Kinetics of thermo-oxidative degradation of zinc borate/microcapsulated red phosphorus with magnesium hydroxide in flame retarded polypropylene composites

The flammability and the thermo-oxidative degradation kinetics of zinc borate (ZB) and microcapsulated red phosphorus (MRP) with magnesium hydroxide (MH) in flame-retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), TGA, and FTIR spectroscopy. The results show that ZB/MRP is a good synergist for improving the flame retardancy of the PP composites. The Kissinger and Flynn-Wall-Ozawa methods were used to determine the activation energy (E) for degradation of PP composites. The results from the TGA curves indicate that the thermal stability of PP/MH/ZB and PP/MH/ZB/MRP composites is better than that of PP/MH composites. The kinetic results show that the values of E for degradation of PP/MH/ZB/MRP composites is much higher than those of PP/MH and PP/MH/ZB composites. The FTIR spectra data show that the incorporation of MH improves the thermo-oxidative stability of PP, especially for PP/MH composites with suitable content of MRP at higher temperatures. These data indicate that the synergistic flame retardants used in this work have a great effect on the mechanisms of pyrolysis and combustion of PP/MH composites.     

Structure and properties of polypropylene composites filled with magnesium hydroxide

Silane and silicone oil modified superfine magnesium hydroxide (MH) was filled into polypropylene (PP) as a flame retardant. The PP and flame‐retarded PP composites were studied for their mechanical properties and rheological behaviors by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), limiting oxygen index (LOI), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The results showed that the addition of MH improved flame retardancy of PP/MH composites, but seriously deteriorated mechanical properties of the composites. Surface treatment of MH could significantly improve tensile and impact strength of PP/MH composite because of its enhanced interfacial adhesion between MH and PP matrix. DSC results showed that MH had heterogeneous nucleation effect on PP. Surface treatment of MH weakened its heterogeneous nucleation effect. POM results showed that the dispersion of MH particles played an important role in the crystalline morphology and spherulite size of PP crystals. TGA indicated that MH greatly enhanced the thermal stability of PP. The introduction of treatment agent further improved the thermal oxidative stability of the composite. According to LOI, silane‐treated MH greatly enhanced flame retardancy of PP/MH composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4943–4951, 2006     

表面改性对聚丙烯/微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）和原位聚合方法对聚丙烯/微米氢氧化镁（MH）复合材料的力学性能及流变性能的影响。采用DSC、SEM和毛细管流变仪对PP/MH（80/20）复合材料的性能进行了研究。结果表明：原位聚合改性后的微米MH与PP基体间的界面黏结力得到了加强,复合材料的冲击强度较填充未改性MH的复合材料提高了26.4 ％。在PP基体中添加聚合物包覆改性微米MH粒子的复合材料熔体流动速率较纯PP上升了64 ％。在相同剪切速率下,填充聚合物包覆改性MH的复合材料熔体表观黏度明显低于填充未改性微米MH的复合材料,表明聚合物包覆改性后的MH降低了其对PP熔体流动的阻碍作用,改善了PP/MH复合材料的流动性能。     

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.     

PP/纳米SiO2复合材料的研究

采用傅立叶红外光谱仪(FT-IR)表征了改性前后纳米SiO2粉体的性能特征;通过熔融共混法制备了PP/纳米SiO2复合材料。研究了纳米SiO2用量对PP基体性能的影响。通过力学性能测试、DSC热分析和SEM照片观测,对PP/纳米SiO2复合材料的结构和性能进行了系统的研究。结果表明:当纳米SiO2含量为2%时,PP/纳米SiO2复合材料的综合力学性能最好。DSC表明,纳米SiO2对PP基体有异相成核作用。SEM电镜分析得出,经表面改性的纳米SiO2均匀地分散于PP基体中,从而起到良好的改性作用。     

PP/纳米SiO2/PP-g-MAH复合材料的研究

通过熔融共混法制备了PP/纳米SiO2/PP-g-MAH复合材料。研究了纳米SiO2和PP-g-MAH用量对PP基体性能的影响。通过力学性能测试、DSC热分析和SEM照片观测对PP/纳米SiO2和PP/纳米SiO2/PP-g-MAH复合材料的结构和性能进行了系统的研究。结果表明:2%的纳米SiO2和10%PP-g-MAH有较好的协同效应。可以使复合材料的缺口冲击强度提高80%,拉伸强度提高12.5%。DSC表明,纳米SiO2对PP基体有异相成核作用。SEM电镜分析得出,经表面改性的纳米SiO2均匀地分散于PP基体中,从而起到良好的改性作用。     

