Matrix‐polymer‐functionalized multiwalled carbon nanotubes as a highly efficient toughening agent for matrix polymers

Matrix‐polymer‐functionalized multiwalled carbon nanotubes (MWCNTs) are demonstrated as a highly efficient toughening agent for matrix polymers. With poly(vinylidene fluoride) (PVDF) as the matrix polymer, the PVDF/MWCNT‐PVDF nanocomposite films show high toughness. With a small load amount of MWCNT‐PVDF (0.07 wt %), the nanocomposite film shows a yield point and a constant‐stress extension region in stress–strain tests, compared with the typical low‐extensibility feature of neat PVDF film. The PVDF/MWCNT‐PVDF‐0.7 film exhibits a 180‐fold increase of toughness and about 38‐fold increase in strain at break compared with neat PVDF film. This toughening effect is attributed to (a) homogeneous dispersion of MWCNT‐PVDF in PVDF, (b) the high efficiency of load‐transfer across MWCNT/PVDF interface, and (c) the long length of the MWCNTs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Role of radicals in UV‐initiated postplasma grafting of poly‐ε‐caprolactone: An electron paramagnetic resonance study

Electron paramagnetic resonance (EPR) measurements were performed on poly‐ε‐caprolactone (PCL) films at different stages of the postplasma‐grafting process. PCL films prepared by solvent casting (SC) or electrospinning (ESP) yield very similar EPR spectra after Ar‐plasma treatment and subsequent exposure to air, but the EPR signal is much stronger in the PCL‐ESP films. The free radicals appear to be mainly, and possibly exclusively, oxygen centered. The radicals generated by UV irradiation in PCL‐ESP films were studied in situ with EPR, using a UV‐LED (λ = (285 ± 5) nm). Their EPR spectrum is distinctly different from the plasma‐induced signal, indicative of carbon‐centered radicals, and appears to be independent of the plasma pretreatment. UV‐induced homolytic splitting of (hydro)peroxide bonds was not observed. Both the plasma‐ and UV‐induced radicals decay at room temperature (RT), even in an inert atmosphere. This study demonstrates the potential of electrospun films and UV‐LEDs for the study of plasma‐ and UV‐generated free radicals with EPR in polyesters, and raises questions with respect to the validity of some generally accepted molecular mechanisms underpinning the postplasma grafting technique for polyesters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of pyrene bearing amphiphilic miktoarm star polymer and its noncovalent interactions with multiwalled carbon nanotubes

A novel amphiphilic miktoarm star polymer, polystyrene‐poly(ethylene glycol)‐poly(methyl methacrylate), bearing a pyrene group at the end of PS arm (Pyrene‐PS‐PEG‐PMMA) was successfully synthesized via combination of atom transfer radical polymerization and click chemistry. The structure and composition of the amphiphilic miktoarm star polymer were characterized by gel permeation chromatography and ¹H NMR. The functionalization of multiwalled carbon nanotubes (MWCNTs) via “π–π” stacking interactions with pyrene‐PS‐PEG‐PMMA miktoarm star polymer was accomplished and the resulting polymer‐MWCNTs hybrid was analyzed by using ¹H NMR, UV–vis, fluorescence spectroscopy, and thermal gravimetric analysis. The high‐resolution transmission electron microscopy and analytical techniques aforementioned confirmed that the noncovalent functionalization of MWCNT's with the amphiphilic miktoarm star polymer was successfully achieved. The MWCNT/pyrene‐PS‐PEG‐PMMA exhibited significant dispersion stability in common organic solvents such as dimethyl formamide, chloroform, and tetrahydrofuran. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymorphism and Thermal Behaviour of Syndiotactic Poly(propylene)/Carbon Nanotube Composites

Summary: Nanocomposite materials were obtained by blending multi‐wall carbon nanotubes (CN), obtained by acetylene catalytic chemical vapour deposition (CVD) on Co/Fe‐modified NaY zeolite, with syndiotactic poly(propylene) (sPP). The nanotubes, well dispersed in the polymer matrix, favour the crystallization of the sPP helical chains and significantly improve the sPP thermal stability either in nitrogen or in air. The morphology of the sPP affects the behaviour of the sPP degradation in air.

Thermogravimetric analysis in air of pure sPP and the nanocomposite material.     

