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Synergistic effects of metal hydroxides and fumed nanosilica as fire retardants for polyethylene 金属氢氧化物和气相纳米二氧化硅作为聚乙烯阻燃剂的协同效应
Pub Date : 2019-01-01 DOI: 10.1515/flret-2019-0004
G. Fredi, A. Dorigato, L. Fambri, J. Lopez‐Cuesta, A. Pegoretti
Abstract This work aims to study the synergistic effect of aluminum/magnesium hydroxide microfillers and organomodified fumed silica nanoparticles as flame retardants (FRs) for linear low-density polyethylene (LLDPE), and to select the best composition to produce a fire-resistant polyethylene-based single-polymer composite. The fillers were added to LLDPE at different concentrations, and the prepared composites were characterized to investigate the individual and combined effects of the fillers on the thermo-oxidation resistance and the fire performance, as well as the microstructural, physical, thermal and mechanical properties. Both filler types were homogeneously distributed in the matrix, with the formation of a network of silica nanoparticles at elevated loadings. Melt flow index (MFI) tests revealed that the fluidity of the material was not considerably impaired upon metal hydroxide introduction, while a heavy reduction of the MFI was detected for silica contents higher than 5 wt%. FRs introduction promoted a noticeable enhancement of the thermo-oxidative stability of the materials, as shown by thermogravimetric analysis (TGA) and onset oxidation temperature (OOT) tests, and superior thermal properties were measured on the samples combining micro- and nanofillers, thus evidencing synergistic effects. Tensile tests showed that the stiffening effect due to a high content of metal hydroxide microparticles was accompanied by a decrease in the strain at break, but nanosilica at low concentration contributed to preserve the ultimate mechanical properties of the neat polymer. The fire performance of the samples with optimized compositions, evaluated through limiting oxygen index (LOI) and cone calorimetry tests, was strongly enhanced with respect to that of the neat LLDPE, and also these tests highlighted the synergistic effect between micro- and nanofillers, as well as an interesting correlation between fire parameters and viscosity.
摘要本工作旨在研究氢氧化铝/镁微填料和有机改性气相二氧化硅纳米颗粒作为线性低密度聚乙烯(LLDPE)阻燃剂的协同作用,并选择最佳组合制备阻燃聚乙烯基单聚合物复合材料。在LLDPE中添加不同浓度的填料,对所制备的复合材料进行表征,考察填料对LLDPE的抗热氧化性能、防火性能、显微组织、物理、热、力学性能的单独和联合影响。两种类型的填料均匀分布在基质中,在高负荷下形成二氧化硅纳米颗粒网络。熔体流动指数(MFI)测试显示,在引入金属氢氧化物后,材料的流动性没有受到很大影响,而二氧化硅含量高于5 wt%时,MFI会大幅降低。热重分析(TGA)和起氧化温度(OOT)测试结果表明,FRs的加入显著提高了材料的热氧化稳定性,微填充剂和纳米填充剂混合后的样品具有优异的热性能,从而证明了协同效应。拉伸试验结果表明,高含量的氢氧化金属微粒对聚合物的强化作用伴随着断裂应变的降低,而低浓度的纳米二氧化硅则有助于保持聚合物的最终力学性能。通过极限氧指数(LOI)和锥量热测试评估,优化后的样品的防火性能明显高于纯LLDPE,这些测试也突出了微填充剂和纳米填充剂之间的协同效应,以及防火参数与粘度之间的有趣相关性。
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引用次数: 8
Synergistic flame-retardant effect between lignin and magnesium hydroxide in poly(ethylene-co-vinyl acetate) 木质素与氢氧化镁在聚乙烯-醋酸乙烯酯中的协同阻燃作用
Pub Date : 2019-01-01 DOI: 10.1515/flret-2019-0002
F. Laoutid, V. Duriez, Loic Brison, S. Aouadi, H. Vahabi, P. Dubois
Abstract In this study, we evaluated the interest of combining magnesium hydroxide (MDH) and lignin for developing complementary flame retardant actions in poly(ethylene-co-vinyl acetate) (EVA). Lignin was selected owing to its char forming ability thatwas supposed to reinforce the endothermic effect provided by MDH. The effect of lignin chemical modification by ammonium phosphate functions also evaluated as a way for enhancing its charring effect. Fire properties and thermal behavior of EVA composites were characterized using cone calorimeter, Pyrolysis Combustion Flow Calorimeter (PCFC) and thermogravimetric analysis (TGA). The effect of the incorporation of lignin alone on EVAcomposite thermal and fire behavior first evaluated. Results evidenced that the incorporation of lignin, whatever its nature, induced important reduction of composite thermal stability during TGA analysis as well as significant reduction of the time to ignition (TTI) in cone calorimeter test. However, a significant reduction of peak of heat release rate (pHRR), higher than that obtained with MDH was observed. The combination of lignin and MDH was led to further reduction of pHRR. Furthermore, it was concluded that the chemical modification of lignin is not required prior obtaining improved flame-retardant properties.
