High thermal conductive m‐xylylenediamine functionalized multiwall carbon nanotubes/epoxy resin composites

In this study, multiwall carbon nanotubes (MWNTs) functionalized by m‐xylylenediamine is used as thermal conductive fillers to improve their dispersibility in epoxy resin and the thermal conductivity of the MWNTs/bisphenol‐A glycidol ether epoxy resin composites. Functionalization with amine groups of MWNTs is achieved after such steps as carboxylation, acylation and amidation. The thermal conductivity, impact strength, flexural strength, and fracture surfaces of MWNTs/epoxy composites are investigated with different MWNTs. The results show that m‐xylylenediamine is successfully grafted onto the surface of the MWNTs and the mass fraction of the organic molecules grafted onto MWNTs is about 20 wt %. The thermal conductivity of MWNTs/epoxy composites is further enhanced to 1.236 W/mK with 2 wt % m‐MWNTs. When the content of m‐MWNTs is 1.5 wt %, the impact strength and flexural strength of the composites are 25.85 KJ/m², 128.1 MPa, respectively. Scanning electron microscope (SEM) results show that the fracture pattern of composites is changed from brittle fracture to ductile fracture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41255.     

Thermal and electrical conductivity of melt mixed polycarbonate hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this work, we present thermoplastic nanocomposites of polycarbonate (PC) matrix with hybrid nanofillers system formed by a melt‐mixing approach. Various concentrations of multi‐walled carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were mixed in to PC and the melt was homogenized. The nanocomposites were compression molded and characterized by different techniques. Torque dependence on the nanofiller composition increased with the presence of carbon nanotubes. The synergy of carbon nanotubes and GnP showed exponential increase of thermal conductivity, which was compared to logarithmic increase for nanocomposite with no MWCNT. Decrease of Shore A hardness at elevated loads present for all investigated nanocomposites was correlated with the expected low homogeneity caused by a low shear during melt‐mixing. Mathematical model was used to calculate elastic modulus from Shore A tests results. Vicat softening temperature (VST) showed opposite pattern for hybrid nanocomposites and for PC‐MWCNT increasing in the latter case. Electrical conductivity boost was explained by the collective effect of high nanofiller loads and synergy of MWCNT and GnP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42536.     

Preparation and characterization of P(AN‐co‐VA‐co‐DEMA) fibers coated with multiwalled carbon nanotubes by electrostatic interactions

P(AN‐co‐VA‐co‐DEMA) terpolymers were synthesized by aqueous precipitation copolymerization of acrylonitrile (AN), vinyl acetate (VA), and 2‐dimethylamino ethyl methacrylate (DEMA) with an Na₂S₂O₅–NaClO₃ redox initiating system and fibers from these terpolymers were thus prepared by a wet spinning method. Functionalized multiwalled carbon nanotube (F‐MWNT) networks were created on the surface of P(AN‐co‐VA‐co‐DEMA) fibers by a simple dipping method. The morphology and interfacial interactions of the obtained F‐MWNTs‐coated fibers were characterized by scanning electron microscope, Raman spectroscopy, and Fourier transform infrared spectroscopy. The results showed that F‐MWNTs were assembled on the fibers and the density of F‐MWNTs can be controlled by adjusting the F‐MWNTs content in the dipping solution. The assembly process was driven by electrostatic interactions between the negative charges on the nanotube sidewalls and the positive charges of the fibers. The F‐MWNTs‐coated fibers had a good conductivity. The volume resistivity of the fibers coated with 1.18 wt % F‐MWNTs reached 0.27 Ω·cm, while the original mechanical properties were preserved. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42545.     