PP/PA6复合材料结构与力学性能的研究

通过熔融共混法制备了聚丙烯/聚酰胺6(PP/PA6)复合材料。研究了PA6和不同增容剂(马来酸酐接枝PP和马来酸酐接枝聚烯烃弹性体)对PP性能的影响。通过力学性能测试、DSC和SEM对PP/PA6复合材料的结构和性能进行了系统研究。结果表明:加入8%PA6和5%增容剂时,复合材料的综合力学性能最佳;PA6对PP有异相成核作用;在增容剂的作用下,PA6均匀地分散于PP基体中,从而起到良好的改性作用。摘要:     

PP/无机纳米粒子/POE-g-MAH三元复合材料的研究

采用熔融共混法分别制备了PP/纳米SiO2/POE-g-MAH和PP/纳米TiO2/POE-g-MAH两种复合材料;通过力学性能测试和SEM照片研究了其力学性能及微观形态结构。结果表明:纳米SiO2和纳米TiO2对PP/POE-g-MAH复合材料具有增强增韧作用,在POE-g-MAH的用量为5%、纳米粒子的用量为2%时,PP/无机纳米粒子/POE-g-MAH复合材料的综合力学性能达到最佳;SEM分析表明,该复合材料在断裂过程中发生塑性变形,因而韧性较佳;由DSC分析可知,纳米SiO2、TiO2均对PP基体有异相成核作用,此作用随POE-g-MAH的加入得到进一步促进。     

Flammability,thermal stability,and mechanical properties of ethylene-propylene-diene monomer/polypropylene composites filled with intumescent flame retardant and inorganic synergists

Three kinds of inorganic particles, zinc borate (ZB), organic montmorillonite (OMMT), and expanded graphite (EG) as synergistic flame retardants, are incorporated into ethylene-propylene-diene monomer/polypropylene (EPDM/PP) composites filled with intumescent flame retardants (IFR). The effect of three synergistic flame retardants on the combustion, thermal stability, and mechanical properties of the EPDM/PP/IFR composites are investigated by limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy, mechanical property testing, and dynamic mechanical analysis (DMA). The results from LOI, UL-94, and CCT show that the synergistic effect of IFR with ZB and EG is better than IFR with OMMT in the flame retardant EPDM/PP/IFR composites. The TGA results indicate that the thermal stability and char residues of the composites is improved with the addition of inorganic particles, which is attributed to the formation of dense char layers to isolate heat flow. DMA results including storage modulus (G'), loss modulus (G"), and loss factor (tan δ) suggest that the composites with inorganic particles exhibit more rubber-filler interaction, which limits the movement of the rubber chains.     

MOS阻燃动态硫化PP/EPDM性能研究

结合碱式硫酸镁晶须（MOS）的补强和阻燃功能，以微胶囊红磷（MRP）为协效剂，制备了无卤阻燃型PP（聚丙烯）／EPDM（三元乙丙橡胶）／MOS／MRP共混物，并与PP／EPDM／Mg（OH）2／MRP共混物进行比较。氧指数（LOI）及垂直燃烧（UL-94）测试表明MOS的阻燃效果优于Mg（OH）2。力学性能测试表明，MOS对PP／EPDM热塑性雌性体具有一定的增强作用，PP／EPDM／MOS／MRP阻燃体系的力学性能明显优于PP／EPDM／／MRP阻燃体系。而PP／EPDM热塑性弹性体的动态硫化进一步提高了PP／EPDM／MOS／MRP阻燃体系的力学与阻燃性能。     

Effects of magnesium hydroxide and its surface modification on crystallization and rheological behaviors of polypropylene

In this article, polypropylene composites filled with magnesium hydroxide (PP filled with MH) were prepared in corotating twin-screw extruder. The effects of MH particles content and types of treatment agents on the crystallization and melting behaviors, crystal structure, and rheological properties of PP/MH composites were studied by differential scanning calorimetry (DSC), a wide-angle X-ray diffraction, and dynamic rheological measurements. The DSC results show that MH particles act as a good heterogeneous nucleation effect on PP. Surface treatment of MH weakens its heterogeneous nucleation effect. The nucleating efficiency of MH on PP is found to depend strongly on its content and type of treatment agents. The dynamic rheological behaviors of MH filled PP is found that the complex viscosity (η*) increases with increasing MH content, whereas with increasing filler concentration the network structure becomes the prevailing process, which raises the η* values, especially at the low frequency zone. The η* values of the composites, however, decrease with the addition of various treatment agents. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

