核壳型纳米粒子填充PP-EVA及阻燃材料的动态燃烧行为

利用锥形量热仪(CONE)和热重分析(TGA),并结合极限氧指数(LOI)和UL-94垂直燃烧测试方法对核(PSt/OMMT)-壳(PBA)结构纳米复合粒子(CSN)填充聚丙烯(PP)-乙烯-醋酸乙烯酯共聚物(EVA)复合材料及加入无卤复配阻燃剂制备的PP-EVA/CSN/聚磷酸铵(APP)/层状氢氧化镁铝(LDH)复合阻燃材料的阻燃性能及热降解行为进行了研究。结果表明,添加10%(wt)CSN可以提高PP-EVA复合材料的阻燃性能,且PP-EVA复合体系燃烧时的热释放速率、有效燃烧热减少,热稳定性增强。CSN与APP/LDH产生阻燃协同作用,使复合阻燃材料的阻燃性能、热稳定性能进一步提高。     

碱式硫酸镁晶须阻燃乙烯-醋酸乙烯酯共聚物的研究

利用极限氧指数、UL-94垂直燃烧试验、锥形量热器、拉伸测试等手段研究了碱式硫酸镁晶须(MOS)填充阻燃乙烯-醋酸乙烯酯共聚物(EVA)的燃烧性能和力学性能,并与氢氧化镁(MH)填充阻燃EVA进行了比较。实验结果表明：MOS是一种性能优良的无卤阻燃剂。当填充量相等时,与EVA／MH相比,EVA／MOS具有更高的极限氧指数和UL-94垂直燃烧级别,更低的热释放速率、有效燃烧热和质量损失速率,以及更高的力学强度。     

有机蒙脱土/天然橡胶纳米复合材料的阻燃性能研究

采用机械混炼插层法制备有机蒙脱土/天然橡胶(TMT/NR)纳米复合材料.使用X-射线衍射(XRD)和红外表征了有机蒙脱土的结构特性,并用锥形量热仪测试了纳米复合材料的燃烧性能.结果表明,有机蒙脱土/NR纳米复合材料的热释放速率(HRR)、生烟速率(SPR)等较纯天然橡胶、未改性蒙脱土/NR复合材料均所有降低,表现出较好的阻燃性能.通过对纳米复合材料的燃烧性能和燃烧残余物分析,探讨了该体系的阻燃机理.     

高抗冲聚苯乙烯/蒙脱土复合材料的阻燃性研究

用经十六烷基三甲基溴化铵有机化改性的蒙脱土 (OMMT)与高抗冲聚苯乙烯 (HIPS)通过熔融插层法制备了HIPS OMMT复合材料 ,用X ray衍射技术对材料结构进行了表征 ,发现钠基蒙脱土 (Na+ MMT)和有机蒙脱土的层间距分别为 1 5 1nm和 2 18nm ,HIPS OMMT(5phr)复合材料中蒙脱土的层间距因聚合物大分子的插入扩大为 3 4 4nm ;而HIPS与Na+ MMT形成的复合材料的层间距与Na+ MMT的层间距相比却没有变化 ,表明未有机化处理土没有形成插层结构 .锥形量热仪的研究结果表明HIPS OMMT复合材料的热释放速率、质量损失速率以及生烟速率等燃烧特性参数均显著降低 ,具有较明显的阻燃性和抑烟性 ,而HIPS Na+ MMT非插层型复合材料只有在Na+ MMT很高填充量下 (>2 0phr)才有一定阻燃效果 .比较了铵盐对HIPS阻燃性的影响 ,结果表明铵盐自身的阻燃作用很小 ,主要是插层复合结构起阻燃作用 .     

