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     

Structural characterization of LDPE/EVA blends containing nanoclay‐flame retardant combinations

The combination of different types of organo‐modified montmorillonite (MMT) with aluminum hydroxide (aluminum trihydrate—ATH), as a flame retardant system for polyethylene‐ethylene vinyl acetate (LDPE/EVA), blends were studied. Five different types of organically modified montmorillonite clays, each with different modifier, were used. The structural characterization was carried out by X‐ray diffraction (XRD) and scanning electron microscopy in transmission mode (STEM). The mechanical and rheological properties were also evaluated. The XRD analysis showed a clear displacement of the d₀₀₁ signal, which indicates a good degree of intercalation, especially for the MMT‐I28 and MMT‐20, from Nanocor and Southern Clay Products, respectively. The presence of ATH and the compatibilizer did not have any effect on the exfoliation of the studied samples. The thermal stability and flame retardant properties were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI—ASTM D2863), and flammability tests (Underwriters Laboratory—UL‐94). The effect of different compatibilizers on the clay dispersion and exfoliation was studied. The results indicated that the addition of montmorillonite makes it possible to substitute part of the ATH filler content while maintaining the flame retardant requirements. The thermal stability of MMT/ATH‐filled LDPE/EVA blends presented a slight increase over the reference ATH‐filled LDPE/EVA blend. Compositions with higher clay content (10 wt %) showed better physicochemical properties. The increased stability of the higher clay content compositions results from the greater inorganic residual formation; this material has been reported to impart better performance in flammability tests. The mechanical properties and flame retardancy remained similar to those of the reference compound. The reduced ATH content resulted in lower viscosities and densities, facilitating the processing of the polymer/ATH/clay compounds. Extrusion of these compounds produced a lower pressure in the extrusion head and required reduced electrical power consumption. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

ZnO/MoO3/Al(OH)3阻燃聚丙烯材料的制备及性能

采用水热法制备了一维材料ZnO和MoO_3纳米线(nanowires,NWs),并通过SEM和XRD对纳米线的形貌和结构进行了表征。将一维纳米线和纳米氢氧化铝(ATH)与聚丙烯(PP)熔融共混制备了ZnO/MoO_3/Al(OH)_3/PP复合材料(NWs/ATH/PP)。利用TGA、极限氧指数(LOI)测定仪和锥形量热仪(CCT)表征了复合材料的热稳定性和燃烧性能,利用万能材料试验机测试了复合材料的力学性能。结果表明:当添加质量分数3.75%ZnO纳米线、质量分数3.25%MoO_3纳米线和质量分数21.00%纳米ATH时,NWs/ATH/PP复合材料的初始分解温度较纯PP增加了17.8℃,残重率为24.6%,峰值热释放速率(PHRR)和总热释放量(THR)分别下降了54.3%和25.7%,LOI提高7.1%。SEM结果显示:NWs/ATH/PP的残炭表面致密、连续且平整。     

Preparation and flame retardancy of a novel flame‐retardant poly(ethylene‐co‐vinyl acetate)/aluminum hydroxide composites containing phosphorus

A novel flame‐retardant (SPDH) containing phosphorus was synthesized through the reaction of 10‐(2,5‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and synthesized intermediate product 3,9‐dichloro‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5] undecane‐3,9‐dioxide, which was used for optimizing the flame retardancy of ethylene‐vinyl acetate copolymer (EVM) rubber/aluminum hydroxide (ATH) composites. The microstructure of SPDH was characterized and determined by Fourier transform infrared and nuclear magnetic resonance spectroscopy. Thermogravimetric analysis (TGA) showed that SPDH had good charring effect at high temperature (600°C). The flame retardancy of the optimized EVM/ATH composites by SPDH was investigated by limiting oxygen index (LOI), cone calorimeter, and UL‐94 vertical burning tests. A higher LOI value (29.8%) and better UL‐94 rating (V‐0) can be achieved for the optimized EVM/ATH composite (EVM‐7) than EVM/ATH composite without SPDH (EVM‐3) with the total loading of additives. The heat release rate decreased and residual mass increased gradually as the loading of SPDH increased for the optimized EVM/ATH composites. There existed distinct synergistic flame‐retardant effect between SPDH and ATH in EVM matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