Dissolution of MWCNTs by using polyoxadiazoles,and highly effective reinforcement of their composite films

Nonmodified multiwalled carbon nanotubes (MWCNTs)/sulfonated polyoxadiazole (sPOD) nanocomposites are successfully prepared by a facile solution route. The pristine MWCNTs are dispersed in a sPOD solution, and the mixtures are fabricated into thin films by solution casting. The homogeneous dispersion of nanotubes in the composites is confirmed by transmission electron microscopy. The mechanical properties, thermal stability, and electrical conductivity are investigated. Tensile strength, elongation at break, and tensile energy to break are shown to increase by more than 28, 45, and 73%, respectively, by incorporating up to 1.0 wt % pristine MWCNTs. The experimental values for sPOD/MWCNTs composite stiffness are compared with Halpin‐Tsai and modified Halpin‐Tsai predictions. The storage modulus is found to increase up to 10% at low CNT loading. The composite films, which have an outstanding thermal stability, show an increase of up to 57 °C in the initial degradation temperature. The addition of 1.0 wt % MWCNTs increases the electrical conductivity of the sPOD matrix by two orders of magnitude. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Polymer coating of carboxylic acid functionalized multiwalled carbon nanotubes via reversible addition‐fragmentation chain transfer mediated emulsion polymerization

In this work, successful polymer coating of COOH‐functionalized multiwalled carbon nanotubes (MWCNTs) via reversible addition fragmentation chain transfer (RAFT) mediated emulsion polymerization is reported. The method used amphiphilic macro‐RAFT copolymers as stabilizers for MWCNT dispersions, followed by their subsequent coating with poly(methyl methacrylate‐co‐butyl acrylate). Poly(allylamine hydrochloride) was initially used to change the charge on the surface of the MWCNTs to facilitate adsorption of negatively charged macro‐RAFT copolymer onto their surface via electrostatic interactions. After polymerization, the resultant latex was found to contain uniform polymer‐coated MWCNTs where polymer layer thickness could be controlled by the amount of monomer fed into the reaction. The polymer‐coated MWCNTs were demonstrated to be dispersible in both polar and nonpolar solvents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Polyelectrolyte‐grafted carbon nanotubes: Synthesis,reversible phase‐transition behavior,and tribological properties as lubricant additives

A novel polyelectrolyte‐grafted multiwalled carbon nanotubes (MWCNTs‐g‐PILs) which possesses a hard backbone of MWCNTs and a soft shell of brush‐like poly (ionic liquids) (PILs) has been synthesized via the surface atom transfer radical polymerization (ATRP). Chemical structure and the grafted PILs quantities of MWCNTs‐g‐PILs were determined by FTIR, TGA, and XPS. TEM and FE‐SEM observations indicate that the nanotubes were coated with a PILs layer, exhibiting core‐shell nanostructures with the PILs chains as the brush‐like or hairy shell and the MWCNTs as the hard backbone. Furthermore, the effect of counter‐anions on the solubility of MWCNTs‐g‐PILs was investigated. The results indicate that relative solubility of MWCNTs‐g‐PILs in various solvents could be switched by anion exchange. This tunable solubility results in the formation of the cycle of reversible phase‐transition. Tribological property of MWCNTs‐g‐PILs as additives in base lubricant 1‐methyl‐3‐butylimidaaolium hexafluorophosphate (LP104) was evaluated using an Optimol SRV oscillating friction and wear tester, confirming that MWCNTs‐g‐PILs are the excellent antiwear and friction‐reducing additives, which can amend the tribological properties of base lubricant significantly. This is attributed to the good dispersibility and core‐shell structure of MWCNTs‐g‐PILs. These results reported in this work may open primarily toward constructing a bridge among carbon nanotues (CNTs), ILs, and lubricant additives and secondarily to prove that CNTs (modified CNTs) as lubricant additives are promising candidates. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7225–7237, 2008     

Enhanced dielectric properties of polymer composite films induced by encapsulated MWCNTs with a one core‐two shell structure