三聚氰胺聚磷酸盐/季戊四醇配比、协效剂组及表面改性对聚丙烯基木塑复合材料的膨胀阻燃影响

通过极限氧指数(LOI)、线性燃烧速率(LBR)、热重分析和锥形量热分析等技术手段研究膨胀型阻燃剂(IFRs)中三聚氰胺聚磷酸盐(MPP)和季戊四醇(PER)的质量比、组成为m(MgO):m(可膨胀石墨,EG):m(SiO₂)=1:5:5的协效剂组(MgO/EG/SiO₂)和硅烷偶联剂(KH550)对聚丙烯基木塑复合材料(WPC)阻燃性能的影响。 结果表明,当IFRs中m(MPP):m(PER)=23:2(IFRs-M1)、质量分数为25%时的阻燃性能最佳,膨胀阻燃复合材料WPC/IFRs-M1的LOI和LBR分别为27.1%和3.89 mm/min,较未添加的WPC分别提高48.1%和下降89.79%,燃烧时的热释放速率、总热释放量、总烟释放量和CO₂释放量分别降低了76.2%、50.1%、6.9%和65.4%,600 ℃时的残炭率提高了498.3%。 协效剂组和KH550表面处理均可进一步改善WPC/IFRs-M1的阻燃性能,均对IFRs-M1具有良好的阻燃增效作用。 相比于WPC/IFRs-M1,同时用这两种阻燃增效手段的WPC/IFRs-M1/MgO/EG/SiO₂/KH550,其LOI提高了3.7%,LBR降低了20.3%;材料的热稳定性明显提高,热失重降低;燃烧时的热释放速率、总热释放量、总烟释放量和CO₂释放量分别降低了36.5%、37.6%、57.5%和33.33%,600 ℃时的残炭率提高了84.02%,显示出二者更好的协同效应。     

本质阻燃聚苯乙烯/蒙脱土纳米复合物的制备及性能

通过原位聚合法制备了本质阻燃聚苯乙烯[P(St-co-AEPPA)]/有机改性蒙脱土(OMMT)纳米复合物[P(St-co-AEPPA)/OMMT], 并用普通聚苯乙烯/有机改性蒙脱土(PS/OMMT)复合物作为对比实验, 研究了含磷、氮单体丙烯酸羟乙基-苯氧基-二乙基磷酰胺(AEPPA)和OMMT等添加物对本质阻燃聚苯乙烯性能的影响.用X射线衍射仪(XRD)和透射电子显微镜(TEM)分析了复合材料的结构与形貌, 并对OMMT在基体中的分散机理进行了讨论.用差示扫描量热仪(DSC)、热重分析(TGA)和微型量热仪(MCC)研究了材料的热性能和燃烧性能.结果表明, AEPPA和OMMT能够显著提高基体的热稳定性和阻燃性.     

协效阻燃聚丙烯的阻燃性能

本文研究了以聚磷酸铵(APP)为主阻燃剂,次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MCA)为辅阻燃剂的协效阻燃体系对聚丙烯(PP)阻燃性能的影响。 采用垂直燃烧测试、极限氧指数(LOI)测试、热重分析、锥形量热仪测试、扫描电子显微镜分析等技术手段对所制备的阻燃样品进行了阻燃性能分析。 结果表明:单独添加任一质量分数30%阻燃剂,均不能使PP获得良好的阻燃性能;当阻燃剂总质量分数保持在30%,m(APP)：m(AHP)：m(MCA)=4：1：1时获得理想阻燃效果,此时阻燃PP的LOI为33%,垂直燃烧测试达到V-0级,热释放速率峰值(PHRR)从765.7 kW/m²降为122.7 kW/m²。     

纳米阻燃高分子材料:现状、问题及展望

纳米阻燃体系是一种新型的聚合物阻燃体系,被誉为阻燃技术的革命.极少量(≤5wt%)纳米阻燃剂的加入即能显著降低高分子材料燃烧时的热释放速率(HRR)和烟密度(SEA),延缓其燃烧过程,还能不同程度地提高材料的力学性能.本文总结了近年来国内外纳米阻燃领域的进展,介绍了本课题组在纳米阻燃方面所做的工作,探讨了纳米阻燃研究中存在的问题,并对其未来的发展进行了展望.     

膨胀型阻燃UPR复合材料的阻燃及抑烟性能

将叶蜡石(PYR)与膨胀型阻燃剂[IFR,聚磷酸铵(APP)/季戊四醇(PER)/三聚氰胺(Mel))复配],应用于不饱和聚酯树脂(UPR),得到膨胀型阻燃UPR复合材料。通过氧指数(LOI)、垂直燃烧(UL94)、烟密度等级(SDR)、热分析(DSC-TG)对阻燃复合材料的阻燃、抑烟及热稳定性能进行了研究。结果表明:在该膨胀型复配阻燃体系中,叶蜡石与IFR存在明显的协效作用,在mPYR∶mAPP∶mPER∶mMel=4∶2∶1∶1,复合阻燃剂的含量为40%的情况下,LOI高达36.4,阻燃级别为UL94 V-0级,SDR为62.95,满足国家对B1级电器类热固性塑料的使用要求。     

用锥形量热仪研究聚乙烯膨胀阻燃体系的燃烧性

利用锥形量热仪在50kW·m^-2热辐照条件下,研究了含淀粉膨胀阻燃线性低密度聚乙烯(LLDPE)体系的燃烧性,获得了最大热释放速率、总热释放、有效燃烧热、最大烟产生速率、总烟释放量及质量损失速度等参数.实验结果表明:含淀粉膨胀阻燃剂能明显降低LLDPE的热释放速率、总热释放和有效燃烧热,淀粉作为膨胀型阻燃剂中的成炭剂,可以部分代替季戊四醇,而对热释放速率影响不大,达到了阻燃和降低成本的目的.该膨胀体系使烟释放变得缓慢,但总烟释放量明显增大.在燃烧时使LLDPE更早地发生热降解,但热降解速度变得缓慢.     

