CuMoO<Subscript>4</Subscript>@hexagonal boron nitride hybrid: an ecofriendly flame retardant for polyurethane elastomer

A novel flame retardant (CuMoO₄@h-BN) was synthesized through the co-precipitation method, and its structure and morphology were systematically characterized. CuMoO₄@h-BN was added to polyurethane elastomer (PUE) to investigate the effect of thermal, flame retardancy and smoke suppression properties on the PUE composites. The results showed that 2 wt% CuMoO₄@h-BN increased the residual char yield of the PUE composite notably to 9.8%. CuMoO₄@h-BN exhibited an excellent charring effect. Compared with pure PUE, 2 wt% CuMoO₄@h-BN decreased the peak heat release rate, total heat release and smoke density of the PUE composite by 73.6, 52.4 and 28.2%, respectively. CuMoO₄@h-BN performed well in flame retardancy and smoke suppression. It may be attributed mainly to the physical barrier effect of h-BN and catalytic carbonization effect of CuMoO₄. It is expected that this simple and inexpensive treatment of PUE may help expand the fire safety applications of the material.     

胶合板表面层层自组装聚磷酸铵-壳聚糖/氮化硼及其阻燃性能

以杨木胶合板为研究对象,以聚磷酸铵-壳聚糖/氮化硼(APP-CS/BN)为阻燃涂层,通过层层自组装的方法将涂层整理到杨木胶合板上,以赋予胶合板一定的阻燃性能。FTIR和SEM结果显示,APP-CS/BN涂层在胶合板表面组装形成膜结构,组装膜均匀分布在材料表面。锥型量热仪(CONE)燃烧测试表明,与未经处理的胶合板相比,APP-CS/BN自组装涂层能有效延长胶合板点燃时间(TTI),降低胶合板的热释放速率(HRR)和总热释放量(THR),同时增加材料燃烧后成炭量。随着自组装涂层层数的增加,15层处理材、20层处理材、25层处理材的点燃时间较未处理材分别提升了100%、105%和125%;热释放速率峰值(Pk-HRR)较未处理材分别降低10.15%、22.34%和31.82%;阻燃处理杨木胶合板的THR,较未处理材分别降低2.89%、13.68%和15.32%;未处理材、15层处理材、20层处理材、25层处理材燃烧后成炭率依次为18.55%、24.07%、26.04%和27.65%。随着自组装层数的增加,杨木胶合板的阻燃性能随之增加,但当自组装层数由20层至25层时,胶合板阻燃能力提升的幅度变缓慢。本研究中,阻燃胶合板适宜自组装涂层数为20-25层。      

Fire and Corrosion Resistances of Intumescent Nano-coating Containing Nano-SiO2 in Salt Spray Condition

The nano-concentrates and fiame retardant nano-coating were prepared in thhis study. The effect of nano-SiO₂ on the corrosion resistance and fire resistance of ammonium polyphosphate-pentaerythritol-melamine (APP-PER-MEL) coating was investigated by differential thermal analysis (DTA), scanning electron microscopy (SEM), effective thermal conductivity (λ/d), X-ray photoelectron spectroscopy (XPS) and fire protection test. The chemical action and endothermic effect of ammonium polyphosphate, pentaerythritol and melamine in traditional flame retardant coating were damaged by salt spray condition, whereas the flame-retardant additives in the nano-coating demonstrated the good chemical interaction in salt spray condition. The uniformly dispersed nano-SiO₂ particles could improve corrosion resistance of the coating, and hence nano-coating could remain the good fire-resistant properties even after 500 h salt spray test.     

水性膨胀型钢结构防火涂料耐火性能研究

以水性乳液为基体,聚磷酸铵(APP)、三聚氰胺(MEL)、季戊四醇(PER)为膨胀阻燃体系,通过添加可膨胀石墨(EG)和绢云母制备了水性膨胀型钢结构防火涂料;研究了基体拼合、膨胀阻燃体系配比、EG与绢云母配比对钢结构防火涂料性能的影响。结果表明,氯偏乳液与纯丙AC261P乳液质量比为22∶3,APP/MEL/PER的质量比为4∶3∶3,可膨胀石墨和绢云母的质量比为5∶3时,制备的防火涂料受热后形成的炭质层与钢板粘附性好、强度高,膨胀倍率大,持续耐火性能最好,受热4500s后钢板背面温度维持在223℃。     

Preparation of a novel type of flame retardant diatomite and its application in silicone rubber composites