阻燃剂对UP复合材料流变性及磨损性能的影响

制备了含有氢氧化铝(ATH)、三聚氰胺多聚磷酸盐(MPP)及十溴二苯醚(DBDE)等不同阻燃剂的干式不饱和聚酯/玻璃纤维(UP/GF)共混复合材料。研究了不同阻燃剂对UP/GF复合材料的阻燃性能、流动性和磨损性能的影响,并借助SEM观察了采用不同阻燃剂的UP/GF复合材料的磨损面微观形貌。结果表明,ATH的添加质量为30%时,其UP/GF复合材料的阻燃性与DBDE添加量为25%的体系相当,达到UL94 V-0级,OLI值为30.0且具有很好的抑烟和防滴落效果;同时ATH、MPP的加入可适当提高复合材料流动性能,ATH还可以改善复合材料的磨损性能,磨损体积为未添加阻燃剂体系的50%左右。     

Flame Retardant Synergism of Hydroxy Silicone Oil and Al(OH)3 in EVA Composites

A synergistic effect on flame retardancy was found when hydroxy silicone oil (HSO) was incorporated into ethylene vinyl acetate/aluminum hydroxide (EVA/ATH) composite. The fire performance of EVA and EVA composites was studied by using limiting oxygen index (LOI), UL 94, and cone calorimeter test (CCT). Compared with the EVA/ATH binary composite, the LOI values of the EVA/ATH/HSO ternary composites at the same additive loading are all decreased. The CCT data indicated that the addition of HSO in EVA/ATH system not only reduces the heat release rate, but also prolonged the ignition time of the composite. Thermogravimetric analysis revealed that ATH accelerated the loss of acetic acid, but hydroxy silicone oil assisted to reduce ATH's accelerating effect.     

Study on char reinforcing of different inorganic fillers for expandable fire resistance silicone rubber

Sodium silicate monohydrate (NSH), glass frits (GF) and aluminum hydroxide (ATH) were incorporated into room temperature vulcanized (RTV) silicone rubber (SR) as char reinforcing materials to improve the fire resistance of intumescent flame retardant silicone rubber. SR composites containing only intumescent flame retardant such as phosphorus nitrogen composite flame retardant (NH₂-C) and expandable graphite (EG) were used as comparison samples. Limiting oxygen index (LOI) test, vertical burning test (UL-94), flame resistance test, scanning electron microscopy (SEM) and X-ray diffraction spectroscopy tests, as well as volume variation and compression strength of char residues were used to discuss the effects of the above-mentioned fillers on the fire resistance, char residue strength and char integrity of SR composites. The results showed that SR composite filled with only intumescent flame retardants EG and NH₂-C had excellent flame retardancy. After adding ATH, the char residue was relatively dense and had good compressive strength, but its thermal insulation performance was reduced. GF or NSH reduced the flame retardancy of SR composites, but it obviously played a role in binding combustion residues, forming new crystals and improving the stability of char residues.     

Effects of platinum compounds/superfine aluminum hydroxide/ultrafine calcium carbonate on the flame retardation and smoke suppression of silicone foams

Environmentally friendly, flame-retardant, and relatively low-density (0.25–0.31 g cm⁻³) silicone foams (SiFs) were successfully obtained through dehydrogenation at room temperature (RT = 25.0 °C). Moreover, a flame-retardant system for SiFs was obtained through a synergistic combination of platinum (Pt) compounds, superfine aluminum hydroxide (ATH), and ultrafine calcium carbonate (CC). The smoke suppression, flame retardance, mechanical properties, and thermal stability of SiFs with Pt compounds, ATH, and CC were tested using the limited oxygen index (LOI), UL-94 test, smoke density test, cone calorimeter, and thermogravimetry–Fourier transform infrared spectroscopy. With only 0.6 wt % Pt compounds, the pure SiF achieved the UL-94-V1 rating (3 mm thick), had an LOI value of 29.6%, and the maximum smoke density (MSD) was 6.5%. After adding ATH and CC, SiF composites could achieve the UL-94-V0 rating (3 mm thick), the LOI increase to 35.2%, and MSD decrease by 45%. Furthermore, the SiF with 0.6 wt % Pt compounds, 15.0 wt % ATH, and 15.0 wt % CC exhibited the optimal comprehensive properties for smoke suppression, flame retardance, mechanical performance, and thermal stability. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47679.     

