Facile preparation of modified carbon nanotube‐reinforced PBT nanocomposites with enhanced thermal,flame retardancy,and mechanical properties

In this study, the carbon nanotube was modified by inorganic acids to introduce the carboxylic acid groups on the surface. The modified carbon nanotube (m‐CNT)‐reinforced poly(1,4‐butylene terephthalate) (PBT) nanocomposites were prepared through melt blending method. Morphological observations revealed that the m‐CNT particles were homogeneously dispersed in PBT matrix. Differential scanning calorimeter (DSC) analysis showed that a very small quantity of m‐CNT can significantly increase the crystallization temperature of PBT. The improvement of thermal stability and tensile strength/modulus of the nanocomposites strongly depended on the uniform dispersion of m‐CNT and the interactions between m‐CNT and PBT through hydrogen‐bonding formation. In the cone calorimeter testing, the PHRR decreased from 1189 kW/m² for neat PBT to 737 kW/m² for PBT/0.9m‐CNT containing 0.9 wt% m‐CNT with a reduction of 38%. The remarkable enhancement of flame retardancy properties was attributed to the condensed‐phase effect acted by the m‐CNT. POLYM. COMPOS., 37:1812–1820, 2016. © 2014 Society of Plastics Engineers     

Study on thermal stability and flame retardancy of polymer/layered silicate nanocomposites based on POE and POE‐g‐MAH

Ethylene‐octene elastomer (POE)/organo‐montmorillonite (OMT) and maleic anhydride‐grafted POE (POE‐g‐MAH)/OMT composites were prepared through melt mixing and influence of clay dispersion on thermal, dynamic mechanical, and flammability properties were investigated. The results showed that OMT forms intercalated/exfoliated structures in POE‐g‐MAH/OMT and agglomerated structure in POE/OMT microcomposites, resulting in more significant improvements of storage modulus and glass transition temperature in the POE‐g‐MAH/OMT rather than the POE/OMT composites. The POE‐g‐MAH/OMT nanocomposites have better thermal stability and significantly reduced flammability than the POE/OMT microcomposites, which was discussed on the basis of cone colorimeter test of the composites and energy dispersive X‐ray spectrum analysis of the combustion chars. POLYM. ENG. SCI., 54:2911–2917, 2014. © 2014 Society of Plastics Engineers     

Ethylene‐vinyl acetate copolymer/multiwalled carbon nanotube/organoclay nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) was melt‐mixed with multiwalled carbon nanotubes (MWCNTs) and organoclays, and the effects of simultaneous use of organoclays and MWCNTs on the surface resistivity and tensile properties of EVA nanocomposites were investigated. The surface resistivity of EVA/MWCNT nanocomposite with 1 phr of MWCNT is out of our measurement range (above 10¹² Ω/square). With increasing content of organoclay from 0 to 3 phr, the surface resistivity of the EVA/MWCNT/organoclay nanocomposites with 1 phr MWCNT remains out of our measurement range. However, the surface resistivity of the nanocomposite decreases to 10⁶ Ω/square with addition of 5 phr organoclay. The tensile properties of EVA/MWCNT/organoclay nanocomposites with 1 phr MWCNT and 5 phr organocaly are similar to those of EVA/MWCNT nanocomposites with 5 phr MWCNT except tensile modulus. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

Flame retardancy and thermal stability of ethylene-vinyl acetate copolymer nanocomposites with alumina trihydrate and montmorillonite

The development of fire retardant for wire and cable sheathing materials has oriented toward low smoke and halogen-free flame retardant technology to achieve better safety for electrical equipment and devices and to satisfy standards. However, many polymer flame resistance materials require a very high proportion of metal hydrate filler within the polymer matrix (60 wt%) to achieve a suitable level of flame resistance, which may lead to inflexibility, poor mechanical properties and problems during compounding and processing. In this study, the alumina trihydrate (ATH) was added to montmorillonite (MMT) as the halogen-free flame retardant of ethylene-vinyl acetate (EVA) copolymer, with various ratios of EVA/ATH/MMT. The prepared nanocomposites were characterized through various techniques of XRD, tensile test, DSC analysis, TGA, LOI evaluation, and FE-SEM to explore the effects of organic modified clay (OMMT) and the layer distance on the mechanical, thermal, and flame resistance properties. In the XRD examinations, the layer-distance of MMT increased from 1.27 to 1.96 nm when polymer was added to the octadecylamine modified MMT. The best tensile strength was obtained at 3 wt% MMT. In addition, the halogen-free flame resistance grade of EVA containing 3 wt% OMMT and 47 wt% ATH revealed the best elongation and fire resistance (LOI = 28). The tensile and flame resistance properties of the nanocomposites were also significantly improved.     