聚丙烯接枝马来酸酐对聚丙烯/凹凸棒石复合体系力学性能的影响

使用聚丙烯接枝马来酸酐(PP-g-MAH)对聚丙烯(PP)/凹凸棒石(AT)复合体系进行了增容,研究了PP-g-MAH对PP/原矿AT和PP/钛酸酯偶联剂改性AT复合体系力学性能的影响,观察了AT在PP中的分散状态以及PP/AT复合体系的断面形貌.结果表明P-g-MAH对AT在PP中分散状态没有明显影响;但加入5%的PP-g-MAH能够改善PP与原矿AT的相容性,提高PP/原矿AT复合体系的力学性能;加入PP-g-MAH对PP/钛酸酯偶联剂改性AT复合体系力学性能的改善不明显.     

One-step synthesis of hydrophobic magnesium hydroxide nanoparticles and their application in flame-retardant polypropylene composites

Hydrophobic magnesium hydroxide (MH) nanoparticles were prepared by a one-step synthesis method in a high-gravity environment generated by a novel impinging stream-rotating packed bed (IS-RPB) reactor. The reactant solutions were simultaneously and continuously pumped into the IS-RPB reactor, and then Tween 80 was added as a surface modifier. The morphology, structure, and properties of blank and hydrophobic MH were characterized. The effects of MH nanoparticles on the flame retardancy, thermal stability, and mechanical properties of PP/MH composites were also studied. We found that the obtained MH nanoparticles exhibited hexagonal lamella with a mean size of 30 nm, excellent hydrophobic properties (e.g., high water contact angle of 112°), and improved thermal stability of MH. The limiting oxygen index (LOI) further showed that increased MH loading can significantly improve flame-retardant performance, which reached 29.3% for PP/MH composites with 30 wt% hydrophobic samples. The thermal stability and mechanical properties of the PP/MH composites with hydrophobic samples were also much higher than those of PP/MH composites with blank MH. Results showed that the one-step synthesis had high potential application in the large-scale production of hydrophobic MH nanoparticles.     

Synergistic effects of expandable graphite with magnesium hydroxide on the flame retardancy and thermal properties of polypropylene

In this study, the flammability characterization and synergistic effects of different particle size of expandable graphite (EG) with modified magnesium hydroxide (MH) in flame‐retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA), and fourier transform infrared (FTIR) spectroscopy. The results showed that the particle size of EG had a great effect on the flammability of the PP/MH/EG composites. The EG2 with smaller particle size could apparently increase the LOI value and improved the UL‐94 flammability properties rating of the PP composites. The data obtained from the TGA and FTIR curves indicated that the thermo‐oxidative stability of PP/MH/EG composites increased with decreasing particle size of EG. And the smaller the particle size of EG, the higher the residues of the composite. POLYM. ENG. SCI., 47:1756–1760, 2007. © 2007 Society of Plastics Engineers     

木粉/聚丙烯复合材料力学性能及结晶行为研究

研究了木粉/聚丙烯复合材料的力学性能,结晶行为和微观结构.在木粉含量很高的情况下材料保持很好的拉伸强度,而材料的韧性随着木粉含量的增加下降很大.增容剂MA-PP的加入对材料的拉伸强度很很大的提高,而对冲击强度的影响不大.木粉/PP复合材料的结晶温度随着木粉含量的增加而增大,表明木粉对PP有异相成核的作用.复合材料电镜照片显示木粉在树脂中即使在较高含量下也分散均匀,马来酸改性聚丙烯(MA-PP)的加入提高木粉与树脂基体的界面结合.     