Multiwalled carbon nanotubes (MWCNTs) can endow high dielectric constant to polymer‐based composites. However, the accompanying poor dispersion of MWCNTs and high dielectric loss for composites severely limit their application in dielectric field. Herein, a modified acid‐treated MWCNTs encapsulated by the polyaniline/poly(sodium 4‐styrenesulfonate) layers (aMWCNTs@PANI‐PSS) with a one core‐two shell structure was fabricated by in situ polymerization followed by electrostatic self‐assembly technique. Furthermore, the composite films based on aMWCNTs@PANI‐PSS/poly(vinylidenefluoride‐hexaflouropropylene) (PVDF‐HFP) were fabricated by a solution‐casting method. An ultrathin insulating PSS shell is wrapped onto aMWCNTs@PANI, resulting in the improvement of dispersibility for aMWCNTs@PANI and the decrease of dielectric loss for composite films. When the content of aMWCNTs@PANI‐PSS is 5.0 wt %, the dielectric constant of aMWCNTs@PANI‐PSS/PVDF‐HFP reaches 430 (100 Hz), which is about 55 times of pure PVDF‐HFP and 1.7 times of aMWCNTs@PANI/PVDF‐HFP (247). Besides, the responding dielectric loss of aMWCNTs@PANI‐PSS/PVDF‐HFP composite film is only 0.67, much lower than that of aMWCNTs@PANI/PVDF‐HFP (25) and aMWCNTs/PVDF‐HFP (3185). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 948–956     

The mechanical and electrical properties of carbon nanotube‐grafted polyimide nanocomposites

Polyimide (PI)‐based nanocomposites containing aminophenyl functionalized multiwalled carbon nanotubes (AP‐MWCNTs) obtained through a diazonium salt reaction was successfully prepared by in situ polymerization. PI composites with different loadings of AP‐MWCNTs were fabricated by the thermal conversion of poly(amic acid) (PAA)/AP‐MWCNTs. The mechanical and electrical properties of the AP‐MWCNTs/PI composites were improved compared with those of pure PI due to the homogeneous dispersion of AP‐MWCNTs and the strong interfacial covalent bonds between AP‐MWNTs and the PI matrix. The conductivity of AP‐MWNTs/PI composites (5:95 w/w) was 9.32 × 10^?1 S/cm which was about 10¹⁵ times higher than that of Pure PI. The tensile strength and tensile modules of the AP‐MWCNTs/PI composites with 0.5 wt % of AP‐MWCNTs were increased by about 77% (316.9 ± 10.5 MPa) and 25% (8.30 ± 1.10 GPa) compared to those of pure PI, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 960–966     

The effect of different treatment methods of multiwalled carbon nanotubes on thermal and flexural properties of their epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were oxidized using four different acid‐treatment methods followed by their functionalization with 3‐aminopropyltriethoxysilane (3‐APTES). Diglycidyl ether of bisphenol A (DGEBA) nanocomposites with unmodified and silanized MWCNTs (0.2 wt %) were prepared by a cast molding method. The effect of functionalization of MWCNTs on thermal, flexural, and morphological properties of the epoxy nanocomposites were studied. The epoxy/MWCNTs nanocomposites were characterized by thermogravimetric analysis, flexural testing, and field emission electron microscopic analysis. The results showed that the silanization of MWCNTs which were oxidized by a two‐step process using nitric acid and hydrochloric acid showed better thermal and flexural properties due to good interfacial adhesion between MWCNTs and the epoxy matrix. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1175–1184, 2010     

Photoresponsive water‐dispersible polyaniline nanoparticles through template synthesis with copolymer micelle containing coumarin groups

A novel kind of photosensitive water‐dispersible polyaniline (PANI) nanoparticles was designed and prepared by template synthesis using a photo‐responsive vinyl‐coumarin (VM)/2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) copolymer micelle containing coumarin moieties. The resulting PANI nanoparticles exhibited reversible photo‐crosslinking and photo‐decrosslinking behavior similar to coumarin moiety upon irradiation with different UV light as verified by UV–vis absorption. In addition, photoinduced size change of the PANI nanoparticles after 365 nm UV light irradiation was successfully monitored by dynamic light scattering and transmission electron microscopy measurements, further confirming the photosensitivity of the obtained PANI nanoparticles by the incorporation of VM/AMPS copolymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