Multiwalled carbon nanotube/montmorillonite hybrid filled ethylene‐co‐vinyl acetate nanocomposites with enhanced mechanical properties,thermal stability,and dielectric response

Homogeneous multiwalled carbon nanotube/montmorillonite hybrid filler (HMM) dispersion was prepared by co‐ultrasonication and was subsequently used to prepare ethylene‐co‐vinyl acetate (EVA) nanocomposites by solution blending method. XRD and TEM analysis of HMM confirm significant interaction between the montmorillonite (MMT) layers and multiwalled carbon nanotubes (MWCNT) in line with previous reports. Analysis of the nanocomposites shows the constituent fillers to be homogeneously dispersed in EVA matrix. Mechanical properties of neat EVA are remarkably improved with HMM content up to 3 wt% followed by reversion. Maximum improvement observed in tensile strength, elongation at break, and toughness are 424%, 109%, and 1122%, respectively. Results show maximum thermal stability at 4 wt% and best dielectric response at 1 wt% HMM content. Exceptional mechanical and dielectric properties of EVA nanocomposites attained may be attributed to homogeneous dispersion of fillers and improved polymer–filler interaction. Comparison shows excellent synergy between MWCNT and MMT towards mechanical reinforcement of EVA. POLYM. ENG. SCI., 58:1155–1165, 2018. © 2017 Society of Plastics Engineers     

Effect of OMMTs on flame retardancy and thermal stability of poly(ethylene‐co‐vinyl acetate)/LDPE/magnesium hydroxide composites

The aim of this study was to prepare poly (ethylene‐co‐vinyl acetate) (EVA)/ low density polyethylene (LDPE)/magnesium hydroxide (MH) composites applicable in cable industry with required flame retardancy. For this reason, two types of organo‐modified montmorillonites (OMMT) with different surface polarites (Cloisite 15A and Cloisite 30B) at various concentrations, and also combination of these two OMMTs with overall loadings of 2 wt % and 5 wt % were used. The samples were compounded using a twin screw extruder with total (MH + OMMT) feeding of 55 wt % and 60 wt %. Limiting oxygen index (LOI) of the samples containing 2 wt % of OMMTs increased about 16% and dripping was suppressed according to vertical burning test (UL‐94V). Thermogravimetric results of EVA/LDPE/MH samples containing OMMT showed that the beginning of second step degradation was shifted about 50°C to higher temperatures. The composite tensile strength results showed enhancement by incorporating some amount of nanoclays with EVA/LDPE/MH composites. Scanning electron microscopy images confirmed that MH particles had better wetting by EVA matrix in presence of nanoclays. Oxidative induction time of the EVA/LDPE/MH/OMMT nanocomposites was 140 min, which was more than that of the samples without OMMT (20 min). Employing the equal weight ratios of the two OMMTs demonstrated a synergistic effect on flame retardancy of the samples according to the both tests results (LOI, UL‐94V). X‐ray diffraction analysis of the samples confirmed the intercalation/semiexfoliation structure of nanosilicate layers in the bulk of EVA/LDPE matrix. This led to longer elongation at break and thermal stability of Cloisite 15A based nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40452.     