An assessment of the role of morphology in thermal/thermo-oxidative degradation mechanism of PP/EVA/clay nanocomposites

In this study, morphological properties of polypropylene (PP)/ethylene vinyl acetate copolymer (EVA) (75/25 wt/wt) blend-based nanocomposites containing various amounts of organically modified montmorillonite (OMMT) were primarily investigated. The incorporation of compatibilizer into nanocomposites decreased EVA droplet size in PP matrix while increasing compatibilizer/OMMT ratio showed a dual behavior with respect to the variations of OMMT interlayer spacing. By a rough estimation it was found that at EVA droplet size of D_n = 0.43 μm, the highest OMMT interlayer spacing would be acheived. Increasing D_n had a negative effect on the OMMT interlayer spacing. Activation energy of thermal/thermo-oxidative degradation based on Flynn model was obtained. Isothermal degradation test was also performed and desired temperature range for predicting degradation behavior was obtained by means of a free prediction model. An attempt was made to establish a correlation between morphological and thermal/thermo-oxidative parameters and also charred residue morphology. A mechanism for degradation process was proposed according to the changes of chemical bonds during the degradation process probed by FTIR analysis.     

Nonisothermal crystallization kinetics and determination of surface‐folding free energy of PP/EVA/OMMT nanocomposites

Crystalline structures, nonisothermal crystallization behavior and surface folding free energy of polypropylene (PP)/poly(ethylene‐co‐vinyl acetate) (EVA) blend‐based organically modified montmorillonite (OMMT) nanocomposites were investigated by use of wide angle X‐ray scattering (WAXS) and differential scanning calorimetry (DSC) techniques. Nonisothermal crystallization kinetic analysis was performed using Avrami equation modified by Jeziorny as well as combined Avrami‐Ozawa method. Surface folding free energy and activation energy for PP and nanocomposite samples were also determined employing Hoffman‐Lauritzen's and Vyazovkins's approaches, respectively. The results obtained from transmission electron microscopy (TEM) showed that presence of EVA, which attracts most of the layered silicates, reduces number density of heterogeneous nuclei in the matrix and as a consequence, decreases the nucleation rate. Incorporation of EVA, PP‐g‐MA and OMMT results in a decrease of the chain surface folding free energy level. It was shown that although, OMMT acts as a barrier against the PP macromolecular motion but interestingly, it increases the overall crystallization rate. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 674–684, 2009     

熔融法制备EVA/OMMT纳米复合材料及其热性能和动态力学性能

熔融法制备EVA/OMMT纳米复合材料及其热性能和动态力学性能;乙烯-醋酸乙烯酯共聚物;蒙脱土;动态储能模量     

STRUCTURAL EVOLUTION AND COMPOSITION CHANGE IN THE SURFACE REGION OF POLYPROPYLENE/CLAY NANOCOMPOSITES ANNEALED AT HIGH TEMPERATURES

A model experiment was done to clear the formation mechanism of protective layers during combustion of polypropylene(PP)/organically modified montmorillonite(OMMT) nanocomposites.The investigation was focused on the effects of annealing temperature on the structural changes and protective layer formation.The decomposition of OMMT and degradation of PP/OMMT nanocomposites were characterized by means of thermogravimetric analysis(TGA).The structural evolution and composition change in the surface region of...     