Synergistic effects of aluminum hydroxide,red phosphorus,and expandable graphite on the flame retardancy and thermal stability of polyethylene

The flame-retardant low-density polyethylene (LDPE) composites loading aluminum hydroxide (ATH), red phosphorus (RP), and expandable graphite (EG) were successfully prepared. The flame retardancy, the thermo-oxidative stability, and the mechanical property of the composites were investigated. The synergistic effect of ATH, RP, and EG on the flame-retardant property and thermal behavior of LDPE were observed. The limiting oxygen index value of LDPE significantly increased from 17.1% to 25.4% upon the incorporation of 15 wt.% of the mixture of three fillers with ATH:RP:EG mass ratio of 1:1:1; and this composite achieved the V-0 classification of the UL94 vertical burning test. The thermogravimetric analysis of this composite under air atmosphere revealed that its residue weight remained 27.89% at 900°C. Furthermore, the results of tension tests indicated that the surface modification of ATH by magnesium stearate and RP by poly(methylhydrosiloxane) noticeably improved the tensile strength and the elongation of the composite.     

Synergistic effects of exfoliated LDH with some halogen‐free flame retardants in LDPE/EVA/HFMH/LDH nanocomposites

The synergistic effects of exfoliated layered double hydroxides (LDH) with some halogen‐free flame retardant (HFFR) additives, such as hyperfine magnesium hydroxide (HFMH), microencapsulated red phosphorus (MRP), and expandable graphite (EG), in the low‐density polyethylene/ethylene vinyl acetate copolymer/LDH (LDPE/EVA/LDH) nanocomposites have been studied by X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermal analysis (TGA and DTG), mechanical properties, limiting oxygen index (LOI), and UL‐94 tests. The XRD results show that EVA as an excellent compatilizer can promote the exfoliation of LDH and homogeneous dispersion of HFMH in the LDPE/EVA/HFMH/LDH nanocomposites prepared by melt‐intercalation method. The TEM images demonstrate that the exfoliated LDH layers can act as synergistic compatilizer and dispersant to make the HFMH particles dispersed homogeneously in the LDPE matrix. The results from the mechanical, LOI, and UL‐94 tests show that the exfoliated LDH layers can also act as the nano‐enhanced and flame retardant synergistic agents and thus increase the tensile strength, LOI values, and UL‐94 rating of the nanocomposites. The morphological structures of charred residues observed by SEM give the positive evidence that the compact charred layers formed from the LDPE/EVA/HFMH/LDH nanocomposites with the exfoliated LDH layers play an important role in the enhancement of flame retardant and mechanical properties. The TGA and DTG data show that the exfoliated LDH layers as excellent flame retardant synergist of MRP or EG can apparently increase the thermal degradation temperature and the charred residues after burning. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of aluminum hydroxide/aluminum phosphinate flame‐retardant poly(vinyl alcohol) foam through thermal processing

A novel flame‐retardant poly (vinyl alcohol) (PVA) composite foam was prepared successfully through thermal processing, which was filled with high content of flame retardant, based on aluminum hydroxide (ATH) and aluminum phosphinate (AlPi) and using water as plasticizer and blowing agent. The flame‐retardant property and mechanism of the prepared foam matrix were studied by vertical burning test, limiting oxygen index (LOI), cone calorimeter, scanning electronic microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The experimental results showed that the PVA/ATH/AlPi (1/1.2/0.05) composite achieved LOI value of 41% and UL94 V‐0 (3.2 mm) rate. The addition of ATH and AlPi into PVA matrix significantly decreased flammability of the composites, because a more compact and continuous char layer of the PVA/ATH/AlPi composite could be formed, due to the involvement of AlPi in the char‐forming reaction. Compared with the pure PVA sample, the peak heat release rate (PHRR) and total heat release (THR) of PVA/ATH/AlPi (1/1.2/0.05) composite were reduced by 76.5% and 58.2%, respectively. Built upon this PVA‐based foam matrix with good flame retardancy, the flame‐retardant PVA‐based foam was successfully prepared through thermal extrusion. In addition, the influence of water content on melt viscosity, foam structure and mechanical strength was also analyzed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42020.     