单宁酸改性制备光敏碳纳米管及UV光固化AESO复合膜的制备

本文以单宁酸（TA）和甲基丙烯酸缩水甘油酯（GMA）为原料，通过开环反应制备出含有双键的光敏单宁酸（pTA），并通过π-π非共价键作用使其吸附到碳纳米管上，得到pTA修饰后的具有良好分散性的光敏碳纳米管（pTA/MWCNTs）。再将该pTA/MWCNTs作为填料添加到环氧大豆油丙烯酸酯（AESO）中，通过UV光固化得到AESO-pTA/MWCNTs复合膜。利用pTA对MWCNTs进行改性，提高了MWCNTs的分散性，同时引入双键，使得pTA/MWCNTs能够参与到光固化过程中，提高了碳纳米管与AESO基质间的界面粘结力，对AESO起到了比较好的增强作用。本文还研究了pTA/MWCNTs的加入对AESO复合涂料光固化动力学及涂膜性能的影响，结果表明该pTA/MWCNTs的掺入提高了光固化AESO复合膜的力学性能，当掺入量为0.8%时，对膜的增强效果最好，与纯AESO比较，其拉伸模量提高了390%，拉伸强度提高了110%。     

Thin films composed of multiwalled carbon nanotubes, gold nanoparticles and myoglobin for humidity detection at room temperature.

Optically transparent and electrically conductive nanocomposite thin films consisting of multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (GNPs) and myoglobin molecules that glue GNPs and MWCNTs together are fabricated for the first time on glass substrates from aqueous solution. The nanocomposite thin film is capable of varying its resistance, impedance or optical transmittance at room temperature in response to changes in ambient humidity. The conductometric sensitivity to relative humidity (RH) of the nanocomposite thin film is compared with those of the pure and Mb-functionalized MWCNT layers. The pure MWCNT layer shows a small increase in its resistance with increasing RH due to the effect of p-type semiconducting nanotubes present in the film. In contrast, a four times higher sensitivity to RH is observed for both the nanocomposite and Mb-functionalized MWCNT thin films. The sensitivity enhancement is attributable to swelling of the thin films induced by water absorption in the presence of Mb molecules, which increases the inter-nanotube spacing and thereby causes a further increase of the film resistance. A humidity change as low as DeltaRH=0.3 % has been readily detected by conductometry using the nanocomposite thin film.     

Effect of carbon nanotubes on the photo-oxidative durability of syndiotactic polypropylene

Polymer nanocomposites with carbon nanotubes as fillers have attracted more attention than any other nanomaterials. A full development of these materials requires a deep understanding of the way they behave in the use conditions. In this work, the resistance to accelerated photooxidation of syndiotactic polypropylene/multi-walled carbon nanotube (sPP/MWCNTs) films was compared to the photooxidation behaviour of unfilled polypropylene films with the same structural organization. The chemical and structural modifications resulting from photooxidation have been followed using infrared spectroscopy and diffractometric analysis. It was found that a good dispersion degree of the nanofiller, evaluated by atomic force microscopy, contributes to reduction in the rate of photooxidation and an increase in the oxidative thermal stability of the polymeric matrix. Different concomitant effects are considered to explain these results, among which morphology and structure of the nanocomposites together with the MWCNT capacity to interact with oxygen molecules making them unavailable in the first stages of photooxidation.     

Structural and morphological studies on the deformation behavior of polypropylene/multi‐walled carbon nanotubes nanocomposites prepared through ultrasound‐assisted melt extrusion process

Structural and morphological behavior under stress–strain of polypropylene/multi‐walled carbon nanotubes (PP/MWCNTs) nanocomposites prepared through ultrasound‐assisted melt extrusion process was studied by means of optical microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, small angle X‐ray scattering (SAXS), and wide angle X‐ray scattering (WAXS). A high ductile behavior was observed in the PP/MWCNT nanocomposites with low concentration of MWCNTs. This was related to an energy‐dissipating mechanism, achieved by the formation of an ordered PP‐CNTs interphase zone and crystal oriented structure in the undeformed samples. Different strain‐induced‐phase transformations were observed by ex situ SAXS/WAXS, characterizing the different stages of structure development during the deformation of PP and PP/MWCNTs nanocomposites. The high concentration of CNTs reduced the strain behavior of PP due to the agglomeration of nanoparticles. A structural pathway relating the deformation‐induced phase transitions and the dissipation energy mechanism in the PP/MWCNTs nanocomposites at low concentration of nanoparticles was proposed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 475–491     