Preparation and characterization of ethylene‐vinyl acetate nanocomposites: enhanced flame retardant

Ethylene‐vinyl acetate (EVA) nanocomposites with enhanced flame retardance were prepared by the sol–gel process in the melt. Two EVAs with different vinyl acetate (VA) contents and aluminium isopropoxide were used as organic and inorganic phases. The nanocomposites were prepared in a batch mixer under constant processing conditions and were analysed by several characterization techniques. Aluminium isopropoxide presented low activation energy, which allows the synthesis of the nanoparticles without a post step treatment. The reaction mechanism is proposed. Nanocomposites with smaller and well dispersed metal nanoparticles were produced with an EVA with higher VA content. EVA nanocomposites achieve the requirements for 94 V‐0 classification. © 2013 Society of Chemical Industry     

Recycled PET‐organoclay nanocomposites with enhanced processing properties and thermal stability

Preparation of thermally stable recycled PET‐organoclay nanocomposites with improved processing and mechanical properties is a challenging task from the environmental as well as industrial and commercial point of view. In this work, both modification of sodium‐type montmorillonite with 1,2‐dimethyl‐3‐octadecyl‐1H‐imidazol‐3‐ium chloride and additional treatment with [3‐(glycidyloxy)propyl]trimethoxysilane was performed. Thermal stability of the organoclays and nanocomposites prepared by melt compounding was tested by thermogravimetric analysis, differential scanning calorimetry, and melt rheology. In comparison with the organoclays modified with quaternary ammonium compounds, the prepared clays showed substantial suppression of matrix degradation during melt mixing. The increase in interlayer distance of silicate platelets and homogeneity of dispersions in the recycled and virgin PET matrices have been evaluated by transmission electron microscopy and wide‐angle X‐ray scattering. The higher degree of delamination in the nanocomposites filled with imidazole organoclays was in a good agreement with improved rheological characteristics and led to significant enhancement in mechanical properties and thermal stability. A difference in structure (besides the level of delamination and homogeneity of silicate platelets) of recycled versus virgin PET nanocomposites was detected by X‐ray diffraction patterns. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Polyester nanocomposite fibers with improved flame retardancy and thermal stability

Polyester (PET) nanocomposite fibers were spun by adding master batches of linear low‐density polyethylene (LLDPE) loaded with Montmorillonite (MMT) nanoclay after compatibilizing the PET and LLDPE. The spun fibers showed increased thermal stability as well as flame retardancy, which increased progressively with the amount of nanoclay loaded into the fiber. There is slight decrease in tensile strength of the fiber accompanied by decrease in elongation % indicating addition of nanoclay makes the filaments stiffer. The onset of crystallization temperature occurred at higher temperature in case of composite fibers than on the neat PET fiber because of nucleating effect of nanoclay. The dyeability of the fibers was not affected and also had very little impact on the flame retardancy of the fiber. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Ethylene vinyl acetate/Mg‐Al LDH nanocomposites by solution blending

Partially exfoliated ethylene vinyl acetate (EVA‐40, 40% vinyl acetate content)/layered double hydroxide (LDH) nanocomposites using organically modified layered double hydroxide (DS‐LDH) have been synthesized by solution intercalation method. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) studies of nanocomposites shows the formation of exfoliated LDH nanolayers in EVA‐40 matrix at lower DS‐LDH contents and partially intercalated/exfoliated EVA‐40/MgAl LDH nanocomposites at higher DS‐LDH contents. These EVA‐40/MgAl LDH nanocomposites demonstrate a significant improvement in tensile strength and elongation at break for 3 wt% of DS‐LDH filler loading compare to neat EVA‐40 matrix. Thermogravimetric analysis also shows that the thermal stability of the nanocomposites increases with DS‐LDH content in EVA‐40. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Metal-phenolic networks: A biobased synergist for EVA/APP composites toward enhanced thermal stability and flame retardancy

In the present study, a biomass-derived metal-phenolic networks (MPN) were used as charring agent and flame-retardant synergist for Ethylene-vinyl acetate/Ammonium polyphosphate (EVA/APP) composites. Compared with the polyphenol, the thermal stability of MPN was improved remarkably, making it a good match for EVA. Meanwhile, Limit oxygen index test revealed that MPN endowed EVA/APP composites with enhanced flame-retardant performance. The reason on improvement in the flame retardancy of composites was also discussed and the corresponding mechanism was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47243.     