A novel strategy was used for preparation of flame retardant based on biomass debris to improve the flame retardant property of silicone rubber (SR). [(6-oxido-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)methyl]butanedioic acid (DDP) was used to modify diatomite by esterification method, and DDP@diatomite was obtained. The structure and morphology of this novel additive was identified using Fourier transform infrared spectroscopy (FTIR), Brunner-Emmet-Teller (BET) measurements, and X-ray photoelectron spectroscopy (XPS) together with scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS) techniques. Thermogravimetric (TG) analysis was performed to evaluate the thermal degradation behaviors of diatomite and DDP@diatomite. This novel additive was applied into silicone rubber (SR) composites. Combustion parameters, including heat release rate (HRR), total heat release (THR), smoke production rate (SPR), carbon monoxide (CO), peak smoke production rate (PSPR), peak carbon monoxide (PCO) and vertical burning time, were characterized by cone calorimeter and vertical burning tests. Results indicated that this flame retardant can reduce fire risk and toxicity effectively. TG and X-ray diffraction (XRD) patterns of SR and its composites were also investigated. The inexpensive property of modified diatomite could also expand its fire safe applications.     

Flame retardancy and thermal properties of epoxy acrylate resin/alpha-zirconium phosphate nanocomposites used for UV-curing flame retardant films

This paper reported the UV-curing flame retardant film, which consisted of epoxy acrylate resin (EA) used as an oligomer, tri(acryloyloxyethyl) phosphate (TAEP) and triglycidyl isocyanurate acrylate (TGICA) used as flame retardant (FR). The flame retardancy and thermal properties of films were reinforced by using alpha-zirconium phosphate (α-Zr (HPO₄)₂H₂O, α-ZrP). The morphology of nanocomposite film was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that the organophilic α-ZrP (OZrP) layers were dispersed well in epoxy acrylate resin. Microscale Combustion Calorimeter (MCC), thermogravimetric analysis (TGA) and thermogravimetric analysis/infrared spectrometry (TGA-IR) were used to characterize the flame retardant property and thermal stability. It was found that the incorporation of TAEP and TGICA can reduce the flammability of EA. Moreover, further reductions were observed due to the addition of OZrP. The char residue for systems with or without OZrP was also explored by scanning electron microscopy (SEM).     

杨木胶合板阻燃性能研究

通过热释放速率(HRR)、总热释放量(THR)、有效燃烧热(EHC)、CO产率、CO2产率以及烟释放总量等指标,研究了杨木胶合板的阻燃性能。实验结果表明:磷酸氢镁和二氧化锆阻燃剂单独使用时,都能够在杨木胶合板燃烧过程中降低热释放速率、总热释放量、有效燃烧热、CO2产率以及烟释放总量,增大CO产生速率,但阻燃效果不理想;而磷酸氢镁与纳米二氧化锆复合阻燃剂,可以在杨木胶合板燃烧过程中产生协同效应,并且使用此复合阻燃剂的杨木胶合板在点燃190 s后即停止燃烧,其阻燃效果最佳。     

有机蒙脱土协同含磷木质素基成炭剂阻燃聚乳酸

将自制含磷木质素基成炭剂（Lig-P）和聚磷酸铵（APP）复配用于制备阻燃聚乳酸（PLA）基复合材料,考察了协效阻燃剂有机蒙脱土（OMMT）对阻燃PLA性能的影响。采用极限氧指数（LOI）仪、垂直燃烧（UL-94）测试仪、锥形量热仪、热失重分析仪分别对Lig-P-APP-OMMT/PLA阻燃复合材料的阻燃性能、热稳定性能和燃烧行为进行了研究。结果发现,OMMT与Lig-P-APP存在明显的协同阻燃作用,当OMMT替代3wt%的Lig-P-APP时,Lig-P-APP-OMMT/PLA阻燃复合材料的LOI由27%增加至32%,UL-94等级由V1级提高至V0级;且Lig-P-APP-OMMT/PLA阻燃复合材料的最大热降解速率有所降低,800℃的残炭量提高了将近50%;此外,OMMT的引入使PLA阻燃复合材料的热释放速率明显降低,热释放速率峰值（PHRR）、烟释放速率峰值（PSPR）及总烟释放量（TSR）分别降低了26.4%、60%及26.3%。OMMT可明显提高阻燃PLA炭层的致密度及石墨化程度。      

Studies on the impact fracture behaviour of flame retardant polymeric material

Two commercial flame retardant (FR) additives, a brominated phosphate ester/antimony trioxide mixture and a magnesium hydroxide were added up to 30 and 60% by weight to polypropylene matrix, respectively. The impact behaviour of the PP/FR composites were studied by the Charpy impact test and the impact fracture toughness (G_c) measurement. As the amount of FR increases, the impact properties decreased accordingly. Such behaviour is strongly related to the morphologies and was investigated by means of scanning electron microscopy (SEM).     

