Preparation and properties of plasticized starch/multiwalled carbon nanotubes composites

In this work we have studied the utilization of multiwalled carbon nanotubes (MWCNTs) as filler‐reinforcement to improve the performance of plasticized starch (PS). The PS/MWCNTs nanocomposites were successfully prepared by a simple method of solution casting and evaporation. The morphology, thermal behavior, and mechanical properties of the films were investigated by means of scanning electron microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, and tensile testing. The results indicated that the MWCNTs dispersed homogeneously in the PS matrix and formed strong hydrogen bonding with PS molecules. Compared with the pure PS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 2.85 to 4.73 MPa and from 20.74 to 39.18 MPa with an increase in MWCNTs content from 0 to 3.0 wt %, respectively. The value of elongation at break of the nanocomposites was higher than that of PS and reached a maximum value as the MWCNTs content was at 1.0 wt %. Besides the improvement of mechanical properties, the incorporation of MWCNTs into the PS matrix also led to a decrease of water sensitivity of the PS‐based materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Interaction of water soluble chitosan with multiwalled carbon nanotubes

A water soluble chitosan derivative (p‐chitosan) was synthesized and used to functionalize multiwalled carbon nanotubes (MWCNTs) through the noncovalent interaction. The interaction of p‐chitosan with MWCNTs was investigated by analyzing the spectra of ultraviolet‐visible, Fourier transform infrared, Raman, and X‐ray photoelectron. Circular dichroism spectroscopy was used to study the interaction as well. The results of the circular dichroism spectra indicate that, the interaction of p‐chitosan with MWCNT makes p‐chitosan less regularly structured. It was found that the interaction of p‐chitosan with MWCNTs at a lower temperature is stronger than that at a higher temperature; pH conditions affect the interaction between p‐chitosan and MWCNTs. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Morphology and tensile properties of polypropylene‐multiwalled carbon nanotubes composite fibers

In this work, we analyzed tensile properties of polypropylene‐multiwalled carbon nonotubes composite fibers. The multiwalled carbon nanotubes (MWCNTS) were used in different contents of 0, 1, 2, 3, 4, and 5 wt %. Dispersing agents were used to disperse MWCNTs in polypropylene matrix. After the dispersing agent was removed, the mixture was melt mixed. The fibers were spun by a home‐made melt spinning equipment and stretching was done at a draw ratio of 7.5. By using 1–5 wt % of MWCNTs, the modulus of composite fibers increased by 69–84% and tensile strength increased about 39% when compared with the virgin polypropylene fibers. In addition, the MWCNTs dispersion in the matrix was monitored by scanning electron microscopy and transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

磷钨酸/多壁碳纳米管催化合成乙酸正丁酯

利用多壁碳纳米管(MWCNTs)为载体,用浸渍法制备了负载磷钨酸(H3PW12O40,简写为HPW)的复合材料磷钨酸/多壁碳纳米管(HPW/MWCNTs)。磷钨酸/多壁碳纳米管具有很高的催化活性,在磷钨酸负载量为30%,醇酸物质的量比为1.4∶1,催化剂用量为反应物总质量的1.3%,反应温度为117℃,反应时间为3h的条件下,酯化率可达96.08%。     

Fabrication of multiwalled carbon nanotubes with polymer shells through surface RAFT polymerization

A core–shell hybrid nanostructure, possessing a hard backbone of multiwalled carbon nanotubes (MWNTs) and a soft shell of brush‐like poly(methyl methacrylate), has been successfully prepared via a reversible addition–fragmentation chain transfer (RAFT) process using a RAFT agent immobilized on MWNTs. Polymer‐modified MWNTs are easily dispersed in good solvents for the grafted polymer, such as toluene, tetrahydrofuran and CHCl₃. This observation has been confirmed by transmission electron microscopy analysis. The content of polymer in the functionalized MWNTs can be well controlled by the feed ratio. It is believed that realizing these hybrid structures, on the basis of such simple grafting, will pave the way for the design, fabrication, optimization and eventual application of more functional carbon nanotube‐related nanomaterials. Copyright © 2007 Society of Chemical Industry     