聚丙烯/环氧树脂复合材料的制备及其性能研究

在聚丙烯(PP)基体中加入环氧树脂(EP)、固化剂、马来酸酐接枝聚丙烯(PP-g-MAH),通过动态固化制备了PP/EP复合材料,并对其相容性、力学性能、结晶性能等进行了研究。结果表明:PP/EP为不相容体系,PP-g-MAH作为反应性增容剂对体系的刚性和模量影响较大;通过EP和PP-g-MAH的接枝反应,增强了两相间的界面作用力,降低了EP分散相的尺寸,改善了PP/EP复合材料的力学性能。力学性能测试结果表明,EP与PP-g-MAH的最佳配比为1:1;等温结晶的偏光照片和DSC数据表明,EP阻碍了PP的结晶,使其球晶微细化、结晶度降低。     

原位共聚合改性HIPS/氢氧化镁复合材料的性能

采用乙烯基硅烷在氢氧化镁(MH)表面引入乙烯基后与苯乙烯原位聚合,制备苯乙烯原位共聚合改性MH。将改性前后的MH、微胶囊红磷(MRP)、高抗冲聚苯乙烯(HIPS)按不同配比熔融复合制备HIPS/MH和HIPS/MH/MRP复合材料。研究了复合材料的力学性能和阻燃性能。结果表明:改性后的MH能显著提高复合材料的冲击强度。改性前后的MH与MRP的协同阻燃效应使HIPS/MH复合材料极限氧指数提高到28.9%,UL 94垂直燃烧达到V-0级。MH与MRP的协同作用增加了HIPS/MH复合材料的点燃难度,有效抑制了HIPS的热释放速率和烟释放速率,对HIPS起到良好的阻燃作用。     

Influence of polyamide 6 as a charring agent on the flame retardancy,thermal, and mechanical properties of polypropylene composites

In this work, polyamide 6 (PA6) as a charring agent has been used in combination with thermoplastic polyurethane (TPU)‐microencapsulated ammonium polyphosphate (MTAPP) forming intumescent flame retardants (IFRs) which applies in polypropylene (PP). The effects of the IFRs on the flame retardancy, morphology of char layers, water resistance, thermal properties and mechanical properties of flame‐retardant PP composites are investigated by limiting oxygen index (LOI), UL‐94 test, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mechanical properties test. The results show that the PP/MTAPP/PA6 composites exhibit much better flame‐retardant performances than the PP/MTAPP composites. The higher LOI values and UL‐94 V‐2 of the PP/MTAPP composites with suitable amount of PA6 are obtained, which is attributed to the thick and compact char layer structure evidenced by SEM. The results from TGA and DSC demonstrate that the introduction of PA6 into PP/MTAPP composites has a great effect on the thermal stability and crystallization behaviors of the composites. Furthermore, the mechanical properties of PP/MTAPP/PA6 composites are also improved greatly due to the presence of PA6 as a charring agent. POLYM. ENG. SCI., 55:1355–1360, 2015. © 2015 Society of Plastics Engineers     

新型热塑性弹性体增韧聚丙烯的研究

以聚烯烃弹性体(POE,乙烯-辛烯共聚物)为PP的增韧性剂,利用转矩流变仪、差示量热扫描(DSC)及力学性能测试方法,比较研究了PP/POE及PP/EPDM共混物的加工性能、结晶性能及力学性能;结果表明,POE在加工性、改性效果等方面比EPDM更具优势。还探讨了POE用量对PP/CaCO     

Investigation of the influence of red phosphorus,expansible graphite and zinc borate on flame retardancy and wear performance of glass fiber reinforced PA6 composites

The flame retarded materials were prepared which used wear‐resistant PA6 composite (PA6/GF/PTFE/UHMWPE/CG, 85/15/5/5/5 by weight) as matrix, red phosphorus (RP), expansible graphite (EG), and zinc borate (ZB) as fire retardant. The flame retarded properties were characterized by LOI and UL‐94 testing. PA6 composite with 15 wt% RP reached V0 rating and had a high LOI value (27.3 vol%). When a combination of 7 wt% ZB and 8 wt% RP was added, increases in LOI (27.9 vol%) and UL‐94 rating(V0) were both observed. Thermogravimetric analysis (TGA) and char residue characterization showed that the combination of RP and ZB can promote the formation of char barrier, reduce the mass loss rate, and thus improve the flame retardancy of PA6 composites. The wear test showed that, the composite filled by 15 wt% RP or a combination of 7 wt% ZB and 8 wt% RP both possessed a low wear rate and a much stable friction coefficient. The presence of EG could also improve the flame retardance but was harmful to the mechanical property as well as wear performance. The results indicated that ZB and RP had synergy effect on improving both flame retardance and wear performance of PA6 composites. POLYM. COMPOS., 38:2090–2097, 2017. © 2015 Society of Plastics Engineers