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     

Mechanical,thermal properties,and flame retardancy of PC/ultrafine octaphenyl‐POSS composites

Composites of ultrafine polyhedral oligomeric octaphenyl silsesquioxane (OPS) and polycarbonate (PC) were prepared by melt blending. The mechanical and thermal properties of the composites were characterized by tensile and flexural tests, impact test, differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), and thermal gravimetric analysis (TGA). Rheological properties of these melts were tested by torque rheometer. The flame retardancy of the composites was tested by limiting oxygen index (LOI), the vertical burning (UL‐94), and cone calorimeter test. The char residue was characterized by scanning electron microscope (SEM) and ATR‐FTIR spectrum. Furthermore, the dispersion of OPS particles in the PC matrix was evidenced by SEM. The results indicate that the glass transition temperatures (T_g) and torque of the composites decrease with increasing OPS loading. The onset decomposition temperatures of composites are lower than that of PC. The LOI value and UL‐94 rating of the PC/OPS composites increase with increasing loading of OPS. When OPS loading reaches 6 wt %, the LOI value is 33.8%, UL‐94 (1.6 mm) V‐0 rating is obtained, and peak heat release rate (PHRR) decreases from 570 to 292 kJ m^?2. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Flammable,thermal, and mechanical properties of intumescent flame retardant PP/LDH nanocomposites with different divalent cations

The flammable, thermal, and mechanical properties of intumescent flame retardant (IFR) polypropylene/layered double hydroxide (PP/IFR/LDH) nanocomposites with the LDHs of different divalent cations and IFR system of ammonium polyphosphate/pentaerythritol (APP/PER) have been studied by X-ray diffraction (XRD), cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), limiting oxygen index (LOI), UL-94 test, and mechanical measurements. The XRD results show that the exfoliated PP/IFR/LDH nanocomposites possess the nanoscaled dispersion characteristic. The data from the CCT tests show the synergistic effect of LDHs with IFR can decrease considerably the HRR, MLR, and EHC values of the PP/IFR/LDH nanocomposites, in which the pk-HRR, pk-MLR, and pk-EHC values of the PP/IFR/ZnAl-LDH sample decrease to 318 kW/m², 0.081 g/m² s, 61.8 MJ/kg from the corresponding values 506 kW/m², 0.115 g/m² s, 71.8 MJ/kg of the PP/IFR sample. The LOI and UL-94 data further support the evidence that the flame retardant synergistic effects of LDHs with IFR increase the LOI values and UL-94 rating, especially for the LDHs with the transition ions (Zn, Cu) the LOI values can reach 33% and the UL-94 pass the V-0 rating. The TGA results demonstrate the LDHs can greatly improve the thermal stabilities of PP/IFR/LDH nanocomposites by increasing the thermo-oxidation decomposition temperature and charred residues. The morphological structures observed by SEM have demonstrated the LDHs can promote formation of compact charred layers. The data from the mechanical tests show the tensile strength and elongation at break of the PP/IFR/LDH samples are basically unchanged compared with the PP/IFR sample. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane nanocomposites

The flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane (POSS) nanocomposites are reviewed. Results are summarized and compared on the basis of structure–property relationships. Because of the variability of groups attached on POSS, they exhibit different performance in polymer nanocomposites: metal‐containing POSS show good catalytic charring ability; vinyl‐containing and phenyl‐containing POSS promote the strength of char. Improvements in the cone calorimeter (such as reduced peak heat release rate) are advantages of POSS as preceramics for fire retardancy compared with traditional flame retardants, and it will pave the way to the design of inorganic–organic hybrid polymer nanocomposites with enhanced flame retardancy and thermal stability. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of HDPE/EPDM‐g‐TMEVS nanocomposites with enhanced electrical and flame properties

Nanoclay reinforced HDPE/silane grafted EPDM composites have been developed using an epoxy functionalized HDPE as compatibilizer.The nanoclay has been varied from 0% to 10% in the composites along with the incorporation of compatibilizer and without compatibilizer in a brabender plasticorder.The dielectric and fire retardant properties of these nanocomposites have been examined. Addition of nanoclay enhanced char formation with increased values of limiting oxygen index. Electrical properties such as volume and surface Resistivity improved with addition of nanoclay and compatibilizer. The values of tan δ increased with increase in grafted EPDM and silanated nanoclay loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,thermal stability,and flame retardancy of PA66, treated with dichlorophenylphsophine derivatives

