Effects of silicon additive as synergists of Mg(OH)2 on the flammability of ethylene vinyl acetate copolymer

The present work dealt with the effects of nine kinds of silicon additives on flame retardancy of ethylene‐vinyl acetate copolymer (EVA)/magnesium hydroxide [Mg(OH)₂] composites, as well as mechanical properties. The limiting oxygen index (LOI) test, horizontal fire test, vertical fire test, and cone calorimeter test were employed to evaluate flame retardancy of the composites. It was found that different silicon additives had different synergistic effects with Mg(OH)₂ on flame retardancy of the EVA matrix and exerted different influences on mechanical properties of the composites. The incorporation of organic montmorillonite (MMT) clay or silicone rubber not only made the composite reach FH‐1 rating in the horizontal fire test and FV‐1 rating in the vertical fire test, respectively, but also dramatically reduced the peak rate of heat release (Peak RHR) and increased the fire performance index (FPI) and ignition time (IT). The composites filled with precipitated SiO₂ exhibited the longest IT, the highest FPI, and FV‐1 rating. However, only the composites filled with silicone rubber could attain a balance between mechanical properties and flame retardancy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Effect of particle size on the flame retardancy of poly(butylene succinate)/Mg(OH)2 composites

Poly(butylene succinate)/magnesium hydroxide (PBS/Mg(OH)₂) composites were prepared by melt compounding to investigate the effect of particle size on the flame retardancy of PBS. Their flammability properties were investigated by limiting oxygen index, UL‐94, and cone calorimeter tests, which suggested that the medium‐sized Mg(OH)₂‐5 µm displayed the best flame retardancy. The residual char structure were analyzed and indicated that Mg(OH)₂‐5 µm could form a better protective layer than other sized particles, leading to the better flame retardancy to PBS. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.     

Al（OH）3和Mg（OH）2阻燃EVA性能的研究

选用形貌、粒径尺寸及分布相近的两种无机阻燃剂氢氧化铝（Al（OH）3）和氢氧化镁（Mg（OH）2），研究了二者用量对乙烯-醋酸乙烯酯共聚物（EVA）复合材料的力学性能和阻燃性能的影响，并比较了添加红磷的复合材料的力学性能和阻燃性能。研究表明：Al（OH）3和Mg（OH）2用量对复合材料性能影响比较相似，随着阻燃剂用量的增加，复合材料的阻燃性能提高，拉伸强度增加，但断裂伸长率下降；通过锥形量热仪数据看出：Al（OH），的点燃时间短，最大热释放速率和平均热释放速率低，火行为指数大，阻燃效果比Mg（OH）2好；红磷的加入对复合材料力学性能影响不大，而对阻燃性能影响较大。Mg（OH）2与红磷复配能提高复合材料的氧指数，但是，从水平和垂直燃烧角度考虑，Al（OH）3与红磷之间的阻燃协效效果更好。     

Effect of particle size on the properties of Mg(OH)2‐filled rubber composites

A novel nanomagnesium hydroxide powder and three kinds of micro‐Mg(OH)₂, with different particle sizes, were chosen as fillers and mixed with ethylene–propylene–diene monomer rubber (EPDM) to form a series of composites by a traditional rubber‐processing technique. The results showed that the mechanical properties of composites improved with decreasing particle size. The nanocomposites were far stronger than the microcomposites, which also supported the view that rubber reinforcement requires nanoreinforcement. The effect of particle size on the fire resistance of composites was investigated by cone calorimetry and limiting oxygen index analysis, which showed that the particle size of powder had an impact on the fire resistance of composites. For the composites filled with untreated powder, the peak value of heat release rate decreased and T_ign increased with decreasing particle size. In conclusion, the fire resistance of nanocomposites was better than that of microcomposites. Surface modification of particles sometimes substantially improved the mechanical properties of nanocomposites, but had no effect on either the mechanical properties of microcomposites or the fire resistance of nanocomposites and flame retardance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2341–2346, 2004     

Effects of shell thickness of polystyrene‐encapsulated Mg(OH)2 on flammability and rheological properties of high‐impact polystyrene composites