Effect of different nanoparticles on HDPE UV stability

In the present study different series of HDPE nanocomposites were prepared by melt mixing on a Haake-Buchler Reomixer, containing 2.5 wt% of multiwall carbon nanotubes, pristine and modified montmorillonite, and SiO₂ nanoparticles. Nanocomposites in the form of thin films were exposed to UV irradiation at 280 nm at constant temperature (25 °C) and constant relative humidity (50%) for several times. From tensile strength and Young’s Modulus measurements it was verified a high increase with initial UV irradiation times (till 100 h) and a slight reduction thereafter. The increase was higher in nanocomposites compared with neat HDPE, except these containing MWCNTs, and was attributed to the crystallinity increase in the particular samples. The mechanical properties reduction at higher UV irradiation times was attributed to the extensive macromolecular chain scission causing irregularities and holes in film surfaces. However, from FTIR study it was found that SiO₂ and organically modified montmorillonite cause a serious effect on HDPE during UV degradation. New chemical compounds containing carbonyl, vinyl and hydroxyl groups were formed. It seems that these nanoparticles have an accelerating effect acting as catalysts to HDPE photo-oxidation. This was also verified from micro-Raman analysis. Untreated montmorillonite has also a small influencing effect while neat HDPE and nanocomposites containing multiwall carbon nanotubes have the highest UV stability.     

Viscoelastic behavior of poly(ether imide) incorporated with multiwalled carbon nanotubes

There is significant potential in improving the mechanical, electrical, and thermal properties of engineering plastics, including poly(ether imide) (PEI), with various nanoinclusions such as multiwalled carbon nanotubes (MWCNTs). However, this potential can only be fully realized through a thorough understanding of the rheological behavior and the thermomechanical histories that the nanocomposites are exposed to during their preparation and the resulting effective properties. In this study, nanocomposites of PEI and MWCNTs were prepared using a solution processing method under different dispersion conditions, and the viscoelastic material functions of the nanocomposites were characterized as functions of concentration of CNTs in the 1–5% by weight range (volume fraction, ? = 0.006–0.03) and temperature. The storage modulus and magnitude of complex viscosity values of the PEI nanosuspensions increased by as much as 3500% and 800%, respectively, at ? = 0.03, along with similar orders of magnitude increases observed or predicted in other viscoelastic material functions. Such increases reflect how nanotube incorporation and network formation can drastically alter the flow and deformation behavior of the PEI/CNT nanosuspensions at processing‐relevant temperatures and deformation rates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Covalent surface functionalization of multiwalled carbon nanotubes through bergman cyclization of enediyne‐containing dendrimers

A method for covalent functionalization of multiwalled carbon nanotubes (MWCNTs) was developed using the free radicals generated through Bergman cyclization of enediyne‐containing compounds. Four enediyne‐bearing Frechet type dendrimers were synthesized in good quantities and characterized. Then, the enediyne‐containing molecules were reacted with MWCNTs in N‐methyl‐2‐pyrrolidinone at 206 °C under nitrogen. The structure and morphology of the resulting products were characterized by thermogravimetric analysis, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy. The dendrimer‐functionalized MWCNTs showed good solubility/dispersibility in common organic solvents and polymer solutions. They were used in the formation of polymer composites through electrospinning with polycaprolactone. The results confirmed the surface functionalization of MWCNTs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Toughening of poly(L‐lactide)/multiwalled carbon nanotubes nanocomposite with ethylene‐co‐vinyl acetate

Poly(L ‐lactide)/multiwalled carbon nanotubes (PLLA/MWCNTs) nanocomposite recently attracts much attention because of its excellent comprehensive properties including improved thermostability, tensile strength, and conductivity. However, the nanocomposite exhibits similar brittleness compared with unmodified PLLA. In this work, a polar elastomer, that is, ethylene‐co‐vinyl acetate (EVA), was introduced into PLLA/MWCNTs nanocomposite. The selective distribution of MWCNTs and the effects of EVA on crystalline structure of PLLA were investigated using scanning electron microscope, transmission electron microscope, differential scanning calorimetry, and wide angle X‐ray diffraction. The results show that the presence of EVA induces the change of the distribution of MWCNTs in the nanocomposites, and consequently, the cold crystallization of PLLA is prevented. With the increase of EVA content, both the ductility and the impact resistance of PLLA/FMWCNTs are improved greatly, indicating the toughening effect of EVA on PLLA/MWCNTs nanocomposite. The decreased tensile strength and modulus can be compensated through annealing treatment. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010