Functionalization of carbon nanotubes with (3‐glycidyloxypropyl)‐trimethoxysilane: Effect of wrapping on epoxy matrix nanocomposites

In this work, multiwalled carbon nanotubes (MWCNT), after previous oxidation, are functionalized with excess (3‐glycidyloxypropyl)trimethoxysilane (GLYMO) and used as reinforcement in epoxy matrix nanocomposites. Infrared, Raman, and energy‐dispersive X‐ray spectroscopies confirm the silanization of the MWCNT, while transmission electron microscopy images show that oxidized nanotubes presented less entanglement than pristine and silanized MWCNT. Thickening of the nanotubes is also observed after silanization, suggesting that the MWCNT are wrapped by siloxane chains. Field‐emission scanning electron microscopy reveals that oxidized nanotubes are better dispersed in the matrix, providing nanocomposites with better mechanical properties than those reinforced with pristine and silanized MWCNT. On the other hand, the glass transition temperature of the nanocomposite with 0.05 wt % MWCNT‐GLYMO increased by 14 °C compared to the neat epoxy resin, suggesting a strong matrix–nanotube adhesion. The functionalization of nanotubes using an excess amount of silane can thus favor the formation of an organosiloxane coating on the MWCNT, preventing its dispersion and contributing to poor mechanical properties of epoxy nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44245.     

Reduced graphene oxide/carbon nanotubes nanohybrids as preformed reinforcement for polystyrene composites

Three‐dimensional carbon nanohybrids constructed by reduced graphene oxide (rGO) and carbon nanotubes (CNTs) are prepared via simultaneous hydrothermal and chemical reduction reactions. The macroscopic rGO/CNTs monolith is used as the preformed reinforcement for polystyrene (PS) composites to function as the continuous conductive pathway. During hydrothermal reaction, interconnected network consisting of rGO and CNTs, driven by the hydrophobic and π‐π interactions, is formed and then frozen by the following freeze‐drying processing. Fourier transform infrared and X‐ray diffraction results confirm that CNTs play an important role in tuning the amphiphilicity and pore structure of the as‐prepared rGO/CNTs nanohybrids. rGO/CNTs/PS composites prepared via vacuum‐assisted impregnation process exhibit the highest electrical conductivity of 1.21 × 10^?3 S m^?1, which is 11 orders of magnitude higher than that of neat PS. The functional synergies of rGO and CNTs are identified to establish an efficient route for improving the electrical property of polymer based composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45054.     

In vitro toxicity evaluation of hydrogel–carbon nanotubes composites on intestinal cells

Composite materials based on carbon nanotubes (CNT) and polymeric hydrogels have become the subject matter of major interest for use as carriers in drug delivery research. The aim of this study was to evaluate the in vitro cytotoxicity of the hydrogel–carbon nanotube–chitosan (hydrogel–CNT–CH) composites on intestinal cells. Oxidized CNT were wrapped with chitosan (CH), Fourier transform infrared (FT‐IR) analysis suggest that oxidized CNT interact with CH. Transmission electron microscopy (TEM) images show a CH layer lying around CNT. Chitosan wrapped CNT were incorporated to poly (acrylamide‐co‐acrylic acid) hydrogels. Swelling behavior in buffers at different pH were evaluated and revealed a significantly lower swelling when it is exposed to a acid buffer solution (pH 2.2). Mechanical properties were evaluated by measurements of elasticity and the material with CNT showed better mechanical properties. The incorporation and liberation of Egg Yolk Immunoglobulin from hydrogel–CNT–CH were also assessed and it revealed an improved performance. To evaluate the effect of these nanocomposites on cellular redox balance, intestinal cells were exposed to hydrogel–CNT–CH composites and antioxidant enzymes were assessed. Cytotoxicity and apoptosis were also evaluated. Hydrogel–CNT–CH composites induce no oxidative stress and there were no evidence of cytotoxicity or cell death. These preliminary findings suggest that hydrogel–CNT–CH composites show improved properties and good biocompatibility in vitro making these biomaterials promising systems for drug delivery purposes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41370.     