Polystyrene (PS)‐encapsulated magnesium hydroxide (Mg(OH)₂) particles with various shell thicknesses were successfully prepared using a method of in situ polymerization of styrene in a high‐speed mixer. High‐impact polystyrene (HIPS)/Mg(OH)₂ composites were prepared by melt blending. They were characterized using cone calorimetry, horizontal burning rate, rheology and scanning electron microscopy in order to investigate the effects of the shell thickness of the PS‐encapsulated Mg(OH)₂ on the flame retardancy and rheological properties of the resulting composites. Rheological tests showed that the composites containing encapsulated Mg(OH)₂ had a stronger solid‐like response at low frequency than that of the sample containing untreated Mg(OH)₂. However, with PS/Mg(OH)₂ ratio increasing up to 6.0 wt% and above, the dynamic viscosity, loss modulus and storage modulus of HIPS/Mg(OH)₂ composites decreased. The optimum PS/Mg(OH)₂ ratio, 4.5 wt%, was determined using a new ‘crossover point’ rheological method. The combustion tests showed that compared to the composites containing untreated Mg(OH)₂, the fire retardancy of the composites containing PS‐encapsulated Mg(OH)₂ was improved significantly. Also, there appeared to be a critical PS/Mg(OH)₂ ratio, namely 6.0 wt%, for optimum flame‐retarding properties. However with the continuous increase of PS/Mg(OH)₂ ratio, the fire resistance of the composites declined somewhat, which can be explained by acceleration of combustion of the composites due to the introduction of free PS chains of low molecular weight on the surface of Mg(OH)₂. Copyright © 2007 Society of Chemical Industry     

Effect of the particle size of expandable graphite on the thermal stability,flammability, and mechanical properties of high‐density polyethylene/ethylene vinyl‐acetate/expandable graphite composites

In this article, high‐density polyethylene/ethylene vinyl‐acetate copolymer (HDPE/EVA) composites filled with two different particle sizes (45 and 150 µm) of expandable graphite (EG) were prepared by using a twin‐screw extruder. The thermal stability, flammability, and mechanical properties of HDPE/EVA/EG composites were investigated by thermogravimetric analysis (TGA), cone calorimeter test (CCT), tensile test, and scanning electron microscopy (SEM). The results from TGA and CCT indicated that EG significantly enhanced the thermal stability and fire resistance of HDPE/EVA blend. The thermal stability and flame retardancy of HDPE/EVA/EG composites were improved with decreasing particle size of EG. Although the onset of weight loss of the flame‐retardant composites occurred at a lower temperature than that of HDPE/EVA blend, the flame‐retardant composites produced a large amount of char residue at a high temperature. The consolidated char layer formed a barrier, which could reduce heat, low‐molecular transfer, and air incursion, and thus enhanced the flame retardancy. The data from the tensile test showed that the addition of EG deteriorated the mechanical properties; however, the tensile stress and strain of HDPE/EVA/EG composites increased with decreasing the particle size of EG owing to the strong interface adhesion between polymer matrix and inorganic particles. POLYM. ENG. SCI., 54:1162–1169, 2014. © 2013 Society of Plastics Engineers     

Stearic acid surface modifying Mg(OH)2: Mechanism and its effect on properties of ethylene vinyl acetate/Mg(OH)2 composites

In this article, FTIR spectra and ESEM images were employed to evaluate the effect of stearic acid surface modification of Mg(OH)₂. As a result, the absorbing peak intensity of organic group on Mg(OH)₂ increased with the coating amount of stearic acid increasing and there was no so‐called surface saturation as expected. The results indicated stearic acid surface treatment of Mg(OH)₂ belonged to the acid–base reaction between stearic acid and Mg(OH)₂, and it would not stop until Mg(OH)₂ was reacted completely. In addition, stearic acid surface treatment of Mg(OH)₂ had remarkable influence on the properties of ethylene vinyl acetate/Mg(OH)₂ composites. With the increasing coating amount of stearic acid, the composites had decreased tensile strength, increased elongation at break, and deteriorated flame retardancy, compared with the composites filled with the uncoated Mg(OH)₂. However, stearic acid surface treatment of Mg(OH)₂ benefited processing ability of composites, and the composites had better processing ability as the coating amount of stearic acid increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A study of the flame‐retardant properties of polypropylene/Al(OH)3/Mg(OH)2 composites