Flammability, structure and mechanical properties of PP/OMMT nanocomposites

Polypropylene/organoclay (PP/OMMT) nanocomposites were prepared in a twin-screw corotating extruder using two methods. The first method was the dilution of commercial (PP/50% Nanofil SE3000) masterbatch in PP (or PP with commercial flame retardant). The second method consists of two stages was the extrusion of maleic anhydride grafted polypropylene (PP-g-MAH) with commercially available organobentonite masterbatch in first stage and dilution of the masterbatch in PP (or PP with commercial flame retardant) in second stage. XRD results showed no intercalation in composites obtained from commercial masterbatch without compatibilizer and semi - delamination for compatibilized systems. Tensile tests revealed that nanocomposites with 5% of organoclay have a slightly higher tensile modulus and tensile strength than pristine PP, however addition of the commercial flame retardant (FR) reduces mechanical parameters to roughly the level of those for neat PP. PP/OMMT composites have approx. 25% higher oxygen index than pristine PP, and this changes slightly after the addition of FR. The cone calorimeter tests showed a decrease of a heat release rate (HRR) and a mass loss rate (MLR) after the addition of FR.     

Preparation of urea formaldehyde microsphere and its effect on flame retardant ethylene vinyl acetate composites

Urea formaldehyde microsphere (UFM) was prepared and used with organic montmorillonite (OMMT) to modify the flame retardant efficiency of ethylene vinyl acetate copolymer (EVA)/intumescent flame retardant (IFR) composites. The results show that single IFR may modify the flame retardancy of EVA, but its efficiency is not good enough. The EVA composite containing 21 wt% IFR is just classified the UL_94 V2 and has a limiting oxygen index (LOI) 24.7 vol%. Combining UFM with IFR does not improve the flame retardancy of EVA/IFR composites, and blending OMMT with IFR only improves its LOI. Adding 2 wt% UFM, 2 wt% OMMT, and 17 wt% IFR into EVA, it obtains the UL_94 V0 without melt dripping and a LOI 29.0 vol%. Also, the peak heat release rate and total heat release decrease a lot. Good synergistic effects among IFR, UFM, and OMMT improve the char residues and modify the char micromorphology of EVA composites, which provide better protect for the underlying resin.     

Effect of Different Organic Modifiers on the Tensile Properties of PVC／EVA／Montmorillonite Composites

Poly (vinyl chloride)/ethylene-vinyl acetate/montmorillonite (PVC/EVA/OMMT) composites were prepared by melt blending method. Two kinds of montmorillonites were organically modified by trimethyloctadecyl ammonium and dimethyl bis (hydrogenated tallow) ammonium, respectively. The morphology and tensile properties of the resultant composites were discussed in terms of the modifier type and OMMT content. The PVC/EVA/OMMT composites have intercalated structure, which is independent of the polarity of the modifiers, while the tensile properties show strong dependence on the modifier type. The OMMT modified by polar modifier gives higher tensile ductile and strength of PVC/EVA/OMMT composites.     

Thermal stability and flammability properties of heterophasic PP-EP/EVA/organoclay nanocomposites

A study on the thermal behavior and flammability properties of the heterophasic polypropylene-(ethylene-propylene) copolymer (PP-EP)/poly(ethylene vinyl acetate) (EVA)/montmorillonite nanocomposite is presented. Nanoclay nanocomposites were prepared using a twin screw extruder. Both the fluidity of the EVA phase and compatibility conditions between PP-EP and EVA were used in order to obtain the required nanocomposites. Therefore, no additional compatibilizer was required to achieve the clay dispersion. Products exhibited the partially exfoliated/intercalated nanoclay dispersion. Thermogravimetric analyses indicated that nanoclays retard thermal degradation depending on nanoclay concentration. The retarding process was assigned to the exfoliation and dispersion of the silicate layers which impeded heat diffusion to the macromolecules. Thermal studies, under non-isothermal crystallization, indicated the lack of influence of nanoclay on the thermal behavior. Flammability characteristics were however affected by the nanoclay layers which overall generated flame retardation both in the EVA host and in the complex nanocomposites.     

Glycerol: a promising agent for nanodispersion and compatibility of EVA/organomodified montmorillonite nanocomposites

Ethylene‐vinyl acetate (EVA) nanocomposites were extruded with two types of organomodified montmorillonite (OMMT) and 1 wt% glycerol. The characterization of the nanocomposites was performed by transmission electron microscopy, X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical analysis. The experimental results revealed that glycerol improved the Cloisite 30B clay exfoliation and promoted a rise in aspect ratio of the Cloisite 20A clay. In the rubbery region, the EVA/G showed a higher storage modulus than the EVA, as a result of the network of hydrogen bonds. The entanglements of long chains were more effective in the restrictions of large‐scale movements than the chemical interactions. The addition of glycerol promoted greater reinforcement and an increase in the tenacity of the nanocomposites in the glassy region. The use of glycerol for the production of EVA/OMMT nanocomposites was found to be promising. Copyright © 2015 John Wiley & Sons, Ltd.