Morphology,thermal, and electrical properties of polypropylene hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this study, nanocomposites of polypropylene (PP) with various loadings of multi‐wall carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were formed by masterbatch dilution/mixing approach from individual masterbatches PP‐MWCNT and PP‐GnP. Melt mixing on a twin‐screw extruder at two different processing temperatures was followed by characterization of morphology by transmitted‐light microscopy including the statistical analysis of agglomeration behavior. The influence of processing temperature and weight fractions of both nanofillers on the dispersion quality is reported. Thermal properties of the nanocomposites investigated by DSC and TGA show sensitivity to the nanofillers weight fraction ratio and to processing conditions. Electrical conductivity is observed to increase up to an order of magnitude with the concentration of each nanofiller increasing from 0.5 wt % to 1.0 wt %. This is related with a decrease of electrical conductivity observed for unequal concentration of both nanofillers. This particular behavior shows the increase of electrical properties for higher MWCNT loadings and the increase of thermo‐mechanical properties for higher GnP loadings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42793.     

Effects of amino‐functionalized carbon nanotubes on the properties of amine‐terminated butadiene–acrylonitrile rubber‐toughened epoxy resins

Amino‐functionalized multiwalled carbon nanotubes (MWCNT‐NH₂s) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with amine‐terminated butadiene–acrylonitrile (ATBN). The curing kinetics, glass‐transition temperature (T_g), thermal stability, mechanical properties, and morphology of DGEBA/ATBN/MWCNT‐NH₂ nanocomposites were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis, a universal test machine, and scanning electron microscopy. DSC dynamic kinetic studies showed that the addition of MWCNT‐NH₂s accelerated the curing reaction of the ATBN‐toughened epoxy resin. DSC results revealed that the T_g of the rubber‐toughened epoxy nanocomposites decreased nearly 10°C with 2 wt % MWCNT‐NH₂s. The thermogravimetric results show that the addition of MWCNT‐NH₂s enhanced the thermal stability of the ATBN‐toughened epoxy resin. The tensile strength, flexural strength, and flexural modulus of the DGEBA/ATBN/MWCNT‐NH₂ nanocomposites increased increasing MWCNT‐NH₂ contents, whereas the addition of the MWCNT‐NH₂s slightly decreased the elongation at break of the rubber‐toughened epoxy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40472.     

Poly(styrene–maleic anhydride) functionalized graphene oxide

In this study, poly(styrene–maleic anhydride) functionalized graphene oxide (SMAFG) was fabricated with in situ polymerization. The sample was characterized with Raman spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, and ultraviolet–visible absorption. The results of the experiments show that the thermal stability of SMAFG was improved significantly, and it also possessed a good dispersion in N,N‐dimethylformamide, N,N‐dimethylacetamide, aniline, and certain organic solvents. The calculated Hildebrand parameter of SMAFG was 23.8 MPa^1/2. This new method will broaden the applications of graphene, and the experiment showed that it could effectively improve the strength of polyamide 6 (PA6) compared with the pure PA6 fiber. The tensile strength of the SMAFG/PA6 composite fiber improved 29%, and the Young's modulus improved 33%, so this kind of functionalized graphene oxide can be used in the preparation of polymeric composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41987.     

High performance polyurethane composites with isocyanate‐functionalized carbon nanotubes: Improvements in tear strength and scratch hardness

A microwave‐assisted functionalization of carbon nanotubes (CNTs) with isocyanate groups allowed a reduction of functionalization time from 24 h to 30 min with no change in the degree of functionalization or in the nanotube characteristics. Polymer nanocomposites with enhanced mechanical properties were obtained because of the tailored interface by the covalent linkage between the surface‐modified multiwalled‐carbon nanotubes (MWCNTs) and an elastomeric polyurethane (PUE) matrix. The mechanical data revealed that the composite containing 0.25 wt % of MWCNT‐NCO showed an increase of 31% in tear strength and 28% in static toughness. A good adhesion between the matrix and individually dispersed nanotubes was observed in the scanning electron microscopy and transmission electron microscopy images. Nanoindentation and nanoscratch experiments were conducted to investigate the properties on the sub‐surface. An increase by a factor of 3 in the scratch hardness was observed for the composite with 0.50 wt % of MWCNT‐NCO with respect to the neat PUE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44394.     

