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     

Strengthening and toughening of thermoplastic polyolefin elastomer using polypropylene‐grafted multiwalled carbon nanotubes

In this article, it is demonstrated that simultaneously strengthened and toughened nanocomposites based on polypropylene/EPDM thermoplastic elastomer (TPO) matrix can be achieved through enhanced adhesion between MWNTs and polymer matrix by using PP grafted multiwalled carbon nanotubes (MWNTs). To improve the interface between filler and matrix, MWNTs were treated with acid, or covalently linked to polypropylene. The chemical and morphological transformation of the modified MWNTs, and its effect on the morphology and mechanical properties of the composites are investigated. The strengthening and toughening mechanism is discussed regarding the structural property relationship. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reinforcement of liquid ethylene–propylene–dicyclopentadiene copolymer based elastomer with vinyl functionalized multiwalled carbon nanotubes

A methodology for reinforcement of liquid ethylene–propylene–dicyclopentadiene copolymer (liquid‐EPDM) based elastomer with multiwalled carbon nanotubes (MWCNTs) was proposed. Acid‐treated MWCNTs were first reacted with poly(acryloyl chloride) (PACl) leading to a grafted encapsulation, which were subsequently reacted with hydroxy ethyl acrylate (HEA) to generate vinyl groups. Thus obtained vinyl groups functionalized MWCNTs (vinyl‐MWCNTs) were characterized using Fourier transform infrared spectroscopy, transmission electron microscopy, and thermogravimetric analysis. The vinyl‐MWCNTs were blended with liquid‐EPDM and subjected to co‐curing; an intercrosslinked structure was obtained via the free radical polymerization among the vinyl groups on vinyl‐MWCNTs and the double bonds on liquid‐EPDM. As a result, the vinyl‐MWCNTs and the cured EPDM matrix were covalently linked. The chemical interfacial interaction between vinyl‐MWCNTs and the cured matrix were observed by scanning electron microscope, which provided obvious reinforcement of elastomer. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

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     

Mechanical and thermal properties of functionalized multiwalled carbon nanotubes and multiwalled carbon nanotube–polyurethane composites

Multiwalled carbon nanotube (MWNT)–polyurethane (PU) composites were obtained by an in situ polycondensation approach. The effects of the number of functional groups on the dispersion and mechanical properties were investigated. The results showed that the functionalized MWNTs had more advantages for improving the dispersion and stability in water and N,N′‐dimethylformamide. The tensile strength and elongation at break of the composites exhibited obvious increases with the addition of MWNT contents below 1 wt % and then decreases with additions above 1 wt %. The maximum values of the tensile strength and elongation at break increased by 900 and 741%, respectively, at a 1 wt % loading of MWNTs. Differential scanning calorimetry measurements indicated that the addition of MWNTs resulted in an alteration of the glass‐transition temperature of the soft‐segment phase of MWNT–PU. Additionally, new peaks near 54°C were observed with differential scanning calorimetry because of the microphase‐separation structures and alteration of the segment molecular weights of the hard segment and soft segment of PU with the addition of MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nucleation effect of hydroxyl‐purified multiwalled carbon nanotubes in poly(p‐phenylene sulfide) composites

To investigate the nucleation effect of hydroxyl‐purified multiwalled carbon nanotubes (MWNTs‐OH) in poly(p‐phenylenesulfide) (PPS), a series of composites were prepared by blending PPS with MWNTs‐OH at 1, 2, and 3 wt %, respectively. Under SEM observation MWNTs‐OH were found homogeneously dispersed in the PPS matrix. DSC thermograms revealed that the enthalpy (ΔH_c) of the composites increased with increasing MWNT‐OH content, whereas the crystallization temperature (T_c) decreased progressively. The decrease in T_c was in accordance with the smaller crystallite size determined with WXRD characterization, and the increase in ΔH_c was evidenced by FTIR and XPS analyses. The higher ΔH_c shows that MWNTs‐OH serves as a nucleating agent, providing sufficiently multiplied sites for crystal growth. The lowering of T_c was attributed not only to MWNTs‐OH network hindrance to PPS chain fusing rearrangement, but also to a poorer affinity between MWNTs‐OH and PPS; both effects coordinately govern T_c of PPS/MWNTs‐OH composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Tailoring in thermomechanical properties of ethylene propylene diene monomer elastomer with silane functionalized multiwalled carbon nanotubes

The incorporation of silane treated multiwalled carbon nanotubes (S‐MWCNTs) is used as an effective path for tailoring thermomechanical properties of ethylene propylene diene monomer (EPDM). In this study, S‐MWCNTs were introduced into EPDM using internal dispersion kneader and two roller mixing mill. By altering the mass ratio of S‐MWCNTs from 0 to 1, thermal conductivity, thermal stability and phase transition temperatures and their respective enthalpies are discussed of the fabricated nanocomposites. It is observed that silane modification improves their dispersion and increases the interfacial bonding between MWCNTs and polymer matrix. Scanning electron microscopy along energy dispersive spectroscopy analysis is performed to confirm the silane functionalized MWCNTs are selectively distributed in the host polymer. More importantly, an important increase in mechanical properties like ultimate tensile strength and hardness is achieved through introducing silane functionalized MWCNTs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43221.     

