Inner surface modification of halloysite nanotubes and its influence on morphology and thermal properties of polystyrene/polyamide‐11 blends

The asymmetry of halloysite surface chemistry was used to perform a selective modification of its inner surface via grafting of a synthesized styrene/(methacryloyloxy)methyl phosphonic acid copolymer. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and pyrolysis gas chromatography/mass spectrometry were used to evidence and quantify the grafting. Then, raw and hybrid nanoparticles were incorporated in polystyrene (PS)/polyamide‐11 (PA11) blends (80/20 and 60/40 wt%). Scanning electron micrographs showed differences in localization of the halloysite nanotubes (HNTs), since raw halloysite is concentrated in the PA11 phase while modified halloysite is also located at the PS/PA11 interface, leading to a better interfacial adhesion between PS and PA11. An inhibiting effect of modified halloysite on PA11 coalescence was evidenced by measuring the particle size distribution of the extracted nodules. Moreover, the presence of modified halloysite at the interface shows an improvement in terms of thermal stability as observed by TGA, but with no significant effects on PA11 crystallization behaviour as shown by differential scanning calorimetry results. Rheological measurements were carried out to study the influence of the surface modification of halloysite on the blend morphology. A gel‐like behaviour was observed for the (60/40 wt%) HNTs reinforced composition that was enhanced in the case of 10% functionalized halloysite. © 2016 Society of Chemical Industry     

Highly dispersed polyamide‐11/halloysite nanocomposites: Thermal,rheological, optical,dielectric, and mechanical properties

Bio‐based polyamide 11 and natural halloysite nanotubes (HNTs) were used for the preparation of PA‐11/HNT nanocomposites with varying nanotubes concentrations by melt extrusion using a masterbatch dilution process. The prepared nanocomposites were analyzed for microstructural changes, transparency, thermal stability, rheological behavior, dielectric, and mechanical properties. The HNT nanotubes are well dispersed in PA‐11 matrix in the studied composition range as shown by microscopy and spectrophotometry. Interestingly, good halloysite dispersion in PA‐11 matrix increases the tensile strength and Young modulus of PA‐11 without sacrificing the ductility. Highly dispersed nanotubes also bring favorable changes in the thermal stability, dielectric, and rheological characteristics of PA‐11. Additionally, glass transition temperature, crystallization temperature, and degree of crystallinity of the nanocomposites tend to increase with increase in nanotubes loading. Thus, PA‐11 can become a tailor‐made material with multifunctional characteristics, thanks to the addition of HNTs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synergistic flame‐retardant effect of halloysite nanotubes on intumescent flame retardant in LDPE

Synergistic flame‐retardant effect of halloysite nanotubes (HNTs) on an intumescent flame retardant (IFR) in low‐density polyethylene (LDPE) was investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), cone calorimeter (CC) test, and scanning electronic microscopy (SEM). The results of LOI and UL‐94 tests indicated that the addition of HNTs could dramatically increase the LOI value of LDPE/IFR in the case that the mass ratio of HNTs to IFR was 2/28 at 30 wt % of total flame retardant. Moreover, in this case the prepared samples could pass the V‐0 rating in UL‐94 tests. CC tests results showed that, for LDPE/IFR, both the heat release rate and the total heat release significantly decreased because of the incorporation of 2 wt % of HNTs. SEM observations directly approved that HNTs could promote the formation of more continuous and compact intumescent char layer in LDPE/IFR. TGA results demonstrated that the residue of LDPE/IFR containing 2 wt % of HNTs was obviously more than that of LDPE/IFR at the same total flame retardant of 30 wt % at 700°C under an air atmosphere, and its maximum decomposing rate was also lower than that of LDPE/IFR, suggesting that HNTs facilitated the charring of LDPE/IFR and its thermal stability at high temperature in this case. Both TGA and SEM results interpreted the mechanism on the synergistic effect of HNTs on IFR in LDPE, which is that the migration of HNTs to the surface during the combustion process led to the formation of a more compact barrier, resulting in the promotion of flame retardancy of LDPE/IFR. In addition, the mechanical properties of LDPE/IFR/HNTs systems were studied, the results showed that the addition of 0.5–2 wt % of HNTs could increase the tensile strength and the elongation at break of LDPE/IFR simultaneously. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40065.     