Mechanical properties of low-density polyethylene/nano-magnesium hydroxide composites prepared by an in situ bubble stretching method

Low-density polyethylene/nano-magnesium hydroxide (LDPE/nano-Mg(OH)₂) composites have been prepared by an in situ bubble stretching (ISBS) method and simple shear method. By means of field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM), it was confirmed that the ISBS method leads to a high degree of dispersion of the Mg(OH)₂ nanoparticles in the LDPE matrix. Furthermore, no significant re-aggregation of the nanoparticles was observed after removing the bubbles by means of high-speed grinding. The tensile strengths of nanocomposites prepared by means of the ISBS method were higher than those of materials with the same Mg(OH)₂ loading produced by direct blending/extrusion. The tensile strength of the nanocomposites produced by the ISBS method reached a maximum value at an Mg(OH)₂ content of 15 phr. In contrast, the tensile strength of composites prepared by direct blending/extrusion shows a monotonic decrease with increasing Mg(OH)₂ content. The improvement in mechanical properties of nanocomposites associated with the use of the ISBS method can be attributed to a more homogeneous dispersion of smaller nanoparticles.     

新型低烟无卤阻燃电缆料的制备及表征

研究了以磷酸三甲苯酯(TCP)、水滑石(LDHs)、氢氧化铝(ATH)复配得到的复合阻燃剂对乙烯-醋酸乙烯酯共聚物(EVM:AV含量大于40%)性能的影响。分别通过氧指数、水平燃烧和拉伸性能测试考察了TCP/LDHs/ATH/EVM复合材料的阻燃性能和力学性能。结果表明,当TCP/LDHs/ATH/EVA为20/35/35/100(质量份数)时,复合材料的极限氧指数(LOI)达到35.2,阻燃级别为FH-1;断裂伸长率达到280%,拉伸强度达到11.0MPa。此复合材料可用于制造阻燃电缆。     

水镁石／ATH／APP复合阻燃剂对UPR的阻燃、抑烟性能的影响

将水镁石、氢氧化铝(ATH)、聚磷酸铵(APP)这3种阻燃剂复配,并应用于不饱和聚酯树脂(UPR),得到阻燃型UPR复合材料。通过氧指数、垂直燃烧(UL94)、烟密度等级(SDR)、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,在该复配阻燃体系中,水镁石、ATH、APP三者存在明显的协效作用,在水镁石：ATH：APP为2：1：1(质量比)、复合阻燃剂含量为40%时,复合材料氧指数达33．8%,垂直燃烧达FV-0级,烟密度等级为56．74,满足国家B_1级电器类热固性塑料的使用要求。     

Interface modification and characterization in linear low-density polyethylene highly loaded with aluminium hydroxide

Fire-retardant linear low-density polyethylene (LLDPE) composites were prepared by combining this polymer with uncoated and surface treated forms of aluminum hydroxide (Al(OH)₃). The poor toughness and ductility of polyethylene highly filled with Al(OH)₃ can be significantly improved by addition of a small amount of silicon oil. It is found that silicon oil improves elongation at break of the composite remarkably, but this is accompanied by the deterioration of tensile strength. Silane crosslinked polyethylene substituting for polyethylene as the matrix in Al(OH)₃-filled polyethylene improves the tensile strength of the composite. Fractured surface analysis and limiting oxygen index (LOI) of the composites were also studied. Possible mechanisms accounting for these effects are discussed.     

Cross-linked poly(ethylene vinyl acetate) (EVA)/low density polyethylene (LDPE)/metal hydroxides composites for wire and cable applications

Formulations of chemically cross-linked poly(ethylene vinyl acetate) (EVA) and low density polyethylene (LDPE) blends containing metal hydroxides flame retardants such as aluminum hydroxide (ATH) and magnesium hydroxide (MH) were prepared. Comparison of both type of metal hydroxides in respect of their influence on flammability as well as mechanical, thermal, and electrical properties of EVA/LDPE composites is presented. Most of the investigated properties are better for composites containing MH in comparison with composites containing ATH. Influence of various EVA/LDPE ratios on investigated properties is presented as well. Importance of improving compatibility using compatibilizers to improve some of the investigated properties is described. Polyethylene grafted with maleic anhydride (PEgMA) was found to be better compatibilizer for ATH than vinyl silanes.     

