of flame-retardant PBS composites with BNNS@DOPA

Currently, the flame-retardant modification of polybutylene succinate (PBS) is mainly focused on improving flame-retardant efficiency, ignoring the negative impact of the smoke produced by combustion on the human respiratory tract. To address this problem, PBS composites were prepared by melt blending method in this study. The effect of boron nitride-grafted DOPO flame retardant (BNNS@DOPA) on flame retardancy and smoke suppression of PBS composites was investigated. Incorporating 3% BNNS@DOPA into PBS composites results in a 90% improvement in thermal conductivity. This resulted in a reduction of the peak heat release rate, total heat release rate, and actual smoke rate to 453.7 kW m⁻², 86.3 MJ m⁻², and 1035.9 m², respectively, compared with pure PBS. The latter indicated a decrease of 34.0%, 37.6%, and 51.2%, respectively. Furthermore, the ignition time was extended by 45 s and the limiting oxygen index value increased by 12.5%. This functionalization approach presents a new way to study PBS flame retardancy improvement, consequently boosting its application in fire safety for polymer materials.     

Influences of 4ZnO·B2O3·H2O whisker based intumescent flame retardant on the mechanical,flame retardant and smoke suppression properties of polypropylene composites

In this work, the influences of 4ZnO·B₂O₃·H₂O zinc borate (ZB) whisker based intumescent flame retardant (IFR) containing ammonium polyphosphate and dipentaerythritol on the mechanical, flame retardant and smoke suppression properties of polypropylene (PP) composites were characterized by the universal testing machine, UL-94, limiting oxygen index (LOI), and cone calorimeter tests, respectively. The results indicate that only 1 phr of ZB could effectively improve the LOI value and slow down the burning rate of PP composite. The peak heat release rate, average of HRR, total heat release, peak smoke production rate, and total smoke production values are all decreased from 413.8 kW/m², 166.3 kW/m², 82.3 MJ/m², 0.0995 m²/s, and 17.9 m² for PPc/20IFR composite to 267.8 kW/m², 128.3 kW/m², 66.8 MJ/m², 0.0478 m²/s, and 12.6 m² for PPc/20IFR/1ZB composite, respectively. The scanning electron microscopy images, energy dispersive spectrometry, and Raman spectra of char residue reveal that ZB is helpful to form a compact and graphitized intumescent char residue so that the heat diffusion and oxygen transmission are greatly hindered. The thermogravimetry analysis-fourier transform infrared spectroscopy (TGA-FTIR) results show that less combustible volatiles and more H₂O vapor are generated with the appearance of ZB. Hence, the combustion mechanism in gas phase is suppressed.     

Effect of water erosion on flame retardancy of high-impact polystyrene/magnesium hydroxide composite and its mode of action

High-impact polystyrene (HIPS) flame retarded by magnesium hydroxide (MH) was treated in water at different conditions. The effect of water erosion on flame retardancy of the HIPS/MH composite and its mode of action was investigated by various means. The results indicate that both limiting oxygen index value and UL-94 rating of the HIPS/MH composite decrease observably after water erosion. The average heat release rate, average mass loss rate, total heat release, and total smoke release of the composite all increase remarkably after water erosion. The MH content in the surface layer of the HIPS/MH composite reduces, and the surface of this composite becomes rough and porous after erosion. The water-eroded composite shows a loose and discrete surface morphology after subjected to fire, which favors heat transfer and mass exchange between flame area and the underlying polymers. Consequently, both flame retardancy and smoke suppression of the polymer composite decrease significantly. The decrease in flame retardancy occurs in condensed phase. The result of this work has provided a basis for further investigations to prevent this detrimental effect induced by water erosion.     

Superior thermal stability and smoke suppression of epoxy resin composites with graphene/LDH phosphorus-rich hybrids

In this article, graphene/LDH phosphorus-rich triple hybrid was prepared by a mild method and used to effectively improve the thermal stability and smoke suppression of epoxy resin (EP). The graphene was firstly reacted with hexamethylenediamine (HA) and followed by the treatment with the layered double hydroxide (LDH) and NaH₂PO₄ solutions. Compared to the unmodified graphene, the initial decomposition temperature of the triple hybrids increases significantly from 168.6 to 292.5°C. The residual carbon content is greatly improved and the residual mass is up to 84.1%. Elemental analysis reveals the content of phosphorus in EP composites is as high as 10 wt%. In flame retardancy tests, the peak heat release rate of the EP composite with 5 wt% graphene/LDH phosphorus-rich hybrids decreases to 786.15 KW/m², 41.19% drastic reduction compared to that of EP. These results indicate that the triple functionalization process effectively expands the interval distribution of heat release and makes the heat release process more gradual and spread flames smaller. The smoke production rate and total smoke production rate of EP composite with 5 wt% graphene/LDH phosphorus-rich hybrids are 0.32 m²/s and 40.91 m², which are significantly reduced by 65.22 and 57.83%, respectively. This gentle and efficient process provides a new approach to multi-functional design to improve the thermal stability and smoke suppression of resin-based composites.     

复合型阻燃剂对聚氯乙烯的阻燃抑烟作用研究

采用微胶囊红磷（MRP）、硼酸锌（ZnBO3）、氢氧化铝(ATH)和氢氧化镁(MH)进行复配对软质聚氯乙烯（PVC）进行阻燃处理,通过极限氧指数、热失重、锥形量热方法研究了不同配比阻燃剂对PVC的阻燃抑烟性能的影响。结果表明,当PVC/MRP/ZnBO3/ATH/MH质量比为100:3:1:20:20时,具有良好的阻燃抑烟效果,极限氧指数可达35.9 %;阻燃体系PVC/ATH/MH、PVC/MRP/ZnBO3/ATH/MH相对于纯PVC具有良好的阻燃抑烟性,PVC/MRP/ZnBO3/ATH/MH比PVC/ATH/MH体系在热释放、烟气、一氧化碳和二氧化碳排放指标上数值更低,热稳定性增加,成炭率更高,火灾性能指数提高,火灾蔓延指数减小,火灾危险性降低。     

Facile Synthesis of Zinc-Containing Mesoporous Silicate from Iron Tailings and Enhanced Fire Retardancy of Rigid Polyurethane Foam

Iron tailings (ITS), as solid decay absolved afterward beneficiation, are adverse to the environment. ITS to prepare zinc-containing mesoporous silicate (MAO-Zn) by a calcination-crystallization method are used. An admixture of ammonium polyphosphate (APP) and MAO-Zn can solve the problem of poor flame retardancy in rigid polyurethane foam (RPUF), giving them higher thermal stability and lower heat release. The total heat release rate and smoke factor values exhibited by RPUF-3 are 24.52 MJ m⁻² and 234.29 MW m⁻² respectively, a decrease of 38.45% and 29.60% respectively compared to pure RPUF. Lower combustible and toxic gas release intensities are in RPUF-3. Meanwhile, RPUF-3 possesses enhanced compactness char residue with higher graphitization degree, endowing RPUF-3 with excellent fire observed performance. This work demonstrates the potential of ITS in the fire retardancy field.     

Study on the ablative properties of ethylene propylene diene terpolymer/silsesquioxane insulation materials

Octaphenylsilsesquioxane (OPS), polyphenylsilsesquioxane (PPSQ), and octavinylsilsesquioxane (OVP) have been incorporated into ethylene propylene diene terpolymer (EPDM) in order to study their effects on the ablative properties of the respective EPDM composites. The results show that PPSQ and OVP serve as effective ablative additives for EPDM composites. The linear ablation rates of EPDM composites with 4.4 wt % OVP or PPSQ were reduced by 21 or 16.5%, respectively, compared with the control sample. Moreover, OVP and PPSQ also improved the flame retardancy and suppressed smoke emission. The heat release rate of EPDM composite with 4.4 wt % OVP was measured as 90.6 kW m⁻², 17% lower than that of the control sample, and the same amount of PPSQ reduced the total smoke release from 1946 to 1497 m² s⁻¹. Thermogravimetric analysis results showed EPDM/OVP composite to leave a higher residual mass than the calculated value. Besides, scanning electron microscopy, cone calorimetry (CONE), and BET tests showed that the chars formed during the ablation of EPDM composites containing OVP and PPSQ had better structural stability and thermal stability owing to the fact that they were denser and more homogeneous. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48365.     

Boosting flame retardancy of thermoplastic polyurethane: Synergistic effect of nickel phosphide nanoparticles and molybdenum disulfide nanosheets

For the first time, a novel nanohybrid based on nickel phosphide (Ni₂P) nanoparticles and molybdenum disulfide (MoS₂) nanosheets was facilely synthesized for enhancing flame retardancy and smoke suppression of thermoplastic polyurethane (TPU). The synergistic effect on flame retardancy is proposed. TPU composite with 2 wt% Ni₂P/MoS₂ hybrid exhibits the best overall flame retardancy, while TPU composites with the same amount of individual Ni₂P nanoparticles and MoS₂ nanosheets are average in performance. Specifically, the 41.2% reduction of peak heat release rate (PHRR) is achieved for TPU/Ni₂P/MoS₂ composite, which is only 16.8% and 26.4% for TPU/Ni₂P and TPU/MoS₂ composites, respectively. In addition, a more intact protective char layer of TPU/Ni₂P/MoS₂ composite can be observed. These results clearly suggest the synergistic effect between Ni₂P nanoparticles and MoS₂ nanosheets. It is hypothesized that physical barrier effect and chemical catalytic ability of Ni₂P/MoS₂ hybrid contribute to the dramatic reduction of heat release and smoke production. The strategy proposed here is a simple yet efficient approach to fabricate high-performance MoS₂-based flame retardants.     

Lightweight,robust, porous heterocyclic para-aramid aerogel hollow fibers for multifunctional applications

In nature, many fibers with warmth-retention properties, such as the hair of polar bears and rabbits, both have a hollow cross-section structure. The static air in fiber cavities can effectively inhibit heat conduction and serve as an effective thermal insulator. In this work, the high-performance heterocyclic para-aramid polymer was selected as the spinning solution, and aerogel hollow fiber was prepared by coaxial wet spinning and freeze-drying techniques. The effects of spinning solution concentration and lyophilized solvent on the micromorphology, mechanical properties, and specific surface area of heterocyclic para-aramid aerogel hollow fiber (HPAAHF) were systematically studied. The produced HPAAHF possessed excellent mechanical properties (tensible strength ~3.85 MPa), high specific surface area (~ 260.90 m² g⁻¹), and lightweight advantages. The thermal conductivity of HPAAHF was only 0.0278 W m⁻¹ K⁻¹, indicating its excellent thermal insulation properties. The aerogel fabric exhibited outstanding flame retardancy properties, with a total heat release of only 0.7 MJ m⁻² in the cone calorimetric experiment, making it a self-extinguishing fabric. In addition, phase change material was injected into the hollow structure to obtain aerogel-phase change material composite fibers, which exhibited great energy storage prospects. As a result, the high-performance heterocyclic para-aramid polymer-based aerogel hollow fiber was successfully prepared and had multifunctional applications in thermal insulation, flame retardancy, and heat energy storage fields.     

Enhanced flame retardancy,smoke suppression,and acid resistance of polypropylene/magnesium hydroxide composite by expandable graphite and microencapsulated red phosphorus

Low flame retardant efficiency and poor acid resistance of filled polymer composites are two main drawbacks of magnesium hydroxide (MH) as a flame retardant (FR). To solve these problems, expandable graphite (EG) and microencapsulated red phosphorus (MRP) were introduced into polypropylene/magnesium hydroxide (PP/MH) composite by melt compounding. The obtained PP/MH/EG/MRP quadruple composite was studied regarding its fire behavior as well as acid resistance. Obvious flame retardant synergism among MH, EG, and MRP is found in PP, which diminishes the loading of FR from 63.0 to 37.5 wt% to obtain V-0 rating in UL-94 test and low smoke release. Compact intumescent char with high thermo-oxidative stability was generated on composite surface, which plays a vital role in flame retardancy. The removal of MH by acid erosion on PP/MH/EG/MRP composite surface does not affect production of intumescent char and fire behavior of this composite. The composite displays good fire retardancy, smoke inhibition, and acid resistivity concurrently. This article renders an easy and cheap route to overcome the main faults of MH.     

Enhancement of fire safety in epoxy resin composites through incorporation of microencapsulated diatomite

Diatomite (DIA) particles are commonly employed as flame-retardant additives for polymers, yet their intrinsic inefficiency requires substantial quantities for optimal efficacy. To address this issue, we proposed a novel approach involving the microencapsulation of DIA with polyethylene glycol phosphate (PEGP) to enhance the flame retardancy of epoxy resin (EP). Characterization of the prepared DIA@PEGP utilized scanning electron microscopy with energy-dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The resulting EP composite, DIA@PEGP-4/EP, achieved a limiting oxygen index of 33.2% and achieved a V-0 level in vertical combustion tests. Compared to EP, DIA@PEGP-4/EP demonstrated significantly improved fire performance, with 38.6%, 47.8%, 25.0%, 41.3%, and 60.4% reduction in peak heat release rate, total heat release, peak smoke production rate, total smoke production, and CO yield. Furthermore, the highest FPI value of 0.080 m²·s/kW for DIA@PEGP-1/EP and the lowest FGI value of 8.734 kW/m²·s for DIA@PEGP-4/EP, indicate that the incorporation of DIA@PEGP into EP enhances its fire safety. The flame retardancy mechanism of DIA@PEGP-4 involves the formation of a phosphorus-containing aromatic carbon layer during EP char formation, capturing radicals in the gas phase during combustion.     