Polymeric materials are used extensively, but their applications are limited because many of them are flammable. Therefore ways to make them flame retardant have received much attention. In this work, polypropylene (PP) was used as the matrix resin, aluminium hydroxide (Al(OH)₃) and magnesium hydroxide (Mg(OH)₂) as flame‐retardant additives and zinc borate (ZB) as a flame‐retardant synergist. PP/Al(OH)₃/Mg(OH)₂ and PP/Al(OH)₃/Mg(OH)₂/ZB flame‐retardant composites were prepared with a twin‐screw extruder. The flame‐retardant properties, i.e. oxygen index (OI), burning velocity and smoke density, of the composites were measured. The results showed that OI increased with an increase of the filler content and decreased with an increase of the filler particle diameter. The burning velocity decreased with an increase of the filler content, while it first increased and then decreased with an increase of the filler particle diameter. The smoke density decreased with an increase of the filler content and increased with an increase of the filler particle diameter. There was a flame‐retardant synergy between Al(OH)₃/Mg(OH)₂ and ZB in the composites, and the smoke suppression effect was marked when ZB was added. Copyright © 2009 Society of Chemical Industry     

EVA／Al（OH）3纳米复合材料性能的研究

采用熔融共混挤出法制备了EVA／Al(OH)3纳米复合材料。用TEM、SEM分析了Al(OH)3粉体改性前后在EVA树脂中的分散性与相容性。研究了表面处理对复合材料阻燃与力学性能的影响，并对Al(OH)3阻燃机理进行了探讨。结果表明：采用钛酸酯偶联剂对粉体进行表面改性可有效改善其在树脂中的分散与结合情况，复合材料阻燃级别提高到UL94 V-1级，拉伸性能得到改善。     

Mg(OH)2、红磷协同阻燃PIB/LDPE体系的研究

研究了3种粒径的Mg(OH)2阻燃剂对聚异丁烯/低密度聚乙烯(PIB/LDPE)体系性能的影响。发现随着Mg(OH)2用量的增加,体系的极限氧指数(LOI)增加,拉伸强度和断裂伸长率下降;Mg(OH)2的粒径对体系的LOI影响不明显,但对力学性能的影响较明显,阻燃剂粒径越大,材料的力学性能下降越多。将Mg(OH)2与红磷复配用于PIB/LDPE体系,发现具有明显的阻燃增效作用。探讨了红磷、Mg(OH)2在此类聚烯烃体系中的阻燃增效机理。     

Preparation of expandable graphite with silicate assistant intercalation and its effect on flame retardancy of ethylene vinyl acetate composite

A halogen‐free intumescent flame retardant expandable graphite composite (EG), with an initial expansion temperature of 202°C and expansion volume of 517 mL g⁻¹, was successfully prepared via a facile two‐step intercalation method, i.e. using KMnO₄ as oxidant and H₂SO₄, Na₂SiO₃·9H₂O as intercalators. The prepared EG flame retardant was characterized by field emission scanning electron microscope, X‐ray diffraction spectroscopy, energy dispersive spectroscopy and Fourier transform infrared spectroscopy. Furthermore, flame retardancy and thermal property of various ethylene vinyl acetate copolymer (EVA) composites, including EVA/EG and EVA/EG/APP (ammonium polyphosphate) specimens, were studied through limiting oxygen index instrument (LOI), vertical combustion UL‐94 rating, thermal gravimetric and differential thermal analysis. The results indicate that the EVA/EG and EVA/EG/APP composites exhibit a better flame retardancy. Addition of EG at a mass fraction of 30% leads LOI of 70EVA/30EG composite improved to 28.7%. Even more, the synergistic effect between EG and APP improves the LOI of 70EVA/10APP /20EG composite to 30.7%. This synergistic efficiency is attributed to the formation of compact and stable layer‐structure, and the prepared EG can make EVA composite reach the UL‐94 level of V‐0. POLYM. COMPOS., 36:1407–1416, 2015. © 2014 Society of Plastics Engineers     

Flame‐retardant and mechanical properties of rigid polyurethane foam/MRP/mg(OH)2/GF/HGB composites

Some rigid polyurethane foam (RPUF) composites modified with microencapsulated red phosphorus (MRP), magnesium hydrate (Mg(OH)₂), glass fiber (GF), and hollow glass bead (HGB) were prepared. The influence of the MRP, Mg(OH)₂, GF, and HGB on the flame‐retardant, combustion, and mechanical properties of the filled RPUF composites was investigated. The results showed that the flame‐retardant and the combustion properties of the composites were obviously improved, the limiting oxygen index, half burning time and the residual mass/original mass ratio increased with increasing MRP/Mg(OH)₂ weight fraction, especially in case of MRP/Mg(OH)₂ weight fraction of 8 wt %; the carbon monoxide (CO) concentration decreased with increasing MRP/Mg(OH)₂ weight fraction, When the composites were loaded appreciate content of the HGB and the GF, the maximum torque and compressive strength of the composites were improved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46551.     