Improved impact strength of epoxy by the addition of functionalized multiwalled carbon nanotubes and reactive diluent

Multiwalled carbon nanotubes (MWCNTs), both oxidized and amine functionalized (triethylenetetramine—TETA), have been used to improve the mechanical properties of nanocomposites based on epoxy resin. The TGA and XPS analysis allowed the evaluation of the degree of chemical modification on MWCNTs. Nanocomposites were manufactured by a three‐roll milling process with 0.1, 0.5, and 1.0 wt % of MWCNT–COOH and MWCNT–COTETA. A series of nanocomposites with 5.0 wt % of reactive diluent was also prepared. Tensile and impact tests were conducted to evaluate the effects of the nanofillers and diluent on the mechanical properties of the nanocomposites. The results showed higher gains (258% increase) in the impact strength for nanocomposites manufactured with aminated MWCNTs. Optical microscopy (OM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to investigate the overall filler distribution, the dispersion of individual nanotubes, and the interface adhesion on the nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42587.     

Uptake and accumulation of multiwalled carbon nanotubes change the morphometric and biochemical characteristics of Onobrychis arenaria seedlings

We have studied the effect of the engineered nanomaterial Taunit, containing multiwalled carbon nanotubes (MWCNTs), on the growth of Onobrychis arenaria seedlings and investigated whether affected plants uptake and accumulate MWCNTs. We found that 100 μg/mL and 1000 μg/mL of Taunit stimulated the growth of roots and stems, and enhanced the peroxidase activity in these parts of plants. Microscopy studies showed the presence of MWCNTs in the root and leaf tissues of seedlings exposed to Taunit, suggesting that MWCNTs have a capacity to penetrate the cell walls, accumulate in roots and translocate to the leaves. Thus the stimulating effect of MWCNTs on seedlings of O. arenaria may be associated with the primary uptake and accumulation of MWCNTs by plant roots followed by translocation to the other plant tissues.     

Preparation and properties of multiwalled carbon nanotube/polycaprolactone nanocomposites

Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby as‐received MWNTs (P‐MWNTs) and purified MWNTs (A‐MWNTs) were used as reinforcing materials. The A‐MWNTs were purified by nitric acid treatment, which introduced the carboxyl groups (COOH) on the MWNT. The micrographs of the fractured surfaces of the nanocomposites showed that the A‐MWNTs in A‐MWNT/PCL were better dispersed than P‐MWNTs in PCL matrix (P‐MWNT/PCL). Percolation thresholds of the P‐MWNT/PCL and A‐MWNT/PCL, which were studied by rheological properties, were found at ～2 wt % of the MWNT. The conductivity of the P‐MWNT/PCL was between 10^?1 and 10^?2 S/cm by loading of 2 wt % of MWNT although that of the A‐MWNT/PCL reached ～10^?2 S/cm by loading of 7 wt % of MWNT. The conductivity of the P‐MWNT/PCL was higher than that of the A‐MWNT/PCL at the entire range of the studied MWNT loading, which might be due to the destruction of π‐network of the MWNT by acid treatment, although the A‐MWNT/PCL was better dispersed than the P‐MWNT/PCL. The amount of the MWNT at which the conductivity of the nanocomposite started to increase was strongly correlated with the percolation threshold. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1957–1963, 2007     

Nickel‐multiwalled carbon nanotubes/polyvinylidene fluoride composites with high dielectric permittivity

Composites with nickel particles coated multiwalled carbon nanotubes (Ni‐MWNTs) embedded into polyvinylidene fluoride (PVDF) were prepared by solution blending and hot‐press processing. The morphology, structure, crystallization behavior, and dielectric properties of composites were studied. The results showed that the crystallization of PVDF was affected by Ni‐MWNTs. With the increment of Ni‐MWNTs, the content of β‐phase in PVDF increased. The dielectric permittivity was as high as 290 at 10³ Hz when the weight fraction of Ni‐MWNTs was 10%. The results can be explained by the space charge polarization at the interfaces between the insulator and the conductor, and the formation of microcapacitance structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3746–3752, 2013     

Toughening of cycloaliphatic epoxy resin by multiwalled carbon nanotubes

The toughness of cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (ERL‐4221) has been improved by using multiwalled carbon nanotubes (MWCNTs) treated by mixed acids. The MWCNT/ERL‐4221 composites were characterized by Raman spectroscopy and their mechanical properties were investigated. A significant increase in the tensile strength of the composite from 31.9 to 55.9 MPa was obtained by adding only 0.05 wt % of MWCNTs. And a loading of 0.5 wt % MWCNTs resulted in an optimum tensile strength and cracking energy, 62.0 MPa and 490 N cm, respectively. Investigation on the morphology of fracture surface of the composites by field emission scanning electron microscopy demonstrated the crack pinning‐front bowing and bridging mechanisms of toughening. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyurethane/amino‐grafted multiwalled carbon nanotube nanocomposites: Microstructure,thermal, mechanical,and rheological properties

A mixture of two different polyols, (polytetramethylene ether glycol and polydimethylsiloxane), were employed to synthesize a new structure of polyurethane (PU) with methylene diphenyl diisocyanate (MDI) and 1,4‐butanediol as chain extender. PU nanocomposites containing variable amount (0.3, 0.5, 1, and 3 wt %) of amino‐grafted multiwalled carbon nanotubes (NH₂‐MWNT) were prepared via in situ polymerization. The dispersion of NH₂‐MWNT into polymer matrix was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FT‐IR) confirmed the urethane‐urea chemical bonding between the PU chains and the NH₂‐MWNT. Thermal stabilities of the nanocomposites were examined with thermogravimetric analysis (TGA) and the results indicated a remarkable improvement with increasing NH₂‐MWNT contents. The results of dynamic mechanical thermal analysis (DMTA) including storage modulus (E′) and glass transition temperature (T_g), as well as tensile properties demonstrated that the yield strength, strain‐at‐break, and young modulus were enhanced by increasing NH₂‐MWNT content. Rheological behavior including complex viscosity and storage and loss moduli of the PU nanocomposites improved with increasing NH₂‐MWNT loading, as well. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44411.     

Polymeric carbon nanocomposites from multiwalled carbon nanotubes functionalized with segmented polyurethane

Multiwalled carbon nanotubes (MWNT) were functionalized with segmented polyurethanes (PU) by the “grafting to” approach. Raman and X‐ray photoelectron spectroscopy (XPS) spectra show that the sidewalls of MWNTs have been functionalized with acid treatment, and the amount of COOH increases with increasing acid treatment time. FTIR and X‐ray diffraction (XRD) spectra confirm that PU is covalently attached to the sidewalls of MWNTs by esterification reaction. Similar to the parent PU, the functionalized carbon nanotube samples are soluble in highly polar solvents, such as dimethyl sulfoxide (DMSO) and N,N‐dimethylformamide (DMF). The functionalized acid amount and the grafted PU amount were determined by thermogravimetric analyses (TGA). Comparative studies, based on SEM images between the PU‐functionalized and chemically defunctionalized MWNT samples, also reveal the covalent coating character. Dynamic mechanical analysis (DMA) of nanocomposite films prepared from PU and PU‐functionalized MWNTs show enhanced mechanical properties and increased soft segment T_g. Tensile properties indicate that PU‐functionalized MWNTs are effective reinforcing fillers for the polyurethane matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Lipase covalently attached to multiwalled carbon nanotubes as an efficient catalyst in organic solvent