Thermally exfoliated graphene oxide reinforced fluorinated pentablock poly(l‐lactide‐co‐ε‐caprolactone) electrospun scaffolds: Insight into antimicrobial activity and biodegradation

Three‐dimensional fluorinated pentablock poly(l ‐lactide‐co‐ε‐caprolactone)‐based scaffolds were successfully produced by the incorporation of thermally exfoliated graphene oxide (TEGO) as an antimicrobial agent with an electrospinning technique. In a ring‐opening polymerization, the fluorinated groups in the middle of polymer backbone were attached with a perfluorinated reactive stabilizer having oxygen‐carrying ability. The fiber diameter and its morphologies were optimized through changes in TEGO amount, voltage, polymer concentration, and solvent type to obtain an ideal scaffold structure. Instead of the widely used graphene oxide synthesized by Hummer's method, TEGO sheets having a low amount of oxygen produced by thermal expansion were integrated into the fiber structure to investigate the effect of the oxygen functional groups of TEGO sheets on the degradation and antimicrobial activity of the scaffolds. There was no antimicrobial activity in TEGO‐reinforced scaffolds in the in vitro tests in contrast to the literature. This study confirmed that a low number of oxygen functional groups on the surface of TEGO restricted the antimicrobial activity of the fabricated composite scaffolds. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43490.     

Epoxy/p‐phenylenediamine functionalized graphene oxide composites and evaluation of their fracture toughness and tensile properties

In an attempt to enhance the mechanical properties of epoxy/graphene‐based composites, the interface was engineered through the functionalization of graphene oxide (GO) sheets with p‐phenylenediamine; this resulted in p‐phenylenediamine functionalized graphene oxide (GO–pPDA). The morphology and chemical structure of the GO–pPDA sheets were studied by spectroscopic methods, thermal analysis, X‐ray diffraction, and transmission electron microscopy. The characterization results show the successful covalent functionalization of GO sheets through the formation of amide bonds. In addition, p‐phenylenediamine were polymerized on graphene sheets to form crystalline nanospheres; this resulted in a GO/poly(p‐phenylenediamine) hybrid. The mechanical properties of the epoxy/GO–pPDA composite were assessed. Although the Young's modulus showed improvement, more significant improvements were observed in the strength, fracture strain, and plane‐strain fracture toughness. These improvements were attributed to the unique microstructure and strong interface between GO–pPDA and the epoxy matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43821.     

Simultaneous enhancements in the mechanical,thermal, and electrical performances of glass‐fiber‐reinforced cyanate ester/epoxy composites with plasma‐functionalized carbon nanotubes at different temperatures

Woven glass‐fiber‐reinforced cyanate ester/epoxy composites modified with plasma‐functionalized multiwalled carbon nanotubes (MWCNTs) were prepared. The mechanical, thermal, and electrical properties of the composites were investigated at different temperatures. The results show that the interlaminar shear strength, thermal conductivity, and electrical conductivity of the composites at room temperature and the cryogenic temperatures were enhanced simultaneously by the incorporation of MWCNTs, whereas the nonconductive behavior of the composites as electrical insulating materials was not changed. Meanwhile, the reinforcing mechanism was also examined on the basis of the microstructure of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41418.     

Tailored dielectric and mechanical properties of noncovalently functionalized carbon nanotube/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) nanocomposites

The preparation of high‐dielectric poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) composites containing functionalized single‐walled carbon nanotubes (f‐SWCNTs) noncovalently appended with dibutyltindilaurate are reported herein. Transmission electron microscopy and X‐ray photoelectron and Raman spectroscopy confirmed the noncovalent functionalization of the SWCNTs. The SEBS‐f‐SWCNT composites exhibited enhanced mechanical properties as well as a stable and high dielectric constant of approximately 1000 at 1 Hz with rather low dielectric loss at 2 wt% filler content. The significantly enhanced dielectric property originates from the noncovalent functionalization of the SWCNTs that ensures good dispersion of the f‐SWCNTs in the polymer matrix. The f‐SWCNTs also acted as a reinforcing filler, thereby enhancing the mechanical properties of the composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improving thermal conductivity and shear strength of carbon nanotubes/epoxy composites via thiol‐ene click reaction

