Mechanical properties and flammability of sisal/PP composites: Effect of flame retardant type and content

In this research, magnesium hydroxide (Mg(OH)₂) and zinc borate, as flame retardants, were incorporated into sisal/PP composites. Maleic anhydride grafted polypropylene was also used as a compatibilizer. Adding flame retardants into sisal/PP composites reduced burning rate and increased thermal stability of the composites. No synergistic effect was observed when both magnesium hydroxide and zinc borate were incorporated in the sisal/PP composites. In addition, the sisal/PP composites exhibited insignificant difference of shear viscosity at high shear rate indicating that types of flame retardants used in this study had no impact on the processability of the composites. Good distribution of flame retardants and sisal fiber in PP matrix was also observed. All PP composites had lower impact strength than the neat PP. However, the sisal/PP composites with the addition of Mg(OH)₂ and zinc borate exhibited comparable tensile and flexural properties to the sisal/PP composites without adding those flame retardants. Therefore, the addition of Mg(OH)₂ and zinc borate enhanced flame retardancy of sisal/PP composites without sacrificing their mechanical properties.     

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.     

Effect of flame retardants on mechanical properties,flammability and foamability of PP/wood–fiber composites

The mechanical properties, flame retardancy, thermal degradation and foaming properties of wood–fiber/PP composites have been investigated. Ammonium polyphosphate (APP) and silica were used as flame retardants. The limiting oxygen index (LOI), thermal gravimetric analysis (TGA) and cone colorimeter (CONE) were employed for the study of fire retardance. At the same time, wood–fiber/PP composite foams were produced with the batch foaming technique using CO₂ as blowing agent. The effects of APP and silica content, pressure and temperature on the final cell structure were investigated. According to LOI, TGA and cone calorimeter results obtained from the experiments, APP and silica are effective flame retardants for wood–fiber/PP composites, and silica was shown to have a flame retardant synergistic effect with APP in wood–fiber/PP composite. The mechanical properties of the composites decreased with addition of flame retardants, except for the tensile strength of small amount of silica filled wood–fiber/PP composite. The results also revealed that the cellular morphologies of the foamed wood–fiber/PP composites are a strong function of the content of APP and silica as well as foaming conditions.     

Mechanical properties and flame-retardant of PP/MRP/Mg(OH)2/Al(OH)3 composites

The flame retardant and mechanical properties of polypropylene (PP) composites filled with microencapsulated red phosphorus (MRP) and magnesium hydrate (Mg(OH)₂)/aluminum hydrate (Al(OH)₃) were measured. It was found that the synergistic effects between the MRP and Mg(OH)₂/Al(OH)₃ on the flame retardant and tensile properties of the composites were significant. The limit oxygen index and smoke density rank of the composites increased nonlinearly while the horizontal combustibility rate decreased nonlinearly with increasing the MRP weight fraction. The Young modulus and the tensile elongation at break increased while the tensile yield strength and tensile fracture strength decreased slightly with increasing the MRP weight fraction. Both the V-notched Izod and Charpy impact strength increased with increasing the MRP weight fraction. Moreover, the tensile yield strength of the composites estimated using an equation published previously was roughly close to the measured data.     

New glass fiber/bismaleimide composites with significantly improved flame retardancy,higher mechanical strength and lower dielectric loss

Novel glass fiber (GF)/bismaleimide composites with significantly improved flame retardancy, higher mechanical strength and lower dielectric loss were developed, of which the resin matrix is a new flame retarding resin system (BDDP) based on 4,4′-bismaleimidodiphenyl methane (BDM), 2,2′-diallyl bisphenol A (DBA) and [(6-oxido-6H-dibenz [c,e] [1,2] oxaphosphorin-6-yl)-methyl]-butanedioic acid (DDP). The influence of the loading of DDP in the matrix on the integrated performances of composites was intensively studied. Results show that GF/BDDP composites not only have significantly improved mechanical and dielectric properties, but also possess excellent flame retardancy. The main flame retarding mechanism of GF/BDDP composites is the condensed phase mechanism. The introduction of DDP significantly strengthens the interfacial adhesion between GF and the resin matrix, this is responsible for the attractive performances of GF/BDDP composites.     

一种膨胀阻燃PP体系及其燃烧性能

制备了一种阻燃聚丙烯/膨胀阻燃剂(IFR)/蒙脱土(MMT)膨胀阻燃体系,研究了不同阻燃组分含量对体系阻燃性能的影响。结果表明,阻燃剂总添加量为30%,其中的成炭剂和聚磷酸铵(APP)的配比为1∶2时,体系的极限氧指数为29%,垂直燃烧试验(UL-94)达到V-2级;而在上述体系中添加0.5%的MMT时,体系的LOI提高到31%,垂直燃烧试验(UL-94)通过V-0级,表现出较好的协同阻燃效果。采用扫描电境(SEM)和红外光谱(FT-IR)对体系的固相残炭进行了观察和分析,探讨了可能的阻燃机理。     

苯甲酸功能化石墨烯-Al(OH)3协同阻燃聚丙烯

以氧化石墨（GO）为原料,制备了苯甲酸功能化石墨烯（BFG）,采用IR和XRD对BFG结构进行了表征。再将BFG作为阻燃协效剂添加到Al（OH）₃/聚丙烯（PP）中,研究不同质量比的BFG与Al（OH）₃对PP材料阻燃和力学性能的影响。通过对阻燃BFG-Al（OH）₃/PP复合材料进行极限氧指数（LOI）测试、热失重分析、锥形量热分析、拉伸测试及残炭SEM分析,考察BFG-Al（OH）₃/PP复合材料的阻燃性能和力学性能。研究结果表明,与其他阻燃PP相比,1.5wt% BFG-38.5wt% Al（OH）₃/PP的阻燃和力学性能最佳,LOI可达到24.6%,拉伸强度为20.64 MPa,且其热释放速率峰值和总热释放量比纯PP分别降低了51.5%和18.6%。     

聚甲醛阻燃的研究

选用氢氧化镁(Mg(OH)2)、聚磷酸铵(APP)作为聚甲醛(POM)的阻燃剂,研究了它们对POM阻燃效果及力学性能的影响。结果表明,加入Mg(OH)2阻燃剂后,POM的阻燃性能有较大的提高,当Mg(OH)2的加入量为60％时．极限氧指数由15提高到40．水平燃烧速度由0．33mm／s降至0．31mm／s。APP阻燃POM的效果优于Mg(OH)2,在APP加入量达到25％时即制得自熄的POM。两种阻燃剂的加入都使POM的力学性能下降。     

Electrical conductive and graphitizable polymer nanofibers grafted on graphene nanosheets: Improving electrical conductivity and flame retardancy of polypropylene

Polyaniline (PANI) nanofibers grafted reduced graphene oxide (PANI–RGO) is prepared using the “grafting-from” strategy and then is incorporated into polypropylene (PP) matrix by way of the master batch-based melt mixing method. Grafted PANI nanofibers can improve the dispersion and electrical conductivity of reduced graphene oxide (RGO). The electrical conductivity of the modified RGO and its composites is not impaired by the grafted polymer, due to the conductive characteristics of PANI. The barrier action of PANI–RGO can greatly inhibit the release of flammable pyrolysis products of PP. PANI–RGO exhibits a marked flame retardancy effect on PP. The smoke release of the composites is slightly retarded. Transmission electron microscopy image and Raman spectrum of the char residue for PANI–RGO based composite indicate the formation of carbon nanofibers during combustion. The in situ formed carbon nanofibers on graphene nanosheets can enhance barrier performance against heat and mass transfer, resulting in enhanced flame retardancy.     

The effect of graphene presence in flame retarded epoxy resin matrix on the mechanical and flammability properties of glass fiber-reinforced composites

The effect of adding graphene in epoxy containing either an additive (MP) or reactive-type (DOPO) flame retardant on the thermal, mechanical and flammability properties of glass fiber-reinforced epoxy composites was investigated using thermal analysis; flexural, impact, tensile tests; cone calorimetry and UL-94 techniques. The addition of MP or DOPO to epoxy had a thermal destabilization effect below 400 °C, but led to higher char yield at higher temperatures. The inclusion of 10 wt% flame retardants slightly decreased the mechanical behavior, which was attributed to the poor interfacial interactions in case of MP or the decreased cross-linking density in case of DOPO flame retarded resin. The additional graphene presence increased flexural and impact properties, but slightly decreased tensile performance. Adding graphene further decreased the PHRR, THR and burning rate due to its good barrier effect. The improved fire retardancy was mainly attributed to the reduced release of the combustible gas products.     

β-环糊精-聚磷酸铵对黄麻/聚丙烯复合材料阻燃性能的影响

将黄麻纤维和聚丙烯纤维（PP）通过梳理、铺网和针刺的方式形成黄麻/PP复合材料毡,采用表面撒粉工艺,将阻燃剂β-环糊精（β-CD）、β-CD与聚磷酸铵（APP）复配热压后在黄麻/PP复合材料表面形成阻燃层,采用FTIR、极限氧指数测试仪、水平燃烧测试仪、锥形量热测试仪、热重分析测试仪、SEM及万能试验机等检测黄麻/PP复合材料阻燃性能、力学性能、成炭性能及样品表面微观形貌。结果表明:β-CD与APP复配后在黄麻/PP复合材料表面热压成膜可以显著提高复合材料的阻燃性能和热稳定性。当β-CD-APP复配阻燃剂质量分数为20wt%、β-CD与APP的质量比为1∶2时,黄麻/PP复合材料水平燃烧58 s后自熄,极限氧指数（LOI）值达到26.6%,根据日本JISD 1201—77标准,属于第三难燃等级材料,此时热释放速率和有效燃烧热值最小,700℃时的残炭量增加了11.68%。力学性能测试表明,在黄麻/PP复合材料表面增加阻燃层后,弯曲强度增加而拉伸强度不受影响。      

聚磷酸铵/次磷酸铝协效阻燃聚丙烯/木粉复合材料

以聚磷酸铵(APP)和次磷酸铝(AHP)为阻燃剂,马来酸酐接枝聚丙烯(MA-g-PP)为界面相容剂,通过熔融共混制备了聚丙烯(PP)/木粉(WF)复合材料。采用UL-94垂直燃烧、氧指数(LOI)、热重分析(TGA)探究了阻燃PP/WF复合材料的阻燃性和热分解过程。实验表明,当APP与AHP质量比为9∶1时,LOI值为28.3%,垂直燃烧UL-94达到V-0级。TGA和DTG测试表明,APP与AHP复配能降低木纤维的分解温度,使复合材料提前成炭,达到阻燃作用;加入APP与AHP的PP/WF复合材料的成炭率提高了141%,其高温稳定性也得到提高。通过SEM观察到,当m(APP)∶m(AHP)=9∶1时,木塑复合材料可形成致密的炭层,具有更好的隔热、隔氧作用,从而提高了阻燃性。结果表明在聚磷酸铵中加入少量的协效剂次磷酸铝可明显提高PP/WF复合材料的阻燃性。     

原位一步合成CuAl-LDHs-聚磷酸铵及其在聚丙烯阻燃中的应用

采用原位一步法合成铜铝类水滑石（CuAl-LDHs）,通过控制铝酸钠/聚磷酸铵（NaAlO₂/APP）的质量比（0.82~3.28）合成CuAl-LDHs-APP。采用XRD、FTIR、SEM和TG对所制备的CuAl-LDHs及CuAl-LDHs-APP进行表征。采用极限氧指数（LOI）、垂直燃烧（UL-94）测试、弯曲及拉伸试验等考察了CuAl-LDHs/聚丙烯（PP）及CuAl-LDHs-APP/PP复合材料的阻燃性能及力学性能。SEM 观察表明:LDHs结构为片状,随着NaAlO₂与APP质量比的减小,CuAl-LDHs-APP颗粒粒径相应减小,当NaAlO₂与APP的质量比为0.82时,CuAl-LDHs-APP颗粒粒径达到20 nm左右,比表面积为183.5 m2/g。TG分析表明:CuAl-LDHs-APP在高温下有较好的热稳定性。当PP中加入质量分数为20%的CuAl-LDHs及CuAl-LDHs-APP时,LDHs/PP复合材料表面形成炭层;当NaAlO₂与APP质量比不大于1.64时,CuAl-LDHs-APP的添加可抑制PP燃烧时产生的熔滴现象;与CuAl-LDHs/PP复合材料相比,CuAl-LDHs-APP/PP复合材料具有更好的阻燃性能和力学性能;与PP材料相比,CuAl-LDHs-APP/PP复合材料的弯曲强度和拉伸强度等力学性能的下降也不明显。      

环氧树脂包覆聚磷酸铵微胶囊的制备及其对聚丙烯的阻燃效果

为了探究环氧树脂包覆聚磷酸(EP@APP)微胶囊对聚丙烯(PP)的阻燃效果,首先,采用原位聚合法以EP为外壳包覆APP,制备了EP@APP微胶囊,并将其与PP进行复合,制备了EP@APP/PP复合材料。然后,测试了EP@APP微胶囊的溶解性,探讨了工艺参数对溶解性的影响;考察了EP@APP微胶囊的耐水性,并借助红外光谱分析了EP@APP微胶囊的表面官能团。最后,测试了PP复合材料的极限氧指数、拉伸强度和热重曲线,并分析了PP复合材料的热分解动力学。结果表明:当EP的加入量为APP的10wt%、固化剂加入量为EP加入量的15wt%时,采用先于40℃下维持1h、再于70℃下维持1h的阶跃升温方法可制备包覆完全的EP@APP微胶囊;该种微胶囊在水中溶解度低,且具有良好的耐水性。在PP中添加EP@APP微胶囊后,PP复合材料的极限氧指数为35.5%,达到V-0燃烧等级,燃烧后的残炭量增多,成炭效果明显优于直接添加APP的PP复合材料。与APP相比,EP@APP微胶囊对PP拉伸强度的破坏程度明显降低。EP@APP微胶囊的加入使PP复合材料的表观活化能由100.8kJ/mol提高到127.5kJ/mol,改变了PP复合材料的热降解氧化过程,且生成的残炭形成了稳定的保护炭层。研究结果表明EP@APP微胶囊可有效提高PP复合材料的阻燃性能。     

三聚氰胺聚磷酸盐对竹纤维/聚丙烯复合材料力学及阻燃性能的影响

采用三聚氰胺聚磷酸盐（MPP）作为阻燃剂,加入到竹纤维/聚丙烯（BF/PP）复合毡中,制备MPP-BF/PP复合材料。采用力学测试和SEM研究MPP对MPP-BF/PP复合材料力学性能和微观形貌的影响;采用极限氧指数（LOI）、热失重（TG）和吸水率为指标研究MPP对MPP-BF/PP复合材料阻燃性、热稳定性和耐水性的影响。测试表明:MPP的质量分数小于30wt%时,MPP-BF/PP复合材料弯曲强度和冲击强度随MPP质量分数的增加先增大后减小,当MPP质量分数达到5wt%时,MPP-BF/PP复合材料呈现出最佳的弯曲强度和冲击强度;MPP在MPP-BF/PP复合材料内部均匀分布,而随着MPP质量分数的增加,MPP-BF/PP复合材料断裂面的粗糙度明显提高,即MPP与PP界面相容性变差,使其力学性能降低。LOI测试结果表明,MPP可以有效提高MPP-BF/PP复合材料的阻燃性能,当MPP质量分数为30wt%时,MPP-BF/PP复合材料LOI达到24.3%。热失重测试表明,MPP的加入可提高MPP-BF/PP复合材料的热分解温度,促进其残炭率明显增大,有利于提高MPP-BF/PP复合材料阻燃性能。耐水性能测试结果表明,MPP质量分数小于20wt%时,MPP对MPP-BF/PP复合材料的耐水性能没有明显影响。采用模糊综合评价法分析表明,MPP质量分数为10wt%时,MPP-BF/PP复合材料性能最优。      

Enhanced mechanical,thermal and flame retardant properties by combining graphene nanosheets and metal hydroxide nanorods for Acrylonitrile–Butadiene–Styrene copolymer composite

Three metal hydroxide nanorods (MHR) with uniform diameters were synthesized, and then combined with graphene nanosheets (GNS) to prepare acrylonitrile–butadiene–styrene (ABS) copolymer composites. An excellent dispersion of exfoliated two-dimensional (2-D) GNS and 1-D MHR in the ABS matrix was achieved. The effects of combined GNS and MHR on the mechanical, thermal and flame retardant properties of the ABS composites were investigated. With the addition of 2 wt% GNS and 4 wt% Co(OH)₂, the tensile strength, bending strength and storage modulus of the ABS composites were increased by 45.1%, 40.5% and 42.3% respectively. The ABS/GNS/Co(OH)₂ ternary composite shows the lowest maximum weight loss rate and highest residue yield. Noticeable reduction in the flammability was achieved with the addition of GNS and Co(OH)₂, due to the formation of more continuous and compact charred layers that retarded the mass and heat transfer between the flame and the polymer matrix.     

Facile synthesis of lanthanum hypophosphite and its application in glass-fiber reinforced polyamide 6 as a novel flame retardant

This work developed flame retarded glass fiber reinforced polyamide 6 (FR-GFPA) composites with excellent mechanical properties, thermal stability and flame retardancy using a novel flame retardant, lanthanum hypophosphite (LaHP). The flame-retarded properties of FR-GFPA composites were characterized by limiting oxygen index, Underwriters Laboratories 94 testing and cone calorimeter test. FR-GFPA composite with 20 wt% LaHP reached V-0 rating and a high LOI value (27.5 vol%). The mechanical performance analysis showed that both the storage modulus and tensile strength increased and then decreased with the increase of LaHP loading. For FR-GFPA composite with 15 wt% LaHP loading, the storage modulus was 164% higher than that of glass fiber reinforced polyamide 6 (GFPA). Thermogravimetric analysis (TGA) and char residue characterization showed that the addition of LaHP can promote the formation of compact physical char barrier, reduce the mass loss rate and thus improve the flame retardancy of FR-GFPA composites.     

表面改性对聚丙烯/纳米氢氧化镁复合材料性能的影响

研究了表面处理剂(钛酸酯和硅烷偶联剂)对聚丙烯/纳米氢氧化镁(MH)阻燃复合材料性能的影响。通过高压毛细管流变仪、LO I、力学测试、DSC和SEM对PP/纳米MH复合体系的结构与性能进行了研究。结果表明,所选偶联剂能有效地降低复合体系的表观黏度,改善体系的流动性。未改性的纳米MH对PP基体有异相成核作用;而表面改性剂能削弱填料对基体的异相成核作用。改性后的纳米MH粒子以独立形式均匀分散在基体中,PP与纳米MH界面的粘接力得到了加强,复合材料的拉伸性能和冲击强度有较大幅度的提高,阻燃性能也得到了改善。     

微胶囊化膨胀型阻燃剂与有机蒙脱土协效阻燃乙烯-醋酸乙烯共聚物性能

通过纳米复合的方式,将微胶囊化的膨胀型阻燃体系—聚磷酸铵(APP)-季戊四醇(PER)与有机改性的片层蒙脱土(OMMT)用于协效阻燃乙烯-醋酸乙烯共聚物(EVA)。采用XRD、TEM、TGA、极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热仪、烟密度和动态机械热分析对微胶囊化APP(MCAPP)-微胶囊化PER(MCPER)-OMMT/EVA复合材料的结构与性能进行研究。研究结果表明,OMMT被完全剥离开,并以层离或插层的状态分散在EVA中;MCAPP-MCPER与OMMT之间存在明显的协效阻燃作用,用3wt%OMMT代替MCAPP-MCPER后,MCAPP-MCPER-OMMT/EVA复合材料的LOI值从25.5vol%提高到29.5vol%,垂直燃烧结果由V-2上升到V-0级别,残炭量也由14.5wt%增大到15.9wt%,烟密度由154.7 g/s降低到97.5 g/s,材料的阻燃性能得到有效提高。此外,万能拉伸测试及动态机械热分析测试表明,通过纳米复合制备的阻燃MCAPP-MCPER-OMMT/EVA复合材料具有更好的力学和动态热机械性能。      

Ternary nano-CaCO3/poly(ethylene terephthalate) fiber/polypropylene composites: Increased impact strength and reinforcing mechanism

The binary nano-CaCO₃/polypropylene (PP), poly(ethylene terephthalate) (PET) fibers/PP and ternary nano-CaCO₃/PET fibers/polypropylene composites were prepared by melt blending method, and their structure and mechanical properties were investigated. The results show that the ternary nano-CaCO₃/PET fibers/PP composite displays significantly enhanced mechanical properties compared with the binary PET fibers/PP and nano-CaCO₃/PP composites, and neat PP. The X-ray diffraction, dynamic mechanical analysis, scanning electron microscopy and analysis of the non-isothermal crystallization kinetics were used to investigate the reinforcement mechanism of composites. The results indicate that the interfacial action and compatibility between PET fiber and PP are obviously enhanced by the addition of modified nano-CaCO₃ particles in the ternary composites and the mechanical property enhancement in the ternary system may be mainly originated from the formation of β-form crystallites of PP induced by the synergistic effect between PET fibers and nano-CaCO_3.