Carbon-family materials for flame retardant polymeric materials

As an abundant and attractive element, the emergence of new carbon-based materials brings revolutionary development in material science and technology. Carbon-based materials have spawned considerable interest for fabricating polymer composites/nanocomposites with greatly improved mechanical, thermal, gas barrier, conductivity, and flame retardant performance. In this review, the importance of carbon-based materials and the necessity of fire resistance for polymeric materials are initially introduced. Then, the fundamental flame retardant mechanisms and experimental analytical techniques are described to understand the relationship between structures and flame retardant properties. The main section is dedicated to the preparation and properties of multifunctional polymer composites/nanocomposites with carbon-based materials, with special emphasis on the flame retardant properties of these materials. A wide variety of carbon-based materials are discussed for use in flame retardant polymer nanocomposite, including graphite, graphene, carbon nanotubes, fullerenes as well as some new emerging carbon forms (carbon nitride, carbon aerogels, etc). Finally, a brief outlook at the developments in carbon-based materials for flame retardant polymeric composites is given by discussing the major progress, opportunities, and challenges.     

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.     

硼酸锌协效二乙基次膦酸铝阻燃PA6

采用硼酸锌(ZB)与二乙基次膦酸铝(ADP)协同阻燃聚酰胺6(PA6).对其阻燃性能和力学性能进行了探讨,并运用垂直燃烧、极限氧指数、锥形量热、热失重分析、扫描电子显微镜以及拉曼光谱对阻燃机理进行了探究.结果表明,ZB作为协效剂,与ADP的协同阻燃效果显著;当在PA6中添加1.5％(质量分数,下同)ZB和8.5％ADP...     

碱式碳酸镁基复合阻燃剂的制备及其阻燃性能研究

采用硅烷表面处理的碱式碳酸镁纳米片和氢氧化镁以及氢氧化铝为复合阻燃剂,通过密炼模压法制备了一系列复配阻燃剂协效阻燃EVA的复合材料。利用拉伸性能测试仪、熔融指数仪、垂直燃烧测试仪和锥形量热仪分别测试了复合材料的力学性能、加工流动性能和阻燃性能,利用热重分析仪测试了复配阻燃剂的热分解行为。结果表明,复配阻燃剂以适当比例协效阻燃EVA在更宽的燃烧温度范围内发生分解,能够起到更好的阻燃效果。并且复配阻燃剂/EVA复合材料的热释放速率和烟释放率大幅度降低,分别为181.06 kW/m²和0.032 m²/s。另外,复配阻燃剂/EVA复合材料的拉伸强度达到9.73 MPa,断裂伸长率为155.07%,每10 min熔融指数为1.00 g,符合电线电缆行业标准。     

Filler blend of carbon nanotubes and organoclays with improved char as a new flame retardant system for polymers and cable applications

Multi wall carbon nanotubes (MWCNTs) or single wall carbon nanotubes (SWCNTs) were used as fillers in polyethylene (PE). Only MWCNTs reduced the heat release rates caused by polymer degradation. MWCNTs can be more effective in heat release reduction than organoclays. The char generated by the filler blend ‘MWCNTs and organoclays’ as a synergistic flame retardant system in an ethylene vinylacetate (EVA) based polymer blend was improved compared with the char generated by the only organoclay based nanocomposite. Initial results indicated that there was a strengthening effect of the char by MWCNTs. The synergistic improvement for heat release reduction by a blend of the two fillers ‘MWCNTs and organoclays’ was used for the development of a flame retardant cable compound. 1.5 kg of MWCNTs was compounded on a Buss ko‐kneader to generate 60 kg of a nanocomposite based on the filler blend. The flame retardant properties of insulated wires made either by the filler blend or by ‘classical’ organoclays were measured. Copyright © 2004 John Wiley & Sons, Ltd.     

Reinforcing and Flame-Retardant Effects of Halloysite Nanotubes on LLDPE

Halloysite nanotubes (HNTs) were used to compound with linear low density polyethylene (LLDPE) to prepare composites with better mechanical properties and higher flame retardancy. The PE graft was used as interfacial modifier in the LLDPE/HNTs composites. HNTs were showed to be a promising reinforcing and flame retardant nano-filler for LLDPE. The mechanical properties and flame retardancy as well as thermal stability of the composites can be further enhanced by the addition of the graft copolymer. Morphological observation revealed that the graft copolymer could facilitate the dispersion of HNTs in LLDPE matrix and enhance the interfacial bonding.     