Thermal properties of tropical wood–polymer composites

Wood–polymer composites (WPC) of Geronggang (GE; Cratoxylon arborescens), a light tropical hardwood, impregnated with methyl methacrylate (MMA), styrene-co-acrylonitrile (3: 2; STAN), methyl methacrylate-co-bis (2-chloroethyl) vinyl phosphonate (3 : 1; MVP) and methyl methacrylate-co-bis (chloropropyl)-2-propene phosphonate (3:1;MPP), were prepared by in situ polymerization using γ-radiation or catalyst-heat treatment. Thermal characterization of these WPC by limiting oxygen index measurements (LOI), thermogravimetry (TG), and differential scanning calorimetry (DSC) showed that the impregnants greatly modified the wood properties. The LOI values of the GE–MVP and GE–MPP composites were much higher than that for GE and the other composites, indicating the effectiveness of the phosphonates as flame retardants. Concomitantly, the flaming characteristics also compared favorably against that for GE and the other composites. The decomposition temperature and maximum rate of weight loss determined by TG for GE–MVP and GE–MPP were substantially reduced, whereas the char yields were greatly higher. These observations again indicate that phosphonates imparted flame-retarding properties to their composites. The thermal properties of GE–MMA and GE–STAN composites were not vastly different from that of untreated GE. Flame retardancy in the phosphonate-containing composites was effected through both the condensed- and gaseous-phase mechanisms due to the presence of phosphorus and chlorine, respectively. Indication of grafting of polymer to wood was found for GE–STAN, GE–MVP, and GE–MPP composites, but not for GE–MMA. Composites prepared by γ-radiation or by the catalyst-heat treatment had similar thermal characteristics.     

Synergistic flame retardant effect of graphite powder in EVA/LDH composites

Abstract

Red mud (RM) is a large quantity waste product in the production of alumina. There is still no efficient way to deal with it in the world. Using RM as a raw material to synthesise Mg–Al–Fe ternary layered double hydroxide (LDH) is a feasible way to solve this global problem. The synthesised LDH was characterised by X-ray diffraction. The flame retardant and thermal degradation properties of ethylene-vinyl acetate/layered double hydroxide/graphite powder (EVA/LDH/GP) composites have been studied using cone calorimeter test (CCT), scanning electron microscopy (SEM), and thermogravimetry–Fourier transform infrared spectrometry (TG–IR). The CCT data indicate that heat release rates of EVA/LDH/GP composites decrease greatly in comparison with those of EVA, EVA/RM and EVA/LDH composites. The morphological structures of charred residues observed by SEM give positive evidence that the compact char residue layers formed from EVA/LDH/GP composites. The TG–IR is used to characterise volatilised products formed in the thermal degradation process.     

Research on the related properties of EVM/Al(OH)3/SiO2 composites applied for halogen‐free flame retardant cable insulation and jacket

The halogen‐free flame retardant (HFFR) ethylene‐vinyl acetate copolymer (EVM)/ATH/SiO₂ composites have been prepared by melting compounding method, and the flame retardant, thermal stability, rheological, electrical, and mechanical properties have been investigated by cone calorimeter, LOI, UL‐94, TG, FE‐SEM, rotational rheometer, dielectric breakdown, and ultimate tensile. The results indicate that the flame retardant of EVM vulcanizates is improved and the fire jeopardizing is dramatically reduced due to the addition of ATH. It is necessary that sufficient loading of ATH (≥120 phr) is needed to reach essential level (LOI > 30; V‐0 rating) of flame retardant for HFFR EVM/ATH/SiO₂ composites used as cable in industry. The rheological characteristics show that at all the measurement frequencies, the storage and loss modulus of the composites increase monotonously as the concentration of ATH filler increases, while the complex viscosity and tan delta present reverse trend. And also, it has been found that the HFFR composites at high filler concentrations still keep good mechanical and electrical properties, which is very important for practical applications as cable. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚磷酸三聚氰胺/季戊四醇/水滑石阻燃体系改性EVA热塑性弹性体的研究

采用聚磷酸三聚氰胺/季戊四醇（MPP/PER）膨胀阻燃体系与水滑石（LDH）并用阻燃改性乙烯—醋酸乙烯酯（EVA）热塑性弹性体。结果表明,当EVA/MPP/PER/LDH质量比为60/20/10/10时,复合材料阻燃级别达到UL94V-0,极限氧指数（LOI）为30.6%。TGA分析结果表明,阻燃体系MPP/PER和LDH协同效应提高了EVA热分解残留率。炭层扫描电镜（SEM）分析表明,MPP/PER与LDH协同作用有利于形成连续致密的炭层,提高了EVA/MPP/PER/LDH复合材料的阻燃性能。