Mg(OH)_2阻燃热塑性聚烯烃弹性体的研究

采用5种表面处理剂对氢氧化镁(Mg(OH)2)进行表面改性,并以热塑性聚烯烃弹性体(TPO)为基体树脂,制备了TPO/Mg(OH)2阻燃材料。通过氧指数(OI)、垂直燃烧和拉伸性能测试,研究了表面处理剂的种类、Mg(OH)2用量和粒径等对TPO/Mg(OH)2阻燃材料燃烧性能和力学性能的影响。OI测试结果表明,钛酸酯改性的粒径为2μm的Mg(OH)2使体系的OI达27.8%;改性Mg(OH)2用量为70份时成为难燃材料。垂直燃烧测试结果表明,100份改性Mg(OH)2使材料的燃烧等级达到FV-0级,无法引燃。力学性能测试结果表明,钛酸酯改性的粒径为2μm的Mg(OH)2使材料保持较高的应变;70份的Mg(OH)2使阻燃材料的拉伸屈服应力和拉伸断裂应力达到最大值。     

Effect of hydrated fillers and red phosphorus on the limiting oxygen index of poly(ethylene‐co‐vinyl actate)‐poly(vinyl butyral) and low density polyethylene‐poly(ethylene‐co‐vinyl alcohol) blends

The limiting oxygen index (LOI) values of EVA‐PVB and low density polyethylene (LDPE)‐poly(ethylene‐co‐vinyl alcohol) (EVOH) polymer blends containing hydrated filler‐type flame retardants and red phosphorus were measured. When used as the sole flame retardant, magnesium hydroxide [Mg(OH)₂] and alumina trihydrate (ATH) performed best in EVA and PVB, respectively. Magnesium hydroxide addition had a limited effect on the LOI of plasticized PVB, and addition of red phosphorus made little difference. This result is attributed to a mismatch between the decomposition temperature of Mg(OH)₂ and the temperature at which the PVB plasticizer vaporizes. Otherwise, low‐level addition of red phosphorus significantly improved LOI values. The presence of hydroxyl groups on the polymer backbone had a beneficial effect with respect to LOI values in ATH‐filled blends. An LOI value of 30 was achieved in EVOH with as little as 32% of ATH and 3% of red phosphorus. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers     

无机填料填充PE-LD/EVA合金的导热及阻燃性能

采用氧化铝（Al2O3）为导热填料、氢氧化镁［Mg(OH)2］为阻燃填料,以低密度聚乙烯（PE-LD）和乙烯醋酸乙烯共聚物（EVA）为基体树脂制备导热阻燃复合材料。通过导热性能测试、燃烧行为表征（极限氧指数和垂直燃烧测试）以及热重分析研究了PE LD/EVA/Al2O3/Mg(OH)2复合材料的导热性能、阻燃性能及热稳定性。结果表明,含有50份Al2O3及50份Mg(OH)2的复合材料,在PE-LD/EVA质量比为1/1时,热导率可达到1.21 W/m·K;材料的阻燃性能及热稳定性都随 EVA 含量的增加而增大,极限氧指数从27.0 % 提高到31.5 %,UL 94 垂直燃烧从无等级提高到V-0级,残炭率从46.5 %提高到57.7 %。     

Polyethylene compounds containing mineral fillers modified by acid coatings. 1: Characterization and processing

Research has been carried out to determine the effect of filler coatings on the processing properties of medium density polyethylene (MDPE) modified by an ultrafine grade of flame‐retardant magnesium hydroxide (Mg(OH)₂) filler. Selected filler coatings were acid‐group terminated and were of varying aliphatic chain length. The filler dry‐coating process has been optimized by characterizing the reaction between Mg(OH)₂ filler surface and the acid group, using spectroscopic techniques including Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS). Using immersion calorimetry, the interactions between the fillers and the polyolefin matrix were shown to decrease on the addition of a fatty‐acid coating. Compounding torque and specific energy data relate to filler dispersion; qualitative analysis has demonstrated how the coatings provide a reduction in both size and number of particle agglomerates. MDPE compound processability was assessed by capillary rheometry; wall slip was evident in compounds containing uncoated Mg(OH)₂ filler. Consequently, the development of molecular orientation of the polymer during injection mold filling, quantified by a reversion analysis, is modified by the effects of filler coating chain length and addition level, an effect that has important implications to link the mechanical properties of MDPE‐Mg(OH)₂ composites to processing history.     

Influence of the pentaerythritol phosphate melamine salt content on the combustion and thermal decomposition process of intumescent flame‐retardant ethylene–vinyl acetate copolymer composites

Pentaerythritol phosphate melamine salt (PPMS) as a single‐molecule intumescent fire retardant was synthesized and characterized. The influence of the PPMS content on the combustion and thermal decomposition processes of intumescent‐flame‐retardant (IFR) ethylene–vinyl acetate copolymer (EVA) composites was studied by limiting oxygen index (LOI) measurement, UL 94 rating testing, cone calorimetry, thermogravimetric analysis, and scanning electron microscopy. The LOI and UL 94 rating results illustrate that PPMS used in EVA improved the flame retardancy of the EVA composites. The cone calorimetry test results show that the addition of PPMS significantly decreased the heat‐release rate, total heat release, and smoke‐production rate and enhanced the residual char fire performance of the EVA composites. The IFR–EVA3 composite showed the lowest heat‐release and smoke‐production rates and the highest char residue; this means that the IFR–EVA3 composite had the best flame retardancy. The thermogravimetry results show that the IFR–EVA composites had more residual char than pure EVA; the char residue yield increased with increasing PPMS content. The analysis results for the char residue structures also illustrated that the addition of PPMS into the EVA resin helped to enhance the fire properties of the char layer and improve the flame retardancy of the EVA composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42148.     

Effects of High-Energy Electron Beam Irradiation on the Properties of Flame-Retardant HDPE/EVA/Mg(OH)2 Composites

The mechanical properties of flame-retardant high-density polyethylene/ethylene vinyl-acetate copolymer/magnesium hydroxide (HDPE/EVA/Mg(OH)₂) composites for cable materials are usually poor due to the high loading of the filler. In this study, high-energy electron beam irradiation was applied to HDPE/EVA/Mg(OH)₂ composites in the presence of triallylisocyanurate, an irradiation sensitizer. The effects of high-energy electron beam irradiation on the properties of irradiated HDPE/EVA/Mg(OH)₂ composites were investigated through the measurements of gel content, limiting oxygen index, tensile testing, thermogravimetric analysis, and scanning electron microscope. The results showed that the thermal, mechanical and flame-retardant properties of the HDPE/EVA/Mg(OH)₂ composites were improved by using high-energy electron beam irradiation.     

氢氧化镁阻燃剂的湿法改性研究

用湿法改性工艺对氢氧化镁阻燃剂进行了改性研究。在氢氧化镁乳液中加入改性剂和抗流失剂对氢氧化镁实施改性，测试了改性后的氢氧化镁性能。结果表明：抗流失剂的加入有效地防止了改性剂的流失，改性后的氢氧化镁表面亲油疏水，粒径和吸油值均减少。将改性后的氢氧化镁填充于EVA塑料体系中研究其材料的各项性能，发现经湿法改性的氢氧化镁可以显著提高EVA塑料的力学性能和阻燃性能。     

Mechanical properties,flame retardancy,hot‐air ageing,and hot‐oil ageing resistance of ethylene‐vinyl acetate rubber/hydrogenated nitrile‐butadiene rubber/magnesium hydroxide composites

The mechanical properties, flame retardancy, hot‐air ageing, and hot‐oil ageing resistance of ethylene‐vinyl acetate rubber (EVM)/hydrogenated nitrile‐butadiene rubber (HNBR)/magnesium hydroxide (MH) composites were studied. With increasing HNBR fraction, elongation at break and tear strength of the EVM/HNBR/MH composites increased, whereas the limited oxygen index and Shore A hardness decreased slightly. Hot‐air ageing resistance and hot‐oil ageing resistance of the composites became better with increasing HNBR fraction. Thermal gravimetric analysis results demonstrated that the presence of MH and low HNBR fraction could improve the thermal stability of the composites. Differential scanning calorimeter revealed that the glass transition temperature (T_g) of the composites shifted toward low temperatures with increasing HNBR fraction, which was also confirmed by dynamic mechanical thermal analysis. Atomic force microscope images showed MH has a small particle size and good dispersion in the composites with high HNBR fraction. The flame retardancy, extremely good hot‐oil ageing, and hot‐air ageing resistance combined with good mechanical properties performance in a wide temperature range (?30°C to 150°C) make the EVM/HNBR/MH composites ideal for cables application. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009