This study investigates the effect of the thiol‐ene click reaction on thermal conductivity and shear strength of the epoxy composites reinforced by various silane‐functionalized hybrids of sulfhydryl‐grafted multi‐walled carbon nanotubes (SH‐MWCNTs) and vinyl‐grafted MWCNTs (CC‐MWCNTs). The results of Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM) show that the sulfhydryl groups and vinyl groups are successfully grafted onto the surface of MWCNTs, after treatment of MWCNT with triethoxyvinylsilane and 3‐mercaptopropyltrimethoxysilane, respectively. Scanning electron microscopy (SEM), HotDisk thermal constant analyzer (HotDisk), optical microscope, and differential scanning calorimetry (DSC) are used to characterize the resultant composites. It is demonstrated that the hybrid of 75 wt % SH‐MWCNTs and 25 wt % CC‐MWCNTs has better dispersion and stability in epoxy matrix, and shows a stronger synergistic effect in improving the thermal conductivity of epoxy composite via the thiol‐ene click reaction with 2,2′‐azobis(2‐methylpropionitrile) as thermal initiator. Furthermore, the tensile shear strength results of MWCNT/epoxy composites and the optical microscopy photographs of shear failure section indicate that the composite with the hybrid MWCNTs has higher shear strength than that with raw MWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44579.     

Advanced ultra‐high molecular weight polyethylene/antioxidant‐functionalized carbon nanotubes nanocomposites with improved thermo‐oxidative resistance

Multiwalled carbon nanotubes (CNTs) functionalized with hindered phenol moieties are dispersed in ultra‐high molecular weight polyethylene (UHMWPE), and the stabilizing action of the antioxidant (AO) functionalized CNTs (AO‐f‐CNTs) is studied through a combination of rheological and spectroscopic (FT‐IR) analyses. The effectiveness of two alternative compounding methods, namely hot compaction (HC) and melt mixing (MM), is compared. The combination of high temperature and mechanical stress experienced during MM brings about noticeable degradation phenomena of the matrix already in the course of the compounding step. Differently, the milder conditions of the HC process preserve the stability of the polymer, making this method preferable when dealing with highly viscous matrices. In addition, HC guarantees a better CNT dispersion, allowing for the maximization of the stabilizing action of the AO grafted on the nanotubes. As a result, the HC samples exhibit improved thermo‐oxidative resistance despite the very low amount of AO grafted onto the CNTs. Besides demonstrating the effectiveness of our AO‐f‐CNTs as stabilizers for polymer matrices, our results prove that CNTs can serve as a support on which grafting specific functional molecules to be dispersed in a host polymer matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42420.     

Polysulfone‐based composite membranes with functionalized carbon nanotubes show controlled porosity and enhanced electrical conductivity

Composite membranes of functionalized (–COOH, –CONH₂, –N₃) carbon nanotubes/polysulfone (CNT/PS) synthesized by the phase‐inversion method show unique properties with respect to surface characteristics and the selective separation of metal ions from aqueous solution. Apart from the reduction in the pore size depending on the type of functionalities on the nanotubes, the pure water permeation could reach up to as high as ～600 L m^?2 h^?1 (LMH) at reduced pressures and could be due to the functionalized tips of the nanotubes on the membrane surface resulting from the phase inversion process used for the membrane fabrication. The membranes were characterized by small angle neutron scattering (SANS) to confirm the uniform distribution of the nanopores and the surface morphology of the membranes. Results show that rejection of Cu(II) was better than Pb(II) depending on the surface functionality. Interestingly, these membranes also showed enhanced conductivities in the range of 1.0 × 10^?2 S cm^?1, the conductivity depending on the type of functionality on the nanotubes, thus confirming the presence of functionalized nanotubes tips on the membrane surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43778.     