摘要在本研究中,我们评估了氢氧化镁(MDH)和木质素在聚乙烯-醋酸乙烯酯(EVA)中形成互补阻燃作用的兴趣。选择木质素是因为木质素的成焦能力可以增强MDH的吸热效应。评价了磷酸铵对木质素进行化学改性以提高木质素的炭化效果。采用锥形量热仪、热解燃烧流量热仪(PCFC)和热重分析(TGA)对EVA复合材料的燃烧性能和热行为进行了表征。首先评价了木质素单独掺入对复合材料热性能和燃烧性能的影响。结果表明,木质素的掺入,无论其性质如何,在TGA分析中引起复合材料热稳定性的显著降低,在锥形量热计测试中引起点火时间(TTI)的显著降低。然而,观察到热释放率峰值(pHRR)显著降低,高于MDH。木质素与MDH的结合使pHRR进一步降低。此外,还得出结论,在获得更好的阻燃性能之前,不需要对木质素进行化学改性。
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引用次数: 11
Rubber toughened flame retardant (FR) polyamide 11 nanocomposites Part 2: synergy between multi-walled carbon nanotube (MWNT) and MMT nanoclay 橡胶增韧阻燃(FR)聚酰胺11纳米复合材料。第2部分:多壁碳纳米管(MWNT)和MMT纳米粘土的协同作用
Pub Date : 2019-01-01 DOI: 10.1515/flret-2019-0003
Hao Wu, R. Ortiz, J. Koo
Abstract In the previous study, flame retardant (FR) polyamide 11 (PA11) nanocomposites formulations designed for selective laser sintering (SLS)were prepared and characterized. The SEBS-g-MA elastomer successfully improved the material’s ductility. Although the nonhalogenated FR additives and montmorillonite (MMT) nanoclay successfully decreased the heat release capacity (HRC) and peak heat release rate (pHRR) as characterized by microscale combustion calorimeter (MCC). None of the rubber toughened formulations achieved UL 94 V0 rating, which is a bench mark for many FR polymer applications. As part two of this study, we explored the synergism between two nanoparticles, nanoclay and multi-walled carbon nanotubes (MWNTs), to see whether better FR properties can be achieved. TEM micrographs indicate that both nanoclay and MWNTs achieved high level of dispersion. Flammability results showed that all formulations achieved UL 94 V0 rating, which is a significant improvement from the previous formulations without MWNTs. Char morphology characterization indicated that a solid carbonaceous char layer was reinforced by nanoclay and MWNTs.