Use of nanoclay as an environmentally friendly flame retardant synergist in polyamide-6

Due to their very high levels of flame retardancy, chlorinated and brominated flame retardants had been the most widely used flame retardant additives in plastics industry. However, these flame retardants lead to formation of very toxic volatiles and by-products during fire. Therefore, the recent trend is to replace all of them with non-halogenated flame retardants. In this respect, the use of nanoclays as a synergist flame retardant is becoming more and more important. Thus, the main aim of this work was to investigate the synergistic flame retardant effect of nanoclays with phosphorous compounds in polyamide-6 composites. For this purpose, exfoliated clay nanocomposites of flame retarded/glass fiber reinforced polyamide-6 were prepared by melt compounding. A flame retardant based on phosphorus compounds was used at various levels in glass fiber reinforced polyamide-6 and nanocomposites. Flammability and fire behaviors were evaluated by limiting oxygen index, UL94 and cone calorimeter tests. Substitution of a certain fraction of the flame retardant with nanoclays was found to significantly reduce the peak heat release rate and delay the ignition in cone calorimeter. Moreover, remarkable improvements were obtained in limiting oxygen index along with maintained UL94 ratings.     

兼具阻燃和导热性能的环氧树脂复合材料：石墨烯纳米片杂化三聚氰胺磷酸盐的作用

研发制备低成本、少缺陷及高效率的石墨烯纳米片杂化阻燃剂对实现复合材料多功能性具有重要意义。以三聚氰胺为助剥离剂将微粉石墨(GRA)经机械球磨后与磷酸液相反应得到一种阻燃导热的石墨烯纳米片杂化三聚氰胺磷酸盐(GMP),在表征GMP形貌、结构、组成和热稳定性的基础上,研究了添加GMP环氧树脂(EP)复合材料的阻燃、热分解和导热性能。GMP的热失重分析结果表明：与三聚氰胺磷酸盐(MP)相比,初始分解温度提升了29.3℃,与环氧树脂的热分解温度更匹配,有助于提高阻燃效率。氧指数仪、锥形量热仪和导热性能研究表明,GMP添加30wt%时,EP复合材料的极限氧指数达到了30.4%,UL 94垂直燃烧达到V-0级,峰值热释放速率(PHRR)和峰值烟释放速率(PSPR)分别下降69%和74.0%;导热系数提升至2.10 W·m^-1·K^-1,相对于EP提升了708%。这是由于GMP中石墨烯纳米片(GNPs)与MP的相互作用促进了EP形成了致密的膨胀炭层,有效提高了EP复合材料的阻燃性;随着GMP添加量的增加,GNPs和石墨微片传热通道的形成改善了EP复合材料的导...     

MCA-MMT的制备及其对玻璃纤维增强聚丙烯复合材料阻燃性能的影响

为了提高玻璃纤维(GF)增强聚丙烯(PP)复合材料(GF/PP)的阻燃性能,通过在蒙脱土(MMT)悬浮液中进行三聚氰胺氰尿酸盐(MCA)分子自组装制备了新型协效成炭剂MCA-MMT,并采用FTIR、XRD、SEM和TGA对MCA-MMT的结构及热性能进行了表征;将MCA-MMT、无卤膨胀型阻燃剂与GF/PP熔融共混制备了阻燃复合材料MCA-MMT/(GF/PP),通过极限氧指数(LOI)测试、垂直燃烧试验和锥形量热测试研究了MCAMMT对GF/PP的阻燃效果和阻燃机制,并测试了复合材料的力学性能。结果表明:MMT的加入会影响氰尿酸和三聚氰胺在MCA合成过程中的氢键作用,干扰和抑制大平面氢键网络的形成,减少MCA氢键复合体的分子体积,使颗粒变小。MCA-MMT/(GF/PP)的UL-94防火等级达到V-0级,LOI为31.3%。MCA-MMT的阻燃效率高于传统MCA的,可降低材料燃烧的热释放程度和总烟释放量,使复合材料的阻燃性能提高,其阻燃机制为片层结构的MMT可提高MCA的成炭量,使MCA-MMT/(GF/PP)燃烧后能形成致密的残留炭层。MCA-MMT/(GF/PP)的拉伸、冲击强度与MCA/(GF/PP)的相比并未下降。     