Interfacial crystallization of low‐crystallinity elastomer incorporated by multi‐walled carbon nanotubes: Mechanical reinforcement,structural evolution and enhanced thermal stability

In this paper, we report interfacial crystallization in olefin block copolymer (OBC) with low crystallinity incorporated by multi‐walled carbon nanotubes (MWCNTs). A hybrid shish‐kebab (HSK) superstructure in nanocomposites is observed that MWCNTs act as central shish and OBC crystals grow perpendicular to the nanotubes axis. The mechanical properties of nanocomposites are significantly improved with incorporation of MWCNTs. The most ideal reinforcing and toughening effect is both observed in nanocomposites with MWCNTs content of 1 wt % that can increase tensile strength by 122% as well as elongation at break by 36%. Efficient load transfer are confirmed with in‐situ Raman spectra that G’ band of MWCNTs in OBC matrix exhibit a downshifting trend and symmetric broadening of line shape which reveals additional macroscale strain from axial extension of MWCNTs in nanocomposites, thus suggesting a certain load is carried by HSK superstructure. The structural evolution of OBC and nanocomposites are investigated by in‐situ wide‐angle X‐Ray Diffraction (WAXD). The Herman's orientation factor of nanocomposites with 2 wt % MWCNTs incorporation is lower than that of neat matrix at mall and intermediate strains, indicating a heterogeneous stress distribution and low compliance of HSK superstructure, which is consistent with in‐situ Raman results. Moreover, the nanocomposites presents significantly enhanced thermal stability. The onset decomposition temperature of nanocomposites with 3 wt % MWCNTs can be 60.2°C higher than that of neat OBC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42368.     

Electrical conductivity and tensile properties of block‐copolymer‐wrapped single‐walled carbon nanotube/poly(methyl methacrylate) composites

Poly(methyl methacrylate) (PMMA) composites containing raw or purified single‐walled carbon nanotubes (SWCNTs) are prepared by in situ polymerization and solution processing. The SWCNTs are purified by centrifugation in a Pluronic surfactant, which consists of polyethyleneoxide and polypropyleneoxide blocks. Both the effects of SWCNT purity and non‐covalent functionalization with Pluronic are evaluated. Electrical conductivity of PMMA increases by 7 orders of magnitude upon the integration of raw or purified SWCNTs. The best electrical properties are measured for composites made of purified SWCNTs and prepared by in situ polymerization. Strains at fracture of the SWCNT/PMMA composites are nearly identical to those of the neat matrix. A certain decrease in the work to fracture is measured, particularly for composites containing purified SWCNTs (?31.6%). Fractography and Raman maps indicate that SWCNT dispersion in the PMMA matrix improves upon the direct addition of Pluronic, while dispersion becomes more difficult in the case of purified SWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41547.     

Surface modification of halloysite nanotubes with l‐lactic acid: An effective route to high‐performance poly(l‐lactide) composites

To improve the interfacial bonding between halloysite nanotubes (HNTs) and poly(l ‐lactide) (PLLA), a simple surface modification of HNTs with l ‐lactic acid via direct condensation polymerization has been developed. Two modified HNTs were obtained: HNTs grafting with l ‐lactic acid (l‐HNTs) and HNTs grafting with poly(l ‐lactide) (p‐HNTs). The structures and properties of l‐HNTs and p‐HNTs were investigated. Then, a series of HNTs/PLLA, l‐HNTs/PLLA and p‐HNTs/PLLA composites were prepared using a solution casting method and were characterized by polarized optical microscopy (POM), field scanning electron microscopy, and tensile testing. Results showed that l ‐lactic acid and PLLA could be easily grafted onto the surface of HNTs by forming an Al carboxylate bond and following with condensation polymerization, and the amounts of the l ‐lactic acid and PLLA grafted on the surface of the HNTs were 5.08 and 14.47%, respectively. The surface‐grafted l ‐lactic acid and PLLA played the important role in improving the interfacial bonding between the nanotubes and matrix. The l‐HNTs and p‐HNTs can disperse more uniformly in and show better compatibility with the PLLA matrix than untreated HNTs. As a result, the l‐HNTs/PLLA and p‐HNTs/PLLA composites had better tensile properties than that of the HNTs/PLLA composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41451.