Lipase was covalently attached to multiwalled carbon nanotubes (MWNTs). Structural changes of the lipase upon attachment onto MWNTs were analyzed through circular dichroism and FTIR spectroscopy. The conjugate was utilized for the resolution of a model compound (R,S)‐1‐phenyl ethanol, and the reaction medium was n‐heptane. The enzymatic resolutions were carried out at temperatures from 35 to 60°C. The results show that the lipase attached onto MWNTs has significantly affected the performance of the enzyme in terms of temperature dependence and resolution efficiency. The activity of MWNT–lipase was less temperature‐dependent compared with that of the native lipase. The resolution efficiency was much improved with MWNT–lipase. MWNT–lipase retained the selectivity of the native lipase for (R)‐1‐phenyl ethanol. The consecutive use of MWNT–lipase showed that MWNT–lipase had a good stability in the resolution of (R,S)‐1‐phenyl ethanol. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Isothermal crystallization kinetics and melting behavior of multiwalled carbon nanotubes/polyamide‐6 composites

Pristine and functionalized multiwalled carbon nanotubes (MWNTs) were used to fabricate polyamide 6 (PA6) composites through melt blending. The functionalized MWNTs were obtained by grafting 1,6‐hexamethylenediamine (HMD) onto the pristine MWNTs to improve their compatibility with PA6 matrix. The effect of MWNTs on the isothermal crystallization and melting behavior of PA6 was investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). The Avrami and Lauritzen–Hoffmann equations are used to describe the isothermal crystallization kinetics. The values of the Avrami exponent found for neat PA6, the pristine MWNTs/PA6 and functionalized MWNTs/PA6 composite samples are about 4.0, 1.7, and 2.3, respectively. The activation energies are determined by the Arrhenius method, which is lower for the composites, ?320.52 KJ/mol for pristine MWNTs/PA6 and ?293.83 KJ/mol for functionalized MWNTs/PA6, than that for the neat PA6 (?284.71 KJ/mol). The following melting behavior reveals that all the isothermally crystallized samples exhibit triple melting endotherms at lower crystallization temperature and double melting endotherms at higher crystallization temperature. The multiple melting endotherms are mainly caused by the recrystallization of PA6 during heating. The resulting equilibrium melting temperature is lower for the composites than for neat PA6. In addition, polarizing microscopy (PLM) and small angle light scanning (SALS) were used to study the spherulite morphology. The results show that the MWNTs reduce the spherulite radius of PA6. This reduction is more significant for pristine MWNTs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Dispersion and noncovalent modification of multiwalled carbon nanotubes by various polystyrene‐based polymers

This article investigated the dispersion and modification of multiwalled carbon nanotubes (MWCNTs) through solution mixing based on the noncovalent interactions between polystyrene (PS) and MWCNTs. It was found that the interactions were robust enough to stabilize the debundled MWCNTs in solution after vigorous sonication. The PS attached, which altered the surface properties of MWCNTs and made them easily soluble in organic solvents, can remain even after careful washing with solvents. Besides, many other PS‐based polymers were proved to retain the ability to disperse MWCNTs to form stable solutions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface modification of multiwalled carbon nanotubes via gliding arc plasma for the reinforcement of polypropylene

To increase the applicability of multiwalled carbon nanotubes (MWCNTs), functional groups were generated on the generally inert surface of MWCNTs using gliding arc (GA) plasma. MWCNTs were modified using plasma polymerization with styrene (St) as monomer. The surface compositional and structural changes that occur on MWCNTs were investigated using FT‐IR, Raman spectroscopy, BET surface area, and elemental analysis. Dispersion of the treated MWCNTs in different solvents was evaluated. Transmission electron microscopy images showed that the plasma‐treated MWCNTs had a better dispersion than the untreated ones in nonpolar solvents. Subsequently, MWCNTs‐reinforced polypropylene (PP) composites were prepared by internal batch mixing with the addition of 1.0 wt % MWCNTs. The morphology of MWCNTs/PP nanocomposites was studied through scanning electron microscopy. Observations of SEM images showed that the plasma‐treated MWCNTs had a better dispersion than the untreated MWCNTs either on the composite fracture surfaces or inside the PP matrix. Moreover, the mechanical tests showed that the tensile strength and elongation at break were improved with the addition of polystyrene‐grafted MWCNTs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microwave absorption performance of nitrile butadiene rubber/ethylene propylene diene monomer rubber filled with multiwalled carbon nanotubes