Thermal decomposition kinetics of dynamically vulcanized polyamide 6–acrylonitrile butadiene rubber–halloysite nanotube nanocomposites

Thermally stable thermoplastic elastomer nanocomposites based on polyamide 6 (PA6), acrylonitrile butadiene rubber (NBR), and halloysite nanotubes (HNTs) were dynamically vulcanized, and their nonisothermal decomposition kinetics were examined. The Friedman, Kissinger–Akahira–Sunose (KAS), Ozawa–Wall–Flynn (FWO), and modified Coats–Redfern (m-CR) isoconversional models were used to obtain information about the kinetics of the thermal decomposition of PA6–NBR–HNTs in terms of the activation energy per partial mass loss monitored through thermogravimetric analyses performed at different heating rates. An erratic trend was due to the Friedman model, especially for systems having higher HNT loadings, whereas the KAS, FWO, and m-CR models revealed very similar meaningful thermal decomposition kinetics. A relatively high activation energy corroborating a reliable thermal stability was obtained by the addition of HNTs to PA6–NBR, and the resistance against decomposition was higher for systems containing more HNT. This signified the role of the HNTs as thermal stability modifiers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47483.     

Natural inorganic nanotubes reinforced epoxy resin nanocomposites

Natural occurred nanotubes, halloysite nanotubes, were modified by silane and incorporated into epoxy resin to form nanocomposites. The morphology of the nanocomposites was characterized by transmission electron microscopy (TEM). Dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were performed on the nanocomposites. Flexural property and coefficient of thermal expansion (CTE) of the nanocomposites were also determined. Comparing with the neat resin, about 40% increase in storage modulus at glassy state and 133% at rubbery state were achieved by incorporating 12 wt% modified HNTs into the epoxy matrix. In addition, the nanocomposites exhibited improved flexural strength, char yield and dimensional stability. TEM examination revealed a uniform dispersion of the nanotubes in the epoxy resin. The remarkably positive effects of the HNTs on the performance of the epoxy resin were correlated with the unique characteristics of the HNTs, the uniform dispersion and the possible interfacial reactions between the modified HNTs and the matrix.     

Effect of halloysite nanotubes on thermal and flame retardant properties of polyamide 6/melamine cyanurate composites

In this study, polyamide 6 (PA6) with various contents of halloysite nanotubes (HNTs) and melamine cyanurate (MCA) were prepared by a twin‐screw extruder. The flame retardant and physical properties of PA6 composites were examined. X‐ray diffraction (XRD) patterns of PA6/HNTs and PA6/MCA/HNTs composites showed that HNTs as a nanoscale material dispersed in PA6 whether with MCA or not. Thermo gravimetric analyzer (TGA) results showed the presence of HNTs can improve thermal stability of PA6 and PA6/MCA composites. The incorporation of HNTs seemed to result the increase of crystallinity of PA6 and PA6/MCA composites from the differential scanning calorimetry (DSC) results. The combined of HNTs and MCA that leads to further improvements limiting oxygen index (LOI) value of PA6 to 31.7% exerted a positive effect on flame retardancy of PA6. What's more, some mechanical enhancements of PA6 with adding of HNTs were achieved and HNTs also made the tensile properties of PA6/MCA composites improved. POLYM. COMPOS., 36:892–896, 2015. © 2014 Society of Plastics Engineers     

PPS/PA66/HNTs复合材料的制备与性能研究

采用熔融共混方法制备了聚苯硫醚(PPS)/尼龙-66(PA66)/埃洛石纳米管(HNTs)复合材料,研究了其力学性能、热性能及其微观形态.结果表明:当PPS/PA66的比为60/40、HNTs的含量为30%时,复合材料具有较好的性能.复合材料的拉伸强度、弯曲模量及缺口抗冲击强度相对纯PPS分别提高了36.6%、163....     

Synthesis of poly(AA‐co‐AM) superabsorbent composites by reinforcement of halloysite nanotubes

A novel poly(acrylic acid‐co‐acrylamide)/halloysite nanotubes [PAA‐AM/HNTs] superabsorbent composite was synthesized by free radical polymerization with using HNTs as an inorganic additive. The composite was characterized by Fourier transform infrared spectroscopy, scanning electron microscope, and thermogravimetric analysis. The results revealed that HNTs and PAA‐AM were combined well together to form a porous structure with a pore size of about 10 μm, and HNTs were uniformly distributed in the composite. The thermal stability was improved by adding HNTs in the composite. The influences of contents of initiator and halloysite, neutralization degree of AA, and molar ratio of AM to AA on water absorbency were investigated. The water absorbency and the water retention capacity were improved after adding HNTs into PAA‐AM. The composite containing 10% HNTs had the highest water absorbency of 1276 g/g in distilled water. Moreover, PAA‐AM/HNTs composite also had a high swelling rate within 60 min and could maintain 78% initial swelling capability after five reswelled test. The substantial enhancement of swelling properties enables PAA‐AM/HNTs suitable for numerous practical applications. POLYM. COMPOS., 36:229–236, 2015. © 2014 Society of Plastics Engineers     

Compatibilizing Effect of Halloysite Nanotubes on Polyetherimide/Silicone Rubber Blend Based Nanocomposites

The present study deals with the preparation of nanocomposites comprising of polyetherimide (PEI) and silicone rubber reinforced with both unmodified and modified halloysite nanotubes (HNTs) by melt blending process with the aid of co-rotating twin screws extruder. The developed nanocomposites have been characterized by various sophisticated analytical instrument viz. TGA, DMA, SEM,TEM, FTIR and UTM. There is remarkable enhancement in various properties of the developed nanocomposites due to incorporation of modified HNTs. This can be attributed to fairly good dispersion of the HNTs in the polymer matrix resulting in reductions of filler-filler interaction.     

PVC/MBS/埃洛石纳米管复合材料的制备及其性能

采用熔融共混法制备了聚氯乙烯(PVC)/甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)/埃洛石纳米管(HNTs)三元复合材料,研究了HNTs对PVC/MBS共混体系力学性能、热性能和微观结构的影响。结果表明:HNTs与MBS可协同增韧PVC,使复合材料的强度和刚性得到改善,当HNTs的填充量为3 phr时,PVC/MBS(100/3)共混体系的冲击强度、拉伸强度、弯曲强度和弯曲模量分别提高了57.7%、12.1%、7.6%和45.9%;其冲击断面呈现韧性断裂特征;TEM观察结果发现,HNTs在PVC/MBS共混体系中具有良好的分散状态;热失重分析显示,HNTs对PVC/MBS共混体系热稳定性的提高能起到一定作用。     

Hemocompatibility of electrospun halloysite nanotube‐ and carbon nanotube‐doped composite poly(lactic‐co‐glycolic acid) nanofibers

One of the major problems of nanofiber scaffold or other devices like cardiovascular or blood‐contacting medical devices is their weak mechanical properties and the lack of hemocompatibility of their surfaces. In this study, halloysite nanotubes (HNTs) and carbon nanotubes (CNTs) were incorporated within poly(lactic‐co‐glycolic acid) (PLGA) nanofibers and the mechanical property and hemocompatibility of both types of composite nanofibers with different doping levels were thoroughly investigated. The morphology and internal distribution of the doped nanotubes within the nanofibers were characterized using scanning electron microscopy and transmission electron microscopy. Mechanical properties of the electrospun nanofibers were tested using a material testing machine. The hemocompatibility of the composite nanofibers was examined through hemolytic and anticoagulant assay, respectively. We show that the doped HNTs or CNTs are distributed in the nanofibers with a coaxial manner and the incorporation of HNTs or CNTs does not significantly change the morphology of the PLGA nanofibers. Importantly, the incorporation of HNTs or CNTs within PLGA nanofibers significantly improves the mechanical property of PLGA nanofibers, and PLGA nanofibers with or without doping of the HNTs and CNTs display good anticoagulant property and negligible hemolytic effect to human red blood cells. With the enhanced mechanical property, great hemocompatibility, and previously demonstrated biocompatibility of both HNTs‐ and CNTs‐doped composite PLGA nanofibers, these composite nanofibers may be used as therapeutic artificial tissue/organ substitutes for tissue engineering applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Application of a novel halogen‐free intumescent flame retardant for acrylonitrile‐butadiene‐styrene

A novel intumescent flame retardant (IFR), containing ammonium polyphosphate (APP) and poly(tetramethylene terephthalamide) (PA4T), was prepared to flame‐retard acrylonitrile‐butadiene‐styrene (ABS). The flame retardation of the IFR/ABS composite was characterized by limiting oxygen index (LOI) and UL‐94 test. Thermogravimetric analysis (TGA) and TGA coupled with Fourier transform infrared spectroscopy (TG‐FTIR) were carried out to study the thermal degradation behavior of the composite and look for the mechanism of the flame‐retarded action. The morphology of the char obtained after combustion of the composite was studied by scanning electron microscopy (SEM). It has been found the intumescent flame retardant showed good flame retardancy, with the LOI value of the PA4T/APP/ABS (7.5/22.5/70) system increasing from 18.5 to 30% and passing UL‐94 V‐1 rating. Meanwhile, the TGA and TG‐FTIR work indicated that PA4T could be effective as a carbonization agent and there was some reaction between PA4T and APP, leading to some crosslinked and high temperature stable material formed, which probably effectively promoted the flame retardancy of ABS. Moreover, it was revealed that uniform and compact intumescent char layer was formed after combustion of the intumescent flame‐retarded ABS composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphological and mechanical behavior of chemically treated jute‐PHBV bio‐nanocomposites reinforced with silane grafted halloysite nanotubes

In this study, at first, thin films of poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) nanocomposites were prepared by adding 1–3 wt % grafted halloysite nanotubes (G‐HNTs). Jute‐PHBV bio‐nanocomposites were then fabricated using these films and chemically treated jute fibers in a compression mold machine. The effect of treatment and modification on jute fiber and halloysite nanotubes (HNTs), and the change in their morphology was investigated using Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), scanning and transmission electron microscopy (SEM, TEM). Flexural and thermomechanical properties were determined using a three‐point bend test and dynamic mechanical analysis (DMA). The results showed separation of fiber bundles with rough fiber surfaces, and grafting of silane coupling agents on fibers and HNTs after the chemical treatment. As a result, a strong bonding was established between the PHBV, G‐HNTs and jute fibers that lead to significant improvements in flexural and thermomechanical properties of jute‐PHBV bio‐nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43994.     

Flame‐retardant materials: synergistic effect of halloysite nanotubes on the flammability properties of acrylonitrile–butadiene–styrene composites

Novel well‐dispersed nanocomposites of halloysite nanotubes and acrylonitrile–butadiene–styrene were prepared. The fire retardancy and thermal stability of these new nanocomposites were improved. A synergistic effect was observed between the halloysite nanotubes and an intumescent flame‐retardant system consisting of ammonium polyphosphate, melamine polyphosphate and pentaerythritol in the acrylonitrile–butadiene–styrene composites. The incorporation of the intumescent flame‐retardant material into the halloysite–polymer nanocomposite system also improved the thermal stability and reduced the peak heat release rate by up to 56.2%, and it significantly reduced the emission of CO and CO₂ gases. The morphology and dispersion of the halloysite nanotubes were characterized using scanning and transmission electron microscopy. The thermal stability and flammability properties were investigated using thermogravimetric analysis and cone calorimeter tests. © 2013 Society of Chemical Industry     

Halloysite nanotubes grafted polylactic acid and its composites with enhanced interfacial compatibility

Polylactic acid (PLA) polymers are promising substitutes for polluting fossil fuel-derived polymers in the field of food safety due to their environmental friendliness, good biocompatibility, and degradability. However, their poor mechanical property limits their practical utilization. In this study, abundant natural halloysite nanotubes (HNTs) were incorporated into PLA to address these issues. To overcome interfacial incompatibility between the matrix (PLA) and nanofillers (HNTs), 3-Aminopropyltrimethoxysilane (APS) were firstly grafted onto HNTs to form end-up amino groups which were served as binding sites for the polycondensation of lactic acid precursors. This formed PLA modified HNTs (pHNTs) precursor was further mixed with bulk PLA polymers to prepare the composite films by the solvent casting method. Compared with the pristine composite, the PLA/pHNTs composites show better thermal stability and mechanical properties, and the composite with 2 wt% pHNTs exhibits the best performance.     

Microcellular poly(hydroxybutyrate‐co‐hydroxyvalerate)‐hyperbranched polymer–nanoclay nanocomposites

The effects of incorporating hyperbranched polymers (HBPs) and different nanoclays [Cloisite® 30B and halloysite nanotubes (HNT)] on the mechanical, morphological, and thermal properties of solid and microcellular poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were investigated. According to the X‐ray diffraction (XRD) and transmission electron microscopy (TEM) analyses, Cloisite 30B exhibited a combination of exfoliation and heterogeneous intercalation structure for both solid and microcellular PHBV–12% HBP–2% Cloisite 30B nanocomposites. TEM images indicated that HNTs were uniformly dispersed throughout the PHBV matrix. The addition of 2% nanoclays improved the thermal stability of the resulting nanocomposites. The addition of HBP+poly(maleic anhydride‐alt‐1‐octadecene) (PA), Cloisite 30B, and HNT reduced the average cell size and increased the cell density of the microcellular components. The addition of (HBP+PA), Cloisite 30B, and HNT also increased the degree of crystallinity for both solid and microcellular components in comparison with neat PHBV. Also, with the addition of 12% (HBP+PA), the area under the tan‐δ curve, specific toughness, and strain‐at‐break of the PHBV–HBP nanocomposite increased significantly for both solid and microcellular specimens, whereas the storage modulus, specific Young's modulus, and specific tensile strength decreased. The addition of 2% nanoclays into the PHBV–HBP nanocomposites improved the storage modulus, specific Young's modulus, and specific tensile strength of the PHBV–HBP–nanoclay‐based nanocomposites, but they were still lower than those of the neat PHBV. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Flammability characteristics and performance of halogen‐free flame‐retarded polyoxymethylene based on phosphorus–nitrogen synergistic effects

The flammability characteristics and thermal stability of a novel halogen‐free flame‐retardant compounding system based on polyoxymethylene (POM) were studied, and a very effective flame retarding formulation for POM was developed from a combination of ammonium polyphosphate (APP), melamine cyanurate (MC), novolak, and dipentaerythritol. The decomposition behavior of POM compounds was evaluated by thermogravimetric analysis. The compound shows optimal flame retardancy with a limiting oxygen index of 52.8 and flammability rating of UL94 V‐0, when 27 wt % APP, 9 wt % MC, 4 wt % novolak, and 4 wt % dipentaerythritol are simultaneously incorporated into POM. The presence of novolak and dipentaerythritol as char‐forming agents results in a dense and compact multicellular char residue for the test bar after combustion, while Fourier transform infrared spectra confirm a characteristic phosphorous‐ and carbon‐rich char resulting from the APP/MC formulation. The pyrolysis–gas chromatography/mass spectrometry analysis indicates that highly flammable formaldehyde gas, the main pyrolysis product of POM, is annihilated by amide derivatives produced by the pyrolysis of MC, imparting better flame retardancy. The comprehensive flame‐retardant mechanisms based on phosphorus–nitrogen synergism promote the high flame retardancy of POM to reach the nonflammability of V‐0 rating. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Phosphorus‐Containing Polymer Flame Retardants for Aliphatic Polyesters

Polyesters with 9,10‐dihydro‐9‐oxy‐10‐phosphaphenanthrene‐10‐oxide‐containing comonomers are synthesized aiming to improve the flame retardancy of aliphatic polyesters such as poly(butylene succinate) and poly(butylene sebacate). The influence of the chemical structure on the thermal decomposition and pyrolysis is examined using a combination of thermogravimetric analysis (TGA), TGA‐Fourier transform infrared (FTIR) spectroscopy, pyrolysis‐gas chromatography/mass spectrometry, and microscale combustion flow calorimetry. Thermal decomposition pathways are derived and used to select suitable candidates as flame retardants for PBS. The fire behavior of the selected polymers is evaluated by forced‐flaming combustion in a cone calorimeter. The materials show two modes of action for flame retardancy: strong flame inhibition due to the release of a variety of molecules combined with charring in the solid state.     

Fatigue and hysteresis behavior of halloysite nanotubes‐filled natural rubber (SMR L and ENR 50) nanocomposites

The effect of various halloysite nanotubes (HNTs) loading on fatigue life, stress–strain behavior, and hysteresis of HNTs/Standard Malaysian Rubber (SMR) L and HNTs/epoxidized natural rubber (ENR) 50 nanocomposites were studied. The addition of HNTs caused decrement in fatigue life for both nanocomposites at any extension ratio. Generally, HNTs/SMR L nanocomposites showed higher fatigue life than ENR 50 nanocomposites. Addition of more HNTs caused decrement of stress for HNTs/SMR L nanocomposites, whereas HNTs/ENR 50 nanocomposites showed vice versa at any strain. This result was supported by the graph of accumulated strain energy against extension ratio. Hysteresis values increased with addition of HNTs in both nanocomposites where of HNTs/ENR 50 nanocomposites exhibited higher hysteresis than HNTs/SMR L nanocomposites at any HNTs loading. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Loading the polyol carbonization agent into clay nanotubes for the preparation of environmentally stable UV‐cured epoxy materials

The halloysite nanotubes (HNTs) were loaded with pentaerythritol (PER). The as‐prepared composite (HNT‐P) and ammonium polyphosphate (APP) was subsequently added to the UV‐curable epoxy resins, giving a new flame‐resistant system. Loading of the hydrophilic PER into HNT can reduce the moisture absorption in the UV‐curable epoxy resins. The flame retardancy was evaluated by means of the cone calorimeter and limit oxygen index test. The results showed that the flame retardancy of the modified epoxy resin was greatly improved with an obvious decrease in both the heat release and smoke release. Moreover, it was revealed that HNT could catalyze the reaction of APP and PER, and the burning surface of the epoxy resin should be covered by the polyphosphoric‐HNT intumescent char layer. We have measured the moisture sorption and dynamic mechanical properties of the UV‐cured epoxy resins. As compared to the use of the simple mixture of PER and HNT, the use of the HNT‐P nearly kept the storage modulus at about 1809 Mpa and reduced the moisture absorption by 58.2 wt % at 40 °C. The results proved that the addition of the HNT‐P obtained lower moisture absorption and higher stability of the mechanical properties than adding the simple mixture. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45045.