无卤阻燃乙烯-醋酸乙烯酯共聚物泡沫复合材料的制备及性能表征

为使得乙烯-醋酸乙烯酯共聚物(EVA)泡沫复合材料具有阻燃功能,分别添加膨胀石墨-聚磷酸铵(EGAPP)和膨胀石墨-聚磷酸铵-热塑性淀粉(EG-APP-TPS)两种不同复配阻燃剂,通过熔融共混和硫化发泡制备了无卤阻燃EVA泡沫复合材料。采用极限氧指数(LOI)、垂直燃烧(UL-94)、热分析质谱联用(TG-MASS)及扫描电镜(SEM)测试等对EG-APP/EVA及EG-APP-TPS/EVA泡沫复合材料进行表征。结果表明:EG-APP复配阻燃剂添加量为30wt%、EG与APP质量比为1∶4时,EG-APP/EVA泡沫复合材料的LOI达28.1%,UL-94为V-1级;而当EG-APP-TPS复配阻燃剂添加量同为30wt%,EG、APP与TPS质量比为1∶4∶1时,EG-APP-TPS/EVA泡沫复合材料的LOI可达29.3%,UL-94为V-0级。TG-MASS和SEM分析表明:EG、APP和TPS在气相和固相中均具有显著的协同阻燃作用。     

环磷腈阻燃剂的开发与应用研究进展

主要综述了近几年有关羟基环三磷腈、氨基环三磷腈、双键环三磷腈等阻燃剂的开发与应用,简要介绍了目前环磷腈阻燃剂的发展现状,并对其研究方向予以展望。     

A novel and multifunctional flame retardant nucleating agent towards superior fire safety and crystallization properties for biodegradable poly (lactic acid)

In engineering application area, it has always been a challenge to simultaneously improve flame-retardant performance and crystallization rate of polylactic acid (PLA) biomaterials, thus restricting their extensive application. In this work, a multifunctional additive (4,4′-(phenylphosphoryl)bis(piperazine-4,1-diyl))bis(diphenylphosphine oxide) (PDPO) was successfully synthesized and used to fabricate flame retardant PLA biocomposites. The crystallization behavior, fire safety, mechanical properties and flame retardant mechanisms of PLA biocomposites were studied in detail. The results indicated that PDPO notably improved the crystallization rate and crystallinity of PLA biocomposites. When 4 wt% PDPO was incorporated, PLA/PDPO biocomposites successfully passed UL-94V-0 grade and their LOI values were improved from 19.0% of pure PLA to 29.4%. The introduction of PDPO promoted the premature degradation and carbonization of PLA substrate, and inhibited the transesterification of the PLA during thermal pyrolysis process. Besides, PDPO decomposed and produced the Ph and PO, which efficiently exerted the free radical trapping effect in vapor phase. Therefore, the spread of fire for PLA/PDPO was declined and even self-extinguished. Meanwhile, the low addition of PDPO presented little effect on the mechanical properties of PLA composites. This flame retardant PLA biocomposites showed broad application prospects in emerging fields such as electronic devices, automobiles, and 3D printing materials.     

Effect of flame retardants on flame retardant,mechanical, and thermal properties of sisal fiber/polypropylene composites

A flame retardant efficiency of flame retardants; ammonium polyphosphate (APP), magnesium hydroxide (Mg(OH)₂), zinc borate (Zb), and combination of APP with Mg(OH)₂ and Zb in sisal fiber/polypropylene (PP) composites was investigated using a horizontal burning test and a vertical burning test. In addition, maleic anhydride grafted polypropylene (MAPP) was used as a compatibilizer to enhance the compatibility in the system; i.e. PP-fiber and PP-flame retardants. Thermal, mechanical, and morphological properties of the PP composites were also studied. Adding the flame retardants resulted in improved flame retardancy and thermal stability of the PP composites without deterioration of their mechanical properties. APP and combination of APP with Zb effectively enhanced flame retardancy of the PP composites. No synergistic effect was observed when APP was used in combination with Mg(OH)₂. SEM micrographs of PP composites revealed good distribution of flame retardants in PP matrix and good adhesion between sisal fiber and PP matrix.     