Synthesis and properties of a phosphate ester as curing agent in an epoxy resin system

Phosphate ester compounds display good flame retardancy effect in epoxy resin systems. In this paper, several novel phosphate esters, used as curing agents for epoxy resins, were synthesized based on P₂O₅, phosphoric acid, and different types of alcohol. The structures of phosphate esters were characterized by ³¹P nuclear magnetic resonance (³¹P NMR). Then, a series of flame retardant epoxy composites were prepared by curing the epoxy resins (E-44) with the phosphate esters. The flame retardancy and thermal degradation behaviors of flame retardant epoxy composites were investigated by cone calorimeter test (CCT) and thermogravimetric analysis (TGA), respectively. The results of CCT indicated that phosphate esters can significantly decrease heat release rate, total heat release (THR), and smoke production rate. The sample cured by butyl phosphate ester from phosphorus pentoxide, phosphoric acid and butanol showed the best flame retardant performance among all samples. The TGA results showed that phosphate esters could enhance char residues of flame retardant epoxy composites when compared with those of a composite using T31 as a curing agent at high temperature. It may be concluded that good flame retardant properties of flame retardant epoxy composites are related to the formation of a protective phosphorus-rich char layer. These phosphate esters have a good future on flame retardant epoxy composites.     

Lightweight and flame retardant fluorosilicone rubber composited foam prepared by supercritical nitrogen

Improving the flame retardancy and lightweight of fluorosilicone rubber (FSR) foam is important for its application in aerospace, rail transportation, petrochemical equipment, etc. In this work, ammonium polyphosphate (APP) and expandable graphite (EG) were used as synergistic flame retardants, and the lightweight FSR composite foam with flame retardancy was prepared by supercritical N₂ foaming. When there were 12.5 phr APP and 7.5 phr EG, the composite foam with density of 0.254 g/cm³ showed superiority in foaming performance and flame retardancy, and the limit oxygen index was 36.4%, the UL-94 grade reached V-0, the ignition time was 12 s and the fire performance index was 0.071 s·m²/kW. In addition, the aging, oil and solvent resistance of FSR foam was not affected. This work provided data support for the production and application of the flame retardant FSR foam.     

氨基硅油对氢氧化镁及有机蒙脱土阻燃LLDPE的影响

用氢氧化镁(MH)和有机蒙脱土(OMMT)作为阻燃剂制备了阻燃线型低密度聚乙烯(LLDPE),研究了氨基硅油(ASO)对阻燃LLDPE力学性能及阻燃性能的影响。通过锥形量热仪(CONE)和热失重分析(TGA)对材料进行了表征。结果表明:ASO提高了阻燃性能和抑烟效果。当ASO用量为2%时,阻燃LLDPE的热释放速率峰值(pHRR)和平均热释放速率(mHRR)分别降低到169.6kW/m2和86.7kW/m2,比加入ASO前下降了20.5%和9.7%;烟产生速率峰值(pSPR)和总生烟量(TSP)分别降低到0.017m2/s和0.4m2。此外,ASO提高了材料的断裂伸长率和冲击强度。     

Synergistic Effect of Mesoporous Nanocomposites with Different Pore Sizes and Structures on Fire Safety and Smoke Suppression of Epoxy Resin

Epoxy resin (EP) is extremely flammable, and smoke release during combusting is considered toxic and harmful for human health. Mesoporous materials offer reliable desorption performance due to their large specific surface area. Therefore, the construction of mesoporous nanocomposites is a novel method for enhanced smoke suppression effect of EP. In this work, zinc hydroxystannate (ZHS)‐mesoporous silica (SBA‐15 and MCM‐41) modified reduced graphene oxide (RGO) is successfully prepared and used to enhance the fire safety of EP. SBA‐15‐RGO‐ZHS/EP exhibits the lowest total smoke production (22.8 m²) and peak heat release rate (416 kW m^?2), which are reduced by 55% and 37% compared with pure EP, respectively. Furthermore, the effect of mesoporous nanoparticles is also investigated. Apparently, the smoke suppression effect and flame retardancy of SBA‐15‐RGO‐ZHS/EP is even more remarkable than that of MCM‐41‐RGO‐ZHS/EP, which indicates that the pore size and structure of mesoporous are important factors for reducing the smoke toxicity of EP. Finally, it is verified that its enhanced fire safety is attributed to the synergistic action of physical barrier properties of RGO, “labyrinth” effect of SBA‐15, and catalytic ability of ZHS.     

A novel phytic acid based flame retardant to improve flame retardancy,hydrophobicity and mechanical properties of linear low-density polyethylene

Exploiting high phosphorus content of phytic acid, it was grafted onto magnesium hydroxide (MH) by neutralization reaction to obtain MGPA, a flame retardant. A current study investigated the effect of MGPA on hydrophobicity, flame retardancy, and mechanical properties of MGPA-linear low-density polyethylene (LLDPE) composites. The LLDPE composite with 50 parts of MGPA has the better flame retardancy and thermal stability with a limiting oxygen index of 23.3%, which is higher than that of neat LLDPE (17%). In addition, MGPA could effectively promoted LLDPE to form a continuous and compact char residue during combustion, which reduce the peak of heat release rate and total smoke production value of LLDPE composite by 70% and 36%, respectively, and the char residue rate increase to 67.5%. Furthermore, the maximum of loss-rate showed by LLDPE composite with MGPA reduce to 1.25%/min while the value of LLDPE composite with MH is 1.8%/min. Meanwhile, the LLDPE composite with MGPA show remarkable elongation at break and hydrophobicity, which are 398% and 99°, respectively. In addition, this study presents a substantial flame retardancy and interfacial compatibility of MGPA for extending the applications of flame-retardant LLDPE composites.     

Preparation and characterization of the halogen-free,smoke suppression,organic–inorganic hybrid flame-retardant expandable polystyrene materials

Expandable polystyrene (EPS) is a plastic widely used in the field of construction, but it is flammable. This work provided a novel strategy for flame-retardant modification of EPS. A kind of polyester polyol (JZP) with the high content of phosphorus and nitrogen was synthesized. Then, intrinsic flame-retardant polyurethane (PFWPU) with the high content of phosphorus and nitrogen was synthesized by JZP acted as soft segment chain extender. Finally, a high-efficiency flame-retardant expandable polystyrene thermal insulation material (AF-EPS) was prepared by the organic–inorganic hybrid flame-retardant synergistic action of PFWPU and ammonium polyphosphate. The effects of different contents of inorganic flame retardants on flame retardancy of materials were studied by limiting oxygen index (LOI), cone calorimetry, thermogravimetric analysis/infrared spectrometry , scanning electron microscopy, and so on. The test results showed that the carbon residue rate of the modified material increased from 0 to 28.5%, the LOI increased from 17 to 35.8%, and the vertical combustion test reached the highest grade V-0. In addition, the total smoke production of AF-EPS samples decreased from 2.33 m² to 0.57 m², the time to ignition was increased to 41 s, and the peak heat release rate and the total heat release were decreased by 90.2 and 62.7%, respectively.     

Preparation and properties of wear-resistant and flame-retardant polyphenylsulfoneurea/monomer casting nylon copolymers

A poly(phenylsulfone)-urea (PPSUU) macro-activator is synthesized by in situ anionic polymerization of 4,4′-diaminodiphenylsulfone and hexamethylene diisocyanate. The PPSUU segment is embedded into the nylon molecular chain through copolymerization to improve the wear resistance and flame retardancy of monomer cast nylon 6 (MC PA6) materials. The mechanical properties, thermal stability, friction and wear properties and combustion heat release rate of copolymers with different macro-activator contents are tested. Results indicate that a small amount of PPSUU can improve the wear resistance and impact properties of nylon materials. The wear loss of MC nylon is 54.8% less than pure MC nylon from 1.049 × 10⁻⁸ to 0.474 × 10⁻⁸ g/Nm with 6 wt% PPSUU. Moreover, better flame retardancy is verified. The peak of HRR reduced 36.8% from 654 to 413 kw/m² with 4 wt% PPSUU, accompanied by advanced ignition time and flame extinction time, thus reducing the risk of fire.