聚醚醚酮/多壁碳纳米管复合材料力学及阻燃性能研究

通过熔融共混法将聚醚醚酮（PEEK）与多壁碳纳米管(MWCNT)混合,利用模压法制备了MWCNT增强型PEEK复合材料,研究了MWCNT对PEEK性能的影响。结果表明,添加一定比例的MWCNT能够提高PEEK的力学和阻燃性能;当MWCNT含量为5%（质量分数,下同）时,PEEK的弯曲强度提高了53%;当MWCNT含量为1%时,锥形量热法测得的热释放速率峰值最低,燃烧性能指数值最大,热重分析显示初始分解温度较纯PEEK提高了13℃,表明MWCNT有效地提高了PEEK的阻燃和热稳定性能。     

基于磷杂菲衍生物多组分无卤阻燃天然橡胶的制备及性能

将磷杂菲/三嗪双基协同阻燃剂（TGD）、甲基膦酸二甲酯（DMMP）、可膨胀石墨（EG）及氢氧化铝（ATH）复配添加到天然橡胶（NR）中制备阻燃NR硫化胶,考察了TGD/DMMP/EG/ATH复配阻燃剂对NR硫化胶的阻燃性能、热稳定性及物理机械性能的影响。结果表明,TGD/DMMP/EG/ATH复配阻燃剂可有效提升NR硫化胶的阻燃性能和热稳定性,并降低燃烧过程中的热释放速率。当TGD/DMMP/EG/ATH复配阻燃剂的用量为60份（质量）时,NR硫化胶的极限氧指数可达28.4%,残炭质量分数可达25.61%,热释放速率可降低95%,总热释放量可降低21%。TGD/DMMP/EG/ATH复配阻燃剂对NR硫化胶的物理机械性能影响不大。     

Charing polymer wrapped carbon nanotubes for simultaneously improving the flame retardancy and mechanical properties of epoxy resin

Molybdenum-phenolic resin (Mo-PR) was grafted onto the surface of multi-walled carbon nanotubes (MWCNTs) to obtain modified MWCNTs (CNT-PR). Compared to epoxy resin, epoxy resin/CNT-PR nanocomposites showed the improvements in flame retardancy and mechanical properties. Structural characterization showed that the grafted Mo-PR improved the dispersion of MWCNTs in epoxy resin and enhanced the interfacial interaction between CNT-PR and epoxy resin. On the other hand, the grafted Mo-PR could show high char yield during the process of combustion. Thus the flame retardancy of nanocomposites was improved, especially for the heat release rate and total smoke production. Furthermore, the combination of CNT-PR with melamine dramatically promoted the LOI value and the level of UL-94 rating.     

A void surface flame retardant strategy for polymeric polyHIPEs

Effective flame retardant strategy for open-cell foam (e.g., polyHIPE) remains of a great challenge. Herein, a void surface flame retardant strategy for polyHIPE was presented. An open-cell polystyrene (PS) polyHIPE was fabricated through an emulsion-templating technique. Polyphosphazene (PSZ), a highly efficient flame retardant polymer, was then in situ fabricated and covalently attached to the void surface of the foam to be a uniform flame retardant protective layer, while the open-cell structure of the foam was perfectly preserved. Compared with the pristine PS polyHIPE, the PSZ modified one had significantly improved thermal stability (char residues yield at 800°C increased from 3.36 to 16.53 wt%) and mechanical properties (Young's modulus increased by 2.6 times); the values of average heat release rate and total heat release of combustion were reduced by 62.36% and 41.57%, respectively. While, the value of limiting oxygen index was increased from 17.39% to 19.75%, owing to the combined action of condensed phase flame retardant and gas phase flame retardant. These results indicate that the in situ surface modification strategy is effective for improving the flame retardancy of highly interconnected polymer foams.     

Mechanical and flame resistant properties of polycarbonate‐carbon nanotubes‐ochre composites

Ochre (Oc), with its high absorption and viscous properties and presence of several inorganic components, was incorporated in a polycarbonate‐unmodified carbon nanotubes using processing methods such as electrospinning and compression molding, to produce strong and flame resistant composites with biaxially oriented nanomaterials. These composites were found to have good mechanical properties (ultimate tensile strength of ～95.3 MPa) and flame resistance (～464 J g^?1K^?1 heat release capacity) when ～1 wt% of single‐walled carbon nanotubes was used with 2.5 wt% Oc, which was used as a compatibilizer and flame retardant. POLYM. ENG. SCI., 54:1289–1299, 2014. © 2013 Society of Plastics Engineers     