Preparation and characterization of nylon610/functionalized multiwalled carbon nanotubes composites

Nylon610 nanocomposites containing functionalized multiwalled carbon nanotubes (MWCNTs) were prepared using wet melt blending method, which is a novel preparation technique. In comparison with the pure nylon610, the elastic modulus, tensile strength, bending modulus, and bending strength of the composites increase significantly with the increase of MWCNTs content, and the mechanical properties of the composites are also improved significantly by adding a small amount of MWCNTs (0.1 wt %). The crystallization peak of the composites shifts to higher temperature with the addition of MWCNTs, and among the two melting peaks, the intensity of melting peak at low temperature decreases with increasing MWCNTs content. The composites are more stable than pure PA610 and decompose at higher temperature, suggesting that the accession of MWCNTs can improve the composites' thermal stability. The storage modulus of the composites decreases with the temperature increasing, but under lower temperature it increases significantly with the addition of MWCNTs–COOH except for PANT‐0.1 sample. Transmission electron microscope (TEM) images of composites exhibit that the wet melt blending technique can avoid the excess agglomeration of MWCNTs under vacuum dryness, which benefits MWCNTs to disperse uniformly in matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of ultrahigh‐molecular‐weight polyethylene nanocomposite films containing different functionalized multiwalled carbon nanotubes

We compared the thermomechanical properties, morphologies, gas permeabilities, and electrical conductivities of ultrahigh‐molecular‐weight polyethylene (UHMWPE) nanocomposite films containing two types of functionalized multiwalled carbon nanotubes (functionalized MWNTs). Both 2‐hydroxyethyl triphenyl phosphonium‐MWNT (Ph3P‐MWNT) and 1,1,1,3,3,3‐hexafluoro‐2‐phenyl‐2‐propanol‐MWNT (CF3‐MWNT) were used as reinforcing fillers in the fabrication of UHMWPE hybrid films. UHMWPE nanocomposites with various functionalized MWNT contents were solution‐cast to produce the films. The thermomechanical properties and morphologies of the UHMWPE hybrid films were then characterized using differential scanning calorimetry, thermogravimetric analysis, electron microscopy, and mechanical tensile analysis. Transmission electron microscopy studies showed that some of the MWNT particles were dispersed homogeneously within the polymer matrix (on the nanoscale), whereas others were agglomerated. We also found that the addition of only a small amount of functionalized MWNTs was sufficient to improve the thermomechanical properties and the gas barrier of the UHMWPE hybrid films. Even, those hybrid films with low functionalized MWNT contents (i.e., <1 wt%) were found to exhibit much better thermomechanical properties than the pure UHMWPE films. On the other hand, the values of the electrical conductivity remained constant, regardless of the amount of functionalized MWNTs. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Transport and deposition kinetics of polymer‐coated multiwalled carbon nanotubes in packed beds

In this study, a modified filtration equation that accounts for the transport and kinetics of polymer‐coated multiwalled carbon nanotubes in columns packed with crushed Berea sandstone is presented. The columns were saturated with brine solution, in which the salt concentration was varied from 0 to 10 wt%. Experimental results show that the polymer effectively eliminates the effects of salt on particle deposition when the salt concentration is less than or equal to 10 wt%. The calculated cumulative particle recovery is as high as 88.47 ± 0.25%. Results show that, at 10 wt% salt concentration, the proposed equation successfully predicts the experimental behavior, especially at the early stages of the breakthrough, where commonly used models fail. It is argued that the new equation accounts for the dynamic change of single collector efficiency as the deposition process advances. When tested against prior results available in the literature, the proposed model agrees with published data from other investigators. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3774–3783, 2016     

Hybrid modification of high‐density polyethylene with hyperbranched polyethylene‐functionalized multiwalled carbon nanotubes and few‐layered graphene

Herein, a facile method has been reported to efficiently prepare debundled multiwalled carbon nanotubes (MWCNT) and few‐layered graphene using a hyperbranched polyethylene (HBPE), and as hybrid fillers, their modification effects on high‐density polyethylene (HDPE) are well demonstrated. Stable dispersions of debundled MWCNT and graphene in chloroform were respectively obtained by sonication using the HBPE as stabilizer, and MWCNT/graphene/HDPE ternary nanocomposites were then fabricated by solution‐assisted premixing and subsequent melt mixing, at a fixed mass ratio of MWCNT/graphene of 3:1 and serially changed filler loadings. It is found that the MWCNT and graphene have good dispersibility in the composites, and as hybrid fillers, they can effectively form composite net‐like structure, which makes them show better modification effects on both the electrically and thermally conductive properties of HDPE, as compared to the single MWCNT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44848.     