在前人的研究中,制备了用于选择性激光烧结(SLS)的阻燃聚酰胺11 (PA11)纳米复合材料配方,并对其进行了表征。SEBS-g-MA弹性体成功地提高了材料的延展性。通过微尺度燃烧量热仪(MCC)表征,非卤化FR添加剂和蒙脱土(MMT)纳米粘土成功地降低了FR的放热能力(HRC)和峰值放热率(pHRR)。没有一种橡胶增韧配方达到UL 94 V0等级,这是许多FR聚合物应用的基准。作为本研究的第二部分,我们探索了纳米粘土和多壁碳纳米管(MWNTs)两种纳米颗粒之间的协同作用,以了解是否可以实现更好的FR性能。TEM显微图显示纳米粘土和纳米碳纳米管都达到了高水平的分散。可燃性结果表明,所有配方都达到了UL 94 V0等级,与之前不含mwnt的配方相比有了显著改善。炭的形态表征表明,纳米粘土和纳米碳管增强了固体碳质炭层。
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引用次数: 1
Design and characterization of flame resistant blended nondrip PA6/Lenzing FR®/PBI fiber nonwoven fabrics 阻燃不滴PA6/Lenzing FR®/PBI纤维混纺无纺布的设计与性能
Pub Date : 2019-01-01 DOI: 10.1515/flret-2019-0005
Lan Yao, Lantao Wu, Hao Wu, J. Koo, M. Krifa
Abstract In current thermal protective clothing systems, maximizing the personal protection performance against fire and heat is in great demand. Additionally, minimizing the manufacturing cost by using low-cost materials is also a critical factor. In previous studies [1–3], a new type of low-cost inherently flame resistant (FR) non-drip Polyamide 6 (PA6) nanocomposite fiber was developed. In this paper, this FR non-drip PA6 fiber was tested in blends with two commercially available inherently FR fibers to form FR nonwoven fabrics. Different formulations of varying blending ratios were processed into nonwoven fabrics. The fiber morphology was observed by Scanning Electron Microscopy (SEM). The fabric flammability and combustion properties were characterized using a Microscale Combustion Calorimeter (MCC), and a vertical flame tester, as well as Thermogravimetric Analysis (TGA). Tensile tests were conducted to characterize mechanical properties of these FR nonwoven fabrics. The water vapor permeability test was also performed to measure the wearability of the fabric. Results of several nonwoven blends were compared to find the one with optimum blend ratio which has the potential to be used as low-cost thermal protective fabric.
摘要在目前的热防护服系统中,最大限度地提高个人对火灾和热的防护性能是一个很大的需求。此外,通过使用低成本材料来降低制造成本也是一个关键因素。在以往的研究中[1-3],开发了一种新型的低成本固有阻燃(FR)不滴漏聚酰胺6 (PA6)纳米复合纤维。在本文中,这种FR不滴PA6纤维与两种市售的固有FR纤维共混,形成FR无纺布。将不同配比的配方加工成非织造布。用扫描电镜(SEM)观察纤维形态。采用微尺度燃烧量热仪(MCC)、垂直火焰测试仪和热重分析(TGA)对织物的可燃性和燃烧性能进行了表征。通过拉伸试验对这些FR非织造布的力学性能进行了表征。同时进行了透气性测试,测试了织物的耐磨性。对几种非织造织物的混纺结果进行了比较,找出了一种具有最佳混纺比的低成本热防护织物。
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引用次数: 4
Flame retardant PP/PA6 blends: A recipe for recycled wastes 阻燃PP/PA6共混物:回收废物的配方
Pub Date : 2019-01-01 DOI: 10.1515/flret-2019-0001
H. Vahabi, L. Dumazert, R. Khalili, M. Saeb, J. L. Cuesta
Abstract Disposal of plastics in the form of discarded scrap or waste is an environmental nightmare to the developed and under-developing countries. In this sense, modern technologies are every day growing; meanwhile recycling wastes are taking credit for higher performance to pave the way towards a cleaner planet. Recycling of polymer blends is associated with serious complexities in finding appropriate additives acting in each phase or at the interface of non-miscible polymers to attain materials with higher properties. A flame retardant system was designed and intended to play the role of typical recycled flame retardant polypropylene/polyamide (PP/PA6) blends by incorporation of two kinds of talc, sepiolite, and a phosphorus-based flame retardant. First, two types of talcs having different physical properties were added to PA6 in combination with melamine cyanurate (MC) or melamine pyrophosphate (MPP) to find the one acting as a barrier during combustion. Then, high-aspect-ratio talc that appeared more effective in the first-stage survey was then used in combination with MC, MPP and ammonium polyphosphate (APP) together with a compatibilizer for PP/PA6 blend. Then, thermogravimetric analysis (TGA), microcalorimeter of combustion (PCFC) and cone calorimeter measurements were performed to study thermal degradation and flammability behavior. The results are indicative of successful formulation of flame retardant system containing the aforementioned precursors to be intended to the recycled PP/PA6 blends.
以废弃废料或废物的形式处理塑料是发达国家和欠发达国家的环境噩梦。从这个意义上说,现代技术每天都在发展;与此同时,回收废物也因其更高的性能而受到赞誉,为更清洁的地球铺平了道路。聚合物共混物的回收与寻找在每一相或在非混溶聚合物界面处起作用的适当添加剂以获得具有更高性能的材料的复杂性有关。通过掺入两种滑石、海泡石和磷系阻燃剂,设计了一种阻燃体系,旨在发挥典型的再生阻燃聚丙烯/聚酰胺(PP/PA6)共混物的作用。首先,将两种具有不同物理性质的滑石粉与三聚氰胺氰尿酸盐(MC)或三聚氰胺焦磷酸(MPP)混合加入PA6中,寻找在燃烧过程中起屏障作用的滑石粉。然后,高纵横比滑石粉在第一阶段的调查中表现得更有效,然后与MC、MPP和聚磷酸铵(APP)以及PP/PA6共混物的增容剂一起使用。然后,通过热重分析(TGA)、燃烧微热量计(PCFC)和锥形量热计测量来研究其热降解和可燃性行为。结果表明,含有上述前驱体的阻燃体系的成功配方将用于再生PP/PA6共混物。
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引用次数: 4
Lignin fractionation as an efficient route for enhancing Polylactide thermal stability and flame retardancy 木质素分馏是提高聚乳酸热稳定性和阻燃性的有效途径
Pub Date : 2018-07-25 DOI: 10.1515/flret-2018-0002
L. Costes, M. Aguedo, Loic Brison, S. Brohez, A. Richel, F. Laoutid
Abstract Due to its variable botanical origin, functionality, reactivity, and heterogeneity, using lignin in industrial application is not an easy task. In the present study, we investigate the effect of lignin fractionation as a simple way for reducing the variability in its properties. Kraft lignin was separated by ultrafiltration membranes in two fractions with a specific molecular weight and the properties of each fraction were characterized through FTIR, XPS, TGA and cone calorimeter test. Lignin fractions display different thermal and combustion behaviors. Thus, the two fractions have been evaluated as flame retardant additives for polylactide (PLA). PLA composites, containing well dispersed lignin (20 wt%), were produced by melt blending in an internal mixer. The thermo-degradant effect of each fraction on PLA during melt processing was investigated by rheological analysis and size exclusion chromatography while the composites thermal stability and fire properties were evaluated using TGA and cone calorimeter test. Results showed that using appropriate lignin fraction enables for obtaining PLA composites presenting enhanced properties
由于其多变的植物来源、功能、反应性和异质性,在工业应用中使用木质素并不是一件容易的事。在本研究中,我们研究了木质素分馏作为一种降低其性质变异性的简单方法的影响。采用超滤膜将硫酸盐木质素分离成具有一定比分子量的两组分,并通过红外光谱(FTIR)、XPS、热重分析(TGA)和锥形量热仪对各组分的性质进行了表征。木质素组分表现出不同的热和燃烧行为。因此,这两个馏分被评价为聚乳酸(PLA)的阻燃添加剂。采用内混炼法制备了分散良好的木质素(20% wt%)的聚乳酸复合材料。采用流变学分析和粒径排除色谱法考察了各组分在熔融加工过程中对PLA的热降解作用,采用热重分析和锥形量热计测试了复合材料的热稳定性和防火性能。结果表明,使用合适的木质素组分可以得到性能增强的聚乳酸复合材料
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引用次数: 7
Rubber toughened flame retardant (FR) polyamide 11 nanocomposites Part 1: the effect of SEBS-g-MA elastomer and nanoclay 橡胶增韧阻燃(FR)聚酰胺11纳米复合材料第1部分:SEBS-g-MA弹性体和纳米粘土的作用
Pub Date : 2018-07-25 DOI: 10.1515/flret-2018-0003
Hao Wu, R. Ortiz, J. Koo
Abstract The objective of this research is to develop a multifunctional polyamide 11 (PA11) with balanced thermal, mechanical, and flammability properties for SLS. In this study, two sets of formulations were prepared by twin-screw extrusion: the first set examined the effect of maleic anhydride modified elastomers on flammability and the mechanical properties, whereas the second set added various amount of nanoclay and discussed thermal stability, flammability and mechanical properties. The addition of 20 wt.% elastomer brought the elongation at break up to 40%. Reduction in heat release capacity as high as 49% was achieved, all nanocomposite samples passed UL 94 V-1 rating. The addition of nanoclay improved the tensile modulus by up to 78%, the elongation at break for all the formulations were negatively affected by the addition of flame retardant and nanoclay.
摘要:本研究的目的是开发一种具有平衡热、力学和可燃性的多功能聚酰胺11 (PA11)。本研究采用双螺杆挤出法制备了两组配方:第一组配方考察了马来酸酐改性弹性体对弹性体可燃性和力学性能的影响,第二组配方研究了添加不同量的纳米粘土对弹性体的热稳定性、可燃性和力学性能的影响。添加20 wt.%的弹性体可使断裂伸长率达到40%。热释放能力降低高达49%,所有纳米复合材料样品均通过UL 94 V-1等级。纳米粘土的加入使拉伸模量提高了78%,阻燃剂和纳米粘土的加入对所有配方的断裂伸长率都有负面影响。
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引用次数: 6
Self-Extinguishing and Non-Drip Flame Retardant Polyamide 6 Nanocomposite: Mechanical, Thermal, and Combustion Behavior 自熄和非滴漏阻燃聚酰胺6纳米复合材料:机械,热和燃烧行为
Pub Date : 2018-01-20 DOI: 10.1515/flret-2018-0001
Hao Wu, R. Ortiz, R. A. Correa, M. Krifa, J. Koo
Abstract Incorporation of flame-retardant (FR) additives and nanoclay fillers into thermoplastic polymers effectively suppresses materials flammability and melt dripping behavior. However, it largely affects other properties, such as toughness and ductility. In order to recover the lost toughness and ductility of flame retardant polyamide 6, various loadings of maleic anhydride modified SEBS elastomer were added and processed by twin screw extrusion. TEM images showed exfoliated nanoclay platelets and reveals that the clay platelets well dispersed in the polymer matrix. By balancing the ratio of flame retardants, nanoclay and elastomers, formulation with elongation at break as high as 76% was achieved. Combining conventional intumescent FR and nanoclay, UL-94 V-0 rating and the LOI value as high as 32.2 were achieved. In conclusion, effective self-extinguishing and non-drip polyamide 6 nanocomposite formulations with significant improvement in toughness and ductility were achieved.
在热塑性聚合物中掺入阻燃剂和纳米粘土填料可以有效地抑制材料的可燃性和熔体滴入行为。然而,它在很大程度上影响其他性能,如韧性和延展性。为了恢复阻燃聚酰胺6失去的韧性和延展性,加入不同载荷的马来酸酐改性SEBS弹性体,采用双螺杆挤出工艺对其进行加工。TEM图像显示脱落的纳米粘土薄片,显示粘土薄片在聚合物基质中分散良好。通过平衡阻燃剂、纳米粘土和弹性体的比例,获得了断裂伸长率高达76%的配方。将常规膨胀FR与纳米粘土相结合,获得了UL-94 V-0额定值和高达32.2的LOI值。综上所述,获得了有效的自熄和不滴漏的聚酰胺6纳米复合材料配方,并显著提高了韧性和延展性。
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引用次数: 11
期刊
Flame Retardancy and Thermal Stability of Materials
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