不饱和聚酯/蒙脱土阻燃纳米复合材料的制备及表征

采用原位插层复合法制备不饱和聚酯/蒙脱土阻燃纳米复合材料.通过XRD、SEM和TEM等手段表征不饱和聚酯/蒙脱土阻燃纳米复合材料的微观结构;通过拉伸、冲击和氧指数实验对不饱和聚酯/蒙脱土阻燃纳米复合材料的力学性能、阻燃性能进行研究.结果表明,当蒙脱土含量为0.5%时阻燃纳米复合材料与纯不饱和聚酯相比氧指数从22上升到24,此时拉伸强度提高8.76%,冲击强度提高68.65%.与阻燃剂/不饱和聚酯复合材料相比,同等阻燃级别下拉伸强度提高23.06%,冲击性能提高93.9%.     

Surface modification of magnesium hydroxide and its application in flame retardant polypropylene composites

In this article, titanate and zinc stearate modified superfine magnesium hydroxide [Mg(OH)₂] was filled into polypropylene (PP) as a flame retardant (FR). The structure and morphologies of untreated and treated Mg(OH)₂ particles were characterized by Fourier transform infrared (FTIR), wide-angle X-ray diffraction (WAXD), and scanning electron microscope (SEM). PP/Mg(OH)₂ (1:1) composites were also prepared in co-rotating twin-screw extruder, and the effects of treatment agents on the rheological behavior, mechanical properties, and flame retardancy of PP/Mg(OH)₂ composites were studied. The results from FTIR and WAXD show that treatment agents are adsorbed onto the surface of Mg(OH)₂ particles. The complex viscosity (η*) values of the composites decrease with the addition of various treatment agents. Surface treatment agent could significantly improve tensile and impact strength of PP/Mg(OH)₂ composites due to its enhanced interfacial adhesion between Mg(OH)₂ particles and the PP matrix. According to limiting oxygen index (LOI), titanate treated magnesium hydroxide (MH) greatly enhanced flame retardancy of PP/Mg(OH)₂ composites.     

Polymer nanocomposites based on epoxy resin and ATH as a new flame retardant for CFRP: preparation and thermal characterisation

Nanoscale aluminium trihydroxide (ATH) is examined to its suitability for carbon fibre reinforced plastics (CFRP) as a novel flame retardant. In particular the influence of particle size and concentration of ATH to the fire behaviour of epoxy polymer matrices is determined. The particle size is adjusted by means of different dispersing techniques. By SEM images and viscosity measurements the homogeneity of the produced ATH dispersions for the liquid ones and of cured epoxy–ATH nanocomposites is determined. Based on these pre-results, selected ATH dispersions are used for the manufacturing of CFRP which are produced by the proved injection technology. The thermal stability of the ATH nanocomposite plates and the corresponding CFRP plates are analyzed by means of quantitative single difference thermoanalysis (QSDTA). The fire behaviour is characterised by using the OSU chamber test. Both tests indicate a reduced heat release rate by decreasing the ATH particle size, i.e. the thermal load decreases. A combined fire protection mechanism is discussed for the improved fire protection through ATH nanoparticles.     

(壳聚糖-聚磷酸铵)/剑麻纤维素微晶层层自组装复合材料的热性能和阻燃性能

采用层层自组装法（LBL）,在剑麻纤维素微晶（SFCM）表面交替吸附壳聚糖（CH）和聚磷酸铵（APP）构筑CH-APP阻燃涂层,成功制备（CH-APP）_n/SFCM阻燃复合材料。通过Zeta电位分析仪、FTIR、TGA、POM、垂直燃烧法（VFT）、SEM手段对复合材料的结构和性能进行表征。FTIR、Zeta电位结果表明,CH和APP在SFCM表面电位正负交替变化,CH-APP涂层成功包覆在SFCM表面; POM和SEM结果显示,组装后（CH-APP）_n/SFCM复合材料表面变得粗糙,其表面包覆了一层较厚涂层; TGA结果表明,随着吸附CH-APP组装层数的增加,（CH-APP）_n/SFCM复合材料的初始分解温度（T_5%）由279.4℃降低至243.1℃,残炭率由11.24%提高至32.06%; VFT测试结果表明,随着组装层数的增加,（CH-APP）_n/SFCM复合材料阻燃性能明显提高,组装10层的（CH-APP）₁₀/SFCM复合材料甚至可以达到离火自熄的程度。