Carbon nanotubes inhibit the free‐radical cross‐linking of siloxane polymers

Carbon nanotubes (CNTs) are found to inhibit the free‐radical cross‐linking of vinyl‐terminated polydimethylsiloxane (PDMS) by trapping the free radicals in a CNT/PDMS composite. The cross‐linking density values measured by swelling test, equilibrium stress‐strain test, glass‐transition temperature and Raman spectroscopy all decrease with the addition of CNTs. The inhibition effect is shown to be more significant with increased functionality and curvature in the CNTs used. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40355.     

Thermal and mechanical properties of carbon nanotube/epoxy nanocomposites reinforced with pristine and functionalized multiwalled carbon nanotubes

In this study, the effects of functionalization and weight fraction of mutliwalled carbon nanotubes (CNTs) were investigated on mechanical and thermomechanical properties of CNT/Epoxy composite. Epoxy resin was used as matrix material with pristine‐, COOH‐, and NH₂‐functionalized CNTs as reinforcements in weight fractions of 0.1, 0.5, and 1.0%. Varying (increasing) the weight fraction and changing type (pristine or functionalized) of CNTs caused increment in Young's modulus and tensile strength as observed during mechanical tests. CNT reinforcement improved thermal stability of the nanocomposites as observed by thermogravimetric analysis. Thermomechanical analysis showed a slight reduction in free volume of the polymer, that is a drop in coefficient of thermal expansion, prior to glass transition temperature (T_g) beside a slight increase in T_g value. Dynamic mechanical analysis indicated an increase in storage modulus and T_g owing to the strength addition of CNT to the matrix alongside the hardener. Scanning electron microscopy analysis of the fractured surface(s) revealed that CNTs were well dispersed with no agglomeration and resulted in reinforcing the matrix. POLYM. COMPOS., 36:1891–1898, 2015. © 2014 Society of Plastics Engineers     

Mechanical reinforcement of polyethylene using n‐alkyl group‐functionalized multiwalled carbon nanotubes: Effect of alkyl group carbon chain length and density

Polyethylene (PE) is one of the most produced synthetic resins in the world. Functionalized multiwalled carbon nanotube (MWCNT) is a potential nanoscale filler to realize the next generation strong and multifunctional PE composites. We demonstrate that MWCNTs grafted with short n‐alkyl groups are effective nanofillers for mechanical reinforcement of PE composites. At 1 wt% filler loading, the yield stress and Young's modulus improve significantly up to 54 and 63% compared with neat PE, respectively. Among ductile properties, tensile strength increases up to 30%; ultimate strain is preserved; and toughness increases up to 33%. More important, we show that short n‐alkyl groups can be grafted on MWCNTs much easier than long chain polymers. Further, we find that alkyl groups of C14–C18 chains have the optimum length for reinforcement. The optimum density of grafted alkyl groups is around 0.390–0.423 μmol/mg when the C14 alkyl groups are used. Overall, the results manifest that MWCNTs grafted with n‐alkyl groups with suitable length and density are efficient nanoscale fillers for high‐performance PE composites. POLYM. ENG. SCI., 54:336–344, 2014. © 2013 Society of Plastics Engineers     

Thermal‐initiated hydroxyethyl methacrylate functionalization of multiwalled carbon nanotubes

Multiwalled‐carbon nanotubes (MWCNTs) were functionalized via thermoinitiated free radical polymerization of 2‐hydroxyethyl methacrylate (HEMA) using benzoyl peroxide. Tip sonication was used during the polymerization reaction to separate agglomerated nanotubes. The functionalization was confirmed by control experiments and attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR). Differential scanning calorimetry indicated that the addition of poly(HEMA)‐MWCNTs to a two‐component polyurethane coating will have little effect on the glass transition temperature of the coating. The poly(HEMA)‐functionalized MWCNTs formed large colloidal structures of highly dispersed nanotubes in both the nonsheared and sheared coatings as determined by atomic force microscopy. This study determined a quick and easy method to functionalize MWCNTs for incorporation into a two‐component polyurethane coating. A simple method for producing ordered structures of the MWCNTs via shear observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fabrication of hybrid ladderlike polysilsesquioxane‐grafted multiwalled carbon nanotubes

Ladderlike polysilsesquioxanes (LPSs) containing chloromethylphenyl groups were synthesized from (p‐chloromethyl)phenyltrimethoxysilane under basic conditions. Functionalized multiwalled carbon nanotubes (MWNT–COOH) were prepared by the acid treatment of pristine multiwalled carbon nanotubes (MWNTs). MWNT–COOH was reacted with LPS to prepare LPS‐grafted MWNTs via ester linkages. The functionalization of MWNTs with LPS significantly altered the surface roughness of the MWNTs; there was a significant increase in the diameter of the MWNTs. The LPS‐grafted MWNTs had a 10–20 nm thickness along the outer walls according to the functionalization of the MWNTs with LPS. An advantage of the hybrid LPS‐grafted MWNTs was shown as improved thermal behavior. The composition, thermal properties, