Influence of the processing methods on the properties of poly(lactic acid)/halloysite nanocomposites

The influence of processing methods on the thermo‐mechanical properties of poly (lactic acid) (PLA) nanocomposites were investigated by preparing nanocomposites reinforced by halloysite nanotubes (HNTs) (from 0 to 10 [w/w%]) using solution casting (SC) and melt compounding (MC) methods. Statistical analysis revealed that the processing methods have a significant influence on the tensile properties, where nanocomposites prepared by MC have higher tensile properties compared to those by SC. Experimental results illustrated higher tensile strength and a drop in ductility under the higher strain rate as compared to the low strain rate for PLA/HNTs nanocomposites. At lower concentrations micrographs revealed that, HNTs dispersion was better for SC films as compared to MC, but more prominent HNTs aggregation at higher loadings. MC nanocomposites exhibited a high crystallinity as compared to SC, due to the recrystallization and nucleation effects. The thermal stability and activation energy increased with addition of HNTs, regardless of the processing methods. POLYM. COMPOS., 37:861–869, 2016. © 2014 Society of Plastics Engineers     

Simultaneous improvement in strength,toughness, and thermal stability of epoxy/halloysite nanotubes composites by interfacial modification

This work investigated the effect of silane modification of halloysite nanotubes (HNTs) on the mechanical properties of epoxy/HNTs nanocomposites. Three kinds of silane coupling agents, including 3‐(2‐aminoethyl)‐aminopropyltrimethoxysilane (AEAPS), (3‐glycidyloxypropyl)‐trimethoxysilane (GPTMS), and octyltriethoxysilane (OTES), were employed. It was shown that the modified HNTs exhibited a better dispersion in the epoxy matrix compared with pristine one. Because of strong interfacial interaction between AEAPS modified HNTs and the epoxy matrix, the nanocomposites exhibited the highest glass transition temperature and modulus among all the samples. On the other hand, AEAPS and GPTMS modified HNTs/epoxy nanocomposites showed enhanced tensile strength and toughness. The toughing mechanisms were identified by the SEM micrographs of the fracture surfaces of the different kinds of samples. In this study, simultaneous enhancement of strength, toughness, and thermal stability of epoxy by the modified HNTs provides a novel approach to produce high‐performance thermosets. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43249.     

Mechanical,thermal, and structural properties of uniaxially drawn polylactic acid/halloysite nanocomposites

The effect of solid-state drawing at different conditions including drawing ratio (DR), drawing temperature (DT), and drawing speed (DS) on mechanical, thermal, and structural properties of polylactic acid (PLA)/halloysite nanotubes (HNTs) composites were studied. PLA/HNTs composite films were prepared by melt mixing process followed by compression molding. Subsequently, drawing was performed using a tensile testing machine. Field emission scanning electron microscopy confirmed alignment and orientation of polymer chains and HNTs after stretching. Thermal and mechanical analysis of the drawn films revealed that glass transition temperature, crystallinity, ultimate tensile strength, and Young's modulus were enhanced by increasing DR, DT, and DS. However, toughness was decreased by increasing DR and DS and increased by increasing DT. In addition, the drawn nanocomposites showed superior mechanical and thermal properties compared to the drawn neat PLA films indicating the high efficiency of solid-state drawing and positive effect of HNTs. Therefore, this study could be helpful to introduce an approach to enhance the properties of biopolymers and renewable polymers by uniaxial drawing.     

Surface‐modified halloysite nanotubes reinforced poly(lactic acid) for use in biodegradable coronary stents

Poly(lactic acid) (PLA) was reinforced halloysite nanotubes (HNTs) in this study. To improve dispersion and interfacial adhesion of HNTs within the PLA matrix, HNTs were surface modified with 3‐aminopropyltriethoxysilane (ASP) prior to compounding with PLA. PLA/ASP‐HNTs nanocomposites were characterized by differential scanning calorimetry (DSC), Fourier transfer infrared spectroscopy (FTIR), surface wettability, thermogravimetric analysis, transmission electron microscopy (TEM), and tensile testing. The hemocompatibility and cytocompatibility of PLA and PLA composites were investigated and the in vitro degradation process of PLA/ASP‐HNTs composites was investigated for a period of 6 months by gel permeation chromatography, FTIR, weight loss measurement, DSC, and tensile testing. PLA and all PLA composites were blood compatibile and non‐cytotoxic. TEM analysis revealed that HNTs agglomeration in PLA matrix was reduced by surface treatment with ASP. ASP‐HNTs had better reinforcing effect than unmodified HNTs evidenced by tensile testing. ASP‐HNTs appeared to increase the hydrolytic degradation process as measured by weight measurement. PLA/ASP‐HNTs composites displayed 12.1% weight loss and 30.6% average molecular weight reduction while retaining 74% of Young's modulus by the 24th week of degradation. Based on this data, the reinforcement of PLA using ASP‐HNTs may prove beneficial for applications such as biodegradable stents. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46521.     

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     

Comparison of the effect of carbon,halloysite and titania nanotubes on the mechanical and thermal properties of LDPE based nanocomposite films

In this study, titania nanotubes(TNTs) were prepared by hydrothermal method with the aim to compare the properties of these one-dimensional tubular nanostructures' reinforced nanocomposites with the carbon and halloysite nanotubes'(CNTs and HNTs, respectively) reinforced nanocomposites. Low density polyethylene(LDPE) was used as the matrix material. The prepared nanocomposites were characterized and compared by means of their morphological, mechanical and thermal properties. SEM results showed enhanced interfacial interaction and better dispersion of TNTs and HNTs into LDPE with the incorporation of a MAPE compatibilizer,however, these interactions seem to be absent between CNTs and LDPE, and the CNTs remained agglomerated.Contact angle measurements revealed that CNT filled nanocomposites are more hydrophilic than HNT composites, and less than TNT composites. CNTs provided better tensile strength and Young's modulus than HNT and TNT nanocomposites, a 42% increase in tensile strength and Young's modulus is achieved compared to LDPE.Tear strength improvement was noticed in the TNT composites with a value of 35.4 N·mm~(-1), compared to CNT composites with a value of 25.5 N·mm~(-1)·s~(-1). All the prepared nanocomposites are more thermally stable than neat LDPE and the best improvement in thermal stability was observed for CNT reinforced nanocomposites.CNTs depicted the best improvement in tensile and thermal properties and the MAPE compatibilizer effectiveness regarding morphological. mechanical and thermal properties was only observed for TNT and HNT systems.     

Effects of halloysite nanotubes on the properties of polypropylene/(recycled natural rubber gloves)/(halloysite nanotubes composites)

The polypropylene/(recycled natural rubber gloves)/(halloysite nanotubes) (PP/rNRg/HNTs) composites were prepared by using an internal mixer. The effect of HNTs loading on processibility, tensile properties, thermal stability, and morphology of PP/rNRg/HNTs composites were investigated. The stabilization torque increased with HNTs loading. Two parts by weight per hundred parts of resin of HNTs‐filled PP/rNRg/HNTs composites shows the highest tensile strength. The scanning electron micrographs show good dispersion of HNTs and good filler‐matrix interaction, particularly at 2 parts by weight per hundred parts of resin of HNTs. The incorporation of HNTs also improved the thermal stability of PP/rNRg/HNTs composite. J. VINYL ADDIT. TECHNOL., 22:487–491, 2016. © 2015 Society of Plastics Engineers     

Compatibilizing effect of halloysite nanotubes in polar–nonpolar hybrid system

This article explores the effect of halloysite nanotubes (HNTs) and modified HNTs (M‐HNTs) on the properties of immiscible blend system based on polar polyoxymethylene (POM) and nonpolar polypropylene (PP) polymers. HNTs have been modified by N‐(β‐aminoethyl)‐γ‐aminopropyltrimethoxysilane (APTMS). Modification is confirmed by Fourier transform infrared spectroscopy (FTIR), also FTIR confirms the interaction between polymer blend and HNTs/M‐HNTs. Morphology of the nanocomposites are demonstrated by scanning electron microscope (SEM) and dispersion of HNTs/M‐HNTs are observed by transmission electron microscope (TEM). In nanocomposites, average dispersed domain sizes reduce in the presence of HNTs/M‐HNTs but significant reduction has been observed in the case of M‐HNT‐filled nanocomposites rather than unmodified HNT‐filled nanocomposites. The M‐HNT acts as a reinforcing agent as well as bridging tool in polar–nonpolar hybrid system. Modification of HNTs brings compatibility in between the blend partners and reveals improved dynamic mechanical, thermal, and tensile properties than that of the pure blend system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39587.     

Ethylene vinyl acetate copolymer/halloysite nanotubes nanocomposites with enhanced mechanical and thermal properties

Ethylene vinyl acetate (EVA) nanocomposites filled with halloysite nanotubes (HNTs) were prepared by melt compounding. The homogenous dispersion of HNTs into the EVA matrix was evaluated by SEM and TEM analysis. The addition of HNTs does not influence on the phase separation structure and crystallinity of EVA nanocomposites. Due to the reinforcing effect of HNTs embedded in the EVA elastomer matrix, along with an increase of HNTs concentration, the improvement in tensile properties, by means of modulus at an elongation of 100% and tensile strength, was observed. It was found that tensile strength increased by 27% for EVA nanocomposite with 8 wt% of the HNTs. The values of elongation at break at low HNTs' loading increase and subsequently at higher loading are comparable to the neat EVA copolymer. The elastic deformability and reversibility of the EVA nanocomposites with different HNTs content was analyzed. The cyclic tensile tests showed that prepared nanocomposites have values of permanent set slightly higher than for neat EVA copolymer. Furthermore, the limiting oxygen index value for the EVA based nanocomposite with the highest HNTs content (8 wt%) increased from 19.5 to 24.8%. The results show, that thermo-oxidative stability were improved by the incorporation of HNTs into EVA copolymer matrix.     

Effect of partial replacement of chitosan with halloysite nanotubes on the properties of polylactic acid hybrid biocomposites

In this study, hybrid chitosan/halloysite nanotubes (Cs/HNTs) reinforced polylactic acid (PLA) were prepared via melt compounding and compression molding techniques. In the fabrication of PLA/Cs/HNTs hybrid biocomposites, the partial replacement of Cs with HNTs was performed at filler loading of 2.5 parts per hundred parts of polymer (php), proceeding from the highest tensile strength of PLA/Cs obtained in our previous study. Cs was partially replaced with different HNTs loadings (0.5, 1, 1.5, 2, and 2.5) php and its effects on the functional group, thermal, tensile, morphological, and water absorption properties were investigated systematically. The results revealed that the combined loading of 1 php Cs and 1.5 php HNTs hybrid fillers into PLA showed the best performance in all properties. Fourier transform infrared spectroscopy (FTIR) analysis indicated that the siloxane (Si O) group of HNTs had chemically interacted with the amine group of Cs. The thermal analysis demonstrated that partial replacement of Cs with 1.5 php HNTs improved the thermal stability of PLA/2.5Cs/0HNTs biocomposite by ~12%. Yet, the percentage of crystallinity (χ_c) reduced with HNTs addition due to the phase adhesion improvement. Moreover, PLA/1Cs/1.5HNTs hybrid biocomposites showed the highest tensile strength and elongation at break of 59 MPa and 2.72%, respectively. This correlated with the uniform dispersion and better interfacial adhesion between Cs/HNTs fillers in the PLA matrix, as confirmed by the field emission scanning electron microscopy (FESEM). In addition, partial replacement of Cs with HNTs exhibited a lower water absorption percentage, which suggested the advantage of hybrid fillers to reduce water uptake, and is beneficial in a wide range of applications.     

Poly(vinylidene fluoride)/halloysite nanotubes nanocomposites: The structures,properties, and tensile fracture behaviors

Poly(vinylidene fluoride)/halloysite nanotubes (HNTs) nanocomposites with good dispersion were prepared. The effect of HNTs on the crystalline structure, dynamic rheological properties, dynamic mechanical properties, and tensile properties was investigated. Results showed that at low concentration, the effect of HNTs on the modulus was minor. However, at high concentration, improvement of the modulus can be observed. The tensile fracture behaviors were investigated, which showed that the addition of HNTs changed the fracture mode. When the concentration of HNTs was 20 phr, a fracture mode change from microductility/brittle to brittle/fibrillation occurred. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study of mechanical and dynamic mechanical behavior of halloysite nanotube-reinforced multiscale syntactic foam

The present study deals with the development of novel cenosphere-epoxy multiscale syntactic foam (MSF) reinforced with halloysite nanotubes (HNTs). Cenospheres with different volume fractions (0, 20, 30, 40, 50 vol%) and HNTs (1 vol%) used in the fabrication of syntactic foams. The addition of HNTs increases the tensile modulus (42%) and flexural modulus (66%) compared with plain syntactic foam (PSF). Furthermore, FTIR studies reveal the strong hydrogen bonding interaction between HNTs and epoxy. Field emission scanning electron microscopy (FESEM) confirms the unique crack deflection phenomenon by HNT, which indicates the structure–property correlation. In addition, the storage and loss modulus of MSFs is 36 and 113%, respectively (at 30°C) higher than the neat epoxy. Improvement in the tensile and flexural properties along with excellent thermal stability at elevated temperature makes MSF a promising material for structural, weight-sensitive, and high-temperature applications.     

Influence of rubber content on mechanical,thermal, and morphological behavior of natural rubber toughened poly(lactic acid)–multiwalled carbon nanotube nanocomposites

The effects of natural rubber (NR) on the mechanical, thermal, and morphological properties of multiwalled carbon nanotube (CNT) reinforced poly(lactic acid) (PLA) nanocomposites prepared by melt blending were investigated. A PLA/NR blend and PLA/CNT nanocomposites were also produced for comparison. The tensile strength and Young's modulus of PLA/CNT nanocomposites improved significantly, whereas the impact strength decreased compared to neat PLA. The incorporation of NR into PLA/CNT significantly improved the impact strength and elongation at break of the nanocomposites, which showed approximately 200% and 850% increases at 20 wt % NR, respectively. However, the tensile strength and Young's modulus of PLA/NR/CNT nanocomposites decreased compared to PLA/CNT nanocomposites. The morphology analysis showed the homogeneous dispersion of NR particles in PLA/NR/CNT nanocomposites, while CNTs preferentially reside in the NR phase rather than the PLA matrix. In addition, the incorporation of NR into PLA/CNT lowered the thermal stability and glass‐transition temperature of the nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44344.     

聚丙烯基高含量埃洛石纳米管复合材料的制备和性能

采用双螺杆挤出机制备聚丙烯(PP)基高含量(33 phr)埃洛石纳米管(HNTs)复合材料,从挤出机沿程3个位置和机头出口处取样,观察样品的微观结构并测试其流变性能和热稳定性。结果表明,本文设置的螺杆结构提供的分散和分布混炼使PP/HNTs复合材料中HNTs团聚体的尺寸快速减小,HNTs在PP基体中分散得越来越均匀,使挤出机沿程3个位置所取复合材料样品的低频区储能模量逐渐提高、末端斜率逐渐降低、松弛时间逐渐变长。机头入口所取复合材料样品的热稳定性要比机头出口样品的高,这归因于前者样品中较为无序且较均匀排列的HNTs纳米空腔能更有效地诱捕降解产物。     

Preparation of waterborne polyurethane nanocomposite reinforced with halloysite nanotubes for coating applications

To construct waterborne polyurethane with excellent water resistance and mechanical properties, an organic‐inorganic hybrid nanocomposite based on modified halloysite nanotubes (mHNTs) and polyurethane was prepared. The HNTs were modified with an amino‐silane coupling agent (KH550) and then reacted with polypropylene glycol, 2,2‐Dimethylol propionic acid, and Toluene diisocyanate to form mHNTs/PU aqueous dispersions. The structure of the siloxane functionalized mHNTs was confirmed by a Fourier transform infrared study. The PU/mHNTs composites were characterized by using differential scanning calorimetry, scanning electronic microscopy, thermal gravimetric analysis, a tensile test, particle size analysis, and a water swelling experiment. The tensile strength, Young's modulus, and elongation at the break of the composite polymer with 0.5 wt % mHNTs was shown to be significantly improved, by approximately 200%, 200%, and 30%, respectively. An excess amount of mHNTs could weaken the reinforcing effect and stability of the composite emulsion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43949.     

Mechanical and thermal properties of SEBS‐g‐MA compatibilized halloysite nanotubes reinforced polyethylene terephthalate/polycarbonate/nanocomposites