Synthesis, thermal stability, and flame retardancy of PA66, treated with derivatives of dichlorophenylphosphine, are reported. With an aim to improve the thermal stability and flame retardancy of PA66, along with improving its consistency, several new derivatives of dichlorophenylphosphine, namely bis-(4-carboxyanilino) phenyl phosphamide (BNPO), N-benzoic acid-(ethyl-N-benzoic acid formamide) phosphamide (NENP), poly-N-aniline-phenyl phosphamide (DPPD), and bis-N-benzoguanamine-phenyl phosphamide (MCPO), were synthesized, which resulted in end amino or carboxyl. FTIR, ¹H NMR, MS, and elemental analysis confirmed the chemical structures of the synthesized flame retardants. Interestingly, thermal stabilities and flame retardancies of PA66 improved, however, the intrinsic viscosities ([η]) and viscosity average molecular weights (M_η) decreased with grafting of the flame retardants. Moreover, the consistency was overcome conformingly using SEM without interfacial effect.     

Thermal stability,flame retardancy and rheological behavior of ABS filled with magnesium hydroxide sulfate hydrate whisker

Summary Halogen-free and flame-retardant acrylonitrile–butadiene–styrene copolymer (ABS) composites were prepared using magnesium hydroxide sulfate hydrate (MHSH) whisker as a flame retardant, and the effect of zinc stearate (ZnSt₂) as a dispersion additive on the morphology and properties of the ABS/MHSH composites was studied. The morphology observation by using scanning electronic microscope (SEM) indicates that the addition of zinc stearate could improve the dispersion of the MHSH whisker in ABS matrix. Cone analysis results show that the heat release rate (HRR) and mass loss rate (MLR) of the composites decrease considerably with increasing MHSH whisker content. The composite with zinc stearate has lower HRR than the composite without zinc stearate, indicating the better dispersion of MHSH whisker could improve the flame retardancy of ABS composites. SEM observation results show that the char residue of ABS/MHSH composites retain its fibrous appearance. Thermogravimetric analysis (TGA) shows that the presence of MHSH enhanced thermal stability of the composites obviously. The viscoelastic behavior of the composites was measured by using a parallel plate rheometer. With increasing MHSH whisker content, the viscosity, storage modulus of the composites increase at low frequency zone, and ABS/MHSH composites exhibit more distinct solid-like response at terminal zone than ABS. The presence of zinc stearate leads to slight increases in the storage modulus.     

PP/PVAc-OMMT纳米复合材料的力学与阻燃性能

利用乳液聚合法引发乙酸乙烯酯(VAc)在有机蒙脱土(OMMT)中原位插层聚合,再与聚丙烯(PP)熔融共混制备PP/聚乙酸乙烯酯(PVAc)-OMMT纳米复合材料.研究了OMMT用量对复合材料力学性能和阻燃性能的影响.并通过X射线衍射仪、透射电子显微镜等对复合材料进行了表征.结果表明:PP/PVAc-OMMT形成了插层与剥离型的纳米复合材料结构;在PP/PVAc-OMMT纳米复合材料中,PVAc-OMMT具有明显的增韧作用,当w(OMMT)为5%时,冲击强度比纯PP提高76%;PP/PVAc-OMMT的极限氧指数最高达23.9%,比纯PP提高了33%.     

Investigation on flame retardancy and rheological and thermomechanical characterisation of multiwall carbon nanotube reinforced nanocomposites

Abstract

In the present work, the influence of multiwalled carbon nanotubes (MWCNTs) on the flame retardancy and rheological, thermal and mechanical properties of polybutilen terephthalate (PBT) and polypropylene (PP) matrixes has been investigated. The carbon nanotube content in the thermoplastic materials was 2 and 5?wt‐%. The nanocomposites were obtained by diluting a masterbatch containing 20?wt‐% nanotubes using a twin‐screw extruder and the thermal properties were analysed by differential scanning calorimetry and thermogravimetric analysis; thermomechanical properties were determined by dynamic mechanical thermal analysis and the rheological behaviour was studied by a Thermo Haake Microcompounder. The results concerning the flame retardancy show that the MWCNTs are not equally effective as flame retardants in PP and PBT. The ignition time is increased only for PBT whereas the extinguishing time is decreased for PP and PBT. The reinforcement of the thermoplastics with multiwall carbon nanotubes is improved regarding the mechanical and thermal properties of the nanocomposites compared to pristine materials and the behaviour of thermoplastic nanocomposites regarding fire retardancy depends on the nature of the polymeric matrix.