聚苯乙烯/多壁碳纳米管复合材料的阻燃性能

综述了近年来聚苯乙烯/多壁碳纳米管复合材料的阻燃研究进展,详细介绍了其热解性能（包括热解温度和玻璃化转变温度）以及燃烧性能（包括热释放速率、质量损失速率和成炭性）,并对相关机理进行了深入的探讨,分析了多壁碳纳米管含量、长径比、杂质及表面改性处理对相应复合材料的热稳定性及阻燃性能的影响。     

Mechanical performance and flame retardancy of polypropylene composites containing zeolite and multiwalled carbon nanotubes

Intumescent‐flame‐retarded polypropylene (PP‐IFR) composites were prepared by the incorporation of methyl hydrogen siloxane treated ammonium polyphosphate and dipentaerythritol in a twin‐screw extruder. The effects of zeolite (Z), multiwalled carbon nanotubes (CNTs), and maleic anhydride grafted polypropylene on the flame retardancy, mechanical properties, and thermal stability of PP‐IFR were investigated. The addition of Z and CNT promoted the flame retardancy of PP‐IFR, and the highest limited oxygen index was 35.6%, obtained on PP‐M‐IFR‐2–Z, for which the heat‐release rate, total heat release, and smoke production rate based on cone calorimetry analyses decreased by 45.0, 51.0, and 66.3%, respectively, in comparison with those values of the PP‐IFR composites. Additionally, scanning electron microscopy analyses showed that there was a good interface interaction between the polypropylene matrix and additives. The flexural, tensile, and impact strengths of the PP‐IFR composites were improved significantly with the incorporation of CNT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42875.     

Influence of ammonium polyphosphate on the flame retardancy and mechanical properties of ramie fiber‐reinforced poly(lactic acid) biocomposites

Fully degradable natural fiber/degradable polymer composites have received much research attention and have various applications such as in automotive components. But flammability limits their application; it is important to improve the flame retardancy of fully degradable composites with environmentally friendly flame retardants. Flame‐retarded ramie fiber‐reinforced poly(lactic acid) (PLA) composites were prepared using three processes: (1) PLA was blended with ammonium polyphosphate (APP), and then the resulting flame‐retarded PLA was combined with ramie fibers; (2) ramie fibers underwent flame‐retardant treatment with APP, which were then compounded with PLA; and (3) PLA and ramie, both of which had been flame‐retarded using APP, were blended together. The APP in the composites is shown to be very effective in improving flame retardancy according UL94 test and limiting oxygen index measurements. Thermogravimetric analysis shows that the improved flame retardancy is due to increased char residue at high temperature. The loading of APP disturbs the compatibility between PLA and fibers, which can be directly observed using scanning electron microscopy. Furthermore it has an influence on the dynamic mechanical properties and mechanical properties according dynamic mechanical analysis and mechanical measurements. The results show that composites produced using the third process not only have the best flame retardancy but also comparatively better mechanical properties. Copyright © 2009 Society of Chemical Industry     

聚磷酸三聚氰胺/季戊四醇膨胀型阻燃剂在天然橡胶中的应用

研究了膨胀型阻燃剂聚磷酸三聚氰胺（MPP）/季戊四醇（PER）对天然橡胶（NR）硫化胶的阻燃性能、热稳定性能、残炭形貌及力学性能的影响。结果表明,MPP/PER对NR硫化胶具有很好的阻燃效果,能有效提高NR复合材料的极限氧指数和热稳定性能,降低NR硫化胶的热释放速率,使NR硫化胶的燃烧过程变得稳定;当MPP/PER燃烧时可在NR硫化胶表面形成连续、致密且可隔绝氧气和热量的膨胀炭层;增加MPP/PER的总加入量会对NR硫化胶的力学性能造成一定的负面影响。     

Bio-based rigid polyurethane foam composites reinforced with flame retardants: From synthesis to performance evaluation

The building and construction industry is under increasing pressure to make insulation materials greener, more sustainable, and less flammable. In this study, sugar beet pulp was liquified under the optimized liquefaction conditions and used as the source of bio-polyol (SBpol) in the production of bio-based rigid polyurethane foam (sPUF). In order to improve the flame retardancy, sPUF composites were prepared with the addition of flame retardants; expandable graphite (EG) and/or dimethyl methyl phosphonate (DMMP). The bio-polyol was used at a fixed ratio of 50 php in sPUF composites whereas the total ratio of flame retardants was fixed at 20 php. The effects of the ratio of EG and/or DMMP on the morphological, physicomechanical, thermal, and flame retardant properties of sPUF composites were evaluated. Although the thermal conductivity values of flame retardant added sPUF composites were increased in comparison to the petroleum-based foam, the compressive strength values were decreased as the amount of DMMP increased in the flame retardant formulation. Thermogravimetric analysis showed that the onset of decomposition of 20 php DMMP-containing sPUF composite decreased to 168.3°C. Although the limiting oxygen index (LOI) value of the petroleum-based PUF was as low as 19.7%, the LOI value of the sPUF/10E/10D foam increased to 24.9% (by about 26%). According to the cone calorimeter results, the peak heat release rate (pHRR) of sPUF was much higher than the petroleum-based foam. The incorporation of both DMMP and EG could further improve the flame retardant properties. The pHRR value of sPUF/10E/10D was 28.1% lower than that of sPUF. The results have shown that flame retardancy of sPUF composites could be improved by the addition of EG which acts in the condensed phase and DMMP, which acts mainly in the gas phase during burning. Flame retardant incorporated sPUF composites are considered as promising materials for use in insulation applications.     

海泡石对三元乙丙橡胶阻燃性能的影响

以三元乙丙橡胶(EPDM)为基体材料,考察了海泡石的用量对复合材料力学性能及阻燃性能的影响,并与填料白炭黑进行了对比.结果表明,随着海泡石用量的增加,EPDM复合材料的力学性能明显提高,但是不如白炭黑增强效果显著.随着海泡石用量的增加,EPDM复合材料的氧指数呈增加趋势,最大热释放速率及总热释放量都呈降低趋势.与白炭黑...     

Polydopamine modified ammonium polyphosphate modified shape memory water-borne epoxy composites with photo-responsive flame retardant property

Shape memory epoxy (SMEP) is a high performance shape memory polymer; however, is extremely flammable which severely restricts its applications. In this work, a novel polydopamine modified ammonium polyphosphate (PDA@APP) flame retardant was prepared to improve the flame retardant and enrich the response method of SMEP. Through flame retardancy test confirmed that the flame retarding properties of the PDA@APP/WEP composites significantly improved than the APP/WEP composites, the limiting oxygen index (LOI) values of the APP/SMEP and the PDA@APP/SMEP samples increased by 29.8% and 32.2%, respectively. Moreover, the PDA@APP/WEP composites had excellent light response shape-memory performance. Interestingly, the PDA@APP/WEP treated polyester fabric exhibited excellent light crease recovery performance and excellent flame retardant property. This work develops a new method for fabric crease recovery and will help broaden the application of WEP and its composites.     

Synergistic effects of hydroxy silicone oil on intumescent flame retardant polypropylene system

The effects of hydroxy silicone oil as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (IFR-PP) were studied, and the IFR system mainly consisted of the ammonium polyphosphate (APP), melamine (MEL) and pentaerythritol (PER). The UL 94 rating, thermogravimetric analysis (TGA), cone calorimeter (CONE) and digital photograph were used to evaluate the synergistic effects of hydroxy silicone oil (HSO). It has been found that the PP composite containing only APP, MEL and PER does not show good flame retardancy at 30% additive level. The cone calorimeter results show that the heat release rate, mass loss rate, mass, total heat release, carbon monoxide and carbon dioxide of PP/APP/MEL/PER/HSO composites decrease in comparison with the PP/APP/MEL/PER composite. The digital photographs demonstrated that HSO could promote to form the homogenous and compact intumescent char layer. Thus, a suitable amount of HSO plays a synergistic effect in the flame retardancy.     

Influence of aging conditions on the mechanical properties and flame retardancy of HIPS composites

In this study, we evaluate the changes in physical properties and flame retardancy of HIPS composites after natural aging tests in Turpan (high sunlight radiation dose and dry) and Qionghai (high temperature and rainy) in China for 21 months. The HIPS composite aged in Turpan revealed a higher chromatic aberration than that in Qionghai due to the higher sunlight radiation dose. After aging tests for 21 months, the mechanical properties and the peak heat release of the HIPS composite aged in Qionghai decreased by more than 50% and increased by 39.7%, respectively, results that were worse than for the HIPS composite in aged Turpan. This was related to the combined effects of light, temperature, rain, and moisture in Qionghai leading to more severe degradation of HIPS composites, which results in breaking of the polymer chains and migration and erosion of the flame retardant. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46339.