In this study, the effect of maleic anhydride grafted styrene‐ethylene‐butylene‐styrene (SEBS‐g‐MA) content on mechanical, thermal, and morphological properties of polyethylene terephthalate/polycarbonate/halloysite nanotubes (PET/PC/HNTs) nanocomposites has been investigated. Nanocomposites of PET/PC (70 : 30) with 2 phr of HNTs were compounded using the counter rotating twin screw extruder. A series of formulations were prepared by adding 5–20 phr SEBS‐g‐MA to the composites. Incorporation of 5 phr SEBS‐g‐MA into the nanocomposites resulted in the highest tensile and flexural strength. Maximum improvement in the impact strength which is 245% was achieved at 10 phr SEBS‐g‐MA content. The elongation at break increased proportionately with the SEBS‐g‐MA content. However, the tensile and flexural moduli decreased with increasing SEBS‐g‐MA content. Scanning electron microscopy revealed a transition from a brittle fracture to ductile fracture morphology with increasing amount of SEBS‐g‐MA. Transmission electron microscopy showed that the addition of SEBS‐g‐MA into the nanocomposites promoted a better dispersion of HNTs in the matrix. A single glass transition temperature was observed from the differential scanning calorimetry test for compatibilized nanocomposites. Thermogravimetric analysis of PET/PC/HNTs nanocomposites showed high thermal stability at 15 phr SEBS‐g‐MA content. However, on further addition of SEBS‐g‐MA up to 20 phr, thermal stability of the nanocomposites decreased due to the excess amount of SEBS‐g‐MA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42608.     

Water-assisted extrusion as a novel processing route to prepare polypropylene/halloysite nanotube nanocomposites: Structure and properties

Naturally occurring halloysite nanotubes (HNTs) are used to prepare Polypropylene (PP)/HNTs nanocomposites using a novel “one step” water-assisted extrusion process with and without the use of a PP-graft-maleic anhydride (PP-g-MA) as compatibilizer. In order to analyze the influence of PP-g-MA and/or water injection on the HNTs dispersion and therefore on nanocomposite properties, structural analysis (SEM and TEM) is combined with rheological and thermo-mechanical experiments. The best clay dispersion is obtained when compatibilizer and water injection are combined together (synergistic effect). As a consequence, the linear viscoelastic properties and the dynamic storage modulus are dramatically enhanced for this system. A mechanism explaining the interaction between HNTs and PP-g-MA in presence of water is proposed. The thermal stability and flame retardant property are also investigated. Thermal analyses reveal two opposite effects of HNTs on the thermal behaviour of PP. A surface catalytic action of the halloysite speeds up thermal degradation of PP. However, this effect is reduced with improved HNTs dispersion, presumably via an entrapment mechanism of the decomposition products inside the lumens. Finally, cone calorimeter results show that low flammability of nanocomposites is only achieved when combining water injection and PP-g-MA. In view of these results, PP/HNTs nanocomposites prepared using this novel processing route are promising candidates for flame retardant applications.     

Properties of Halloysite Nanotube (HNT) Filled SMR L and ENR 50 Nanocomposites

Various HNTs loading filled SMR L and ENR 50 were prepared. Addition of HNTs caused increments in scorch time, cure time, tensile modulus, and thermal stability of nanocomposites. Optimum tensile strength of nanocomposites was achieved at 20 phr loading. Elongation at break, swelling percentage, and fatigue life decreased with increasing HNTs loading. ENR 50 nanocomposites show shorter scorch time, longer cure time, and lower curing rate index than SMR L nanocomposites. ENR 50 nanocomposites also show higher tensile modulus and thermal stability than SMR L nanocomposites. SEM images show that HNTs can be dispersed more uniformly at lower filler loading.     

Facile hydroxylation of halloysite nanotubes for epoxy nanocomposite applications

Polymer nanocomposites have been extensively investigated over the past two decades, resulting in a wide range of applications because of their excellent performance. Halloysite, a type of naturally occurring aluminosilicate, has attracted increasing interest in polymer nanocomposite applications, especially for the enhancement of mechanical properties owing to its tubular structure. Herein, we report a facile approach to achieve a high level of dispersion of halloysite nanotubes (HNTs) in epoxy by treating HNTs with a low concentration of sodium hydroxide (NaOH). The NaOH treatment resulted in the formation of hydroxyl groups on the surface of HNTs, leading to a much higher level of dispersion of HNTs in water, organic polar solvents, and epoxy matrix. The higher density of external silanol groups (Si–OH) of hydroxylated HNTs (h-HNTs) was confirmed by X-ray photoelectron spectroscopy (XPS) characterization. Such a higher level of dispersion and stronger interface led to simultaneous enhancement in both the stiffness and the toughness of epoxy/h-HNT nanocomposites. Systematic characterizations were performed to investigate the related stiffening and toughening mechanism. The implication of the present findings is discussed.     

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。