In recent times, there is an increasing need for effective control of electromagnetic pollution, which can avoid excessive radiation effects on the human body. Microwave absorption materials are attracting wide research interests to reduce electromagnetic pollution due to the rapid development of electronic equipment. In this study, Nitrile butadiene rubber (NBR)/ethylene propylene diene monomer rubber (EPDM) were mixed with multiwalled carbon nanotubes (MWCNT) to prepare microwave absorbing materials. The distribution of fillers, AC conductivity, complex permittivity, and microwave absorption performance of the composites were systematically investigated. It found that the AC conductivity, both real and imaginary parts of the permittivity were significantly improved in the composite with the increasing ratio of MWCNT contents. The NBR/EPDM/MWCNT composites with eight parts per hundred concerning with rubber (phr) MWCNT had a minimum reflection loss (RLmin) of −48.1 dB at the optimum thickness of 2.07 mm. Importantly, the adding sequence of MWCNT and plasticizer dioctyl phthalate (DOP) to the rubber matrix is found to play an important role in determining the distribution of fillers and the structure of polymer blends. The composite with plasticizer added before MWCNT exhibited a better impedance matching and as a result, achieved a good microwave absorption performance.     

Fabrication and characterization of homogeneous composites of polypropylene and multiwalled carbon nanotubes

The polypropylene‐grafted multiwalled carbon nanotubes (PP‐MWCNTs) were produced from the reaction of PP containing the hydroxyl groups and MWCNTs having 2‐bromoisobutyryl groups. The PP‐MWCNTs had a significantly rougher surface than the original MWCNTs. PP‐MWCNTs had PP layers of thickness 10–15 nm on the outer walls of the MWCNTs. PP/PP‐MWCNT composites and PP/MWCNT composites were prepared by solution mixing in o‐xylene. Unlike PP/MWCNT composites, PP‐MWCNTs were homogeneously dispersed in the PP matrix. As a consequence, the thermal stability and conductivity of PP/PP‐MWCNT composites were dramatically improved even if only 1 wt % of PP‐MWNTs was added to the PP matrix. The good miscibility of PP and PP‐MWCNTs plays a critical role in the formation of the homogeneous composites and leads the high thermal stability and conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Protein adsorption on functionalized multiwalled carbon nanotubes with amino‐cyclodextrin

A novel amino‐cyclodextrin was synthesized, and it was covalently attached to multiwalled carbon nanotubes (MWNTs). The functionalized MWNTs (f‐MWNTs) have very good aqueous dispersibility. Bovine serum albumin (BSA) was adsorbed onto f‐MWNTs through noncovalent interactions, including the hydrophobic interaction of the residues of BSA with the wall of MWNT and the guest–host interaction of the residues with the cyclodextrin (CD) moieties of f‐MWNTs. The ultraviolet–visible (UV–vis) absorption of the f‐MWNT‐BSA hybrid was measured with UV–vis spectrometer, and the absorbance can be described well with the Beer–Lambert law. The X‐ray diffraction patterns have indicated that the crystalline form of BSA has been changed after the adsorption of BSA on f‐MWNTs. The circular dichroism spectra have shown that a high percentage of α‐helical content can be retained for BSA adsorbed on f‐MWNTs. The results also indicate that the change of secondary structure of BSA is mainly due to the hydrophobic interaction of the residues of BSA with the wall of f‐MWNT, whereas the secondary structure is much less affected by the interaction of the CD moieties with BSA. © 2011 American Institute of Chemical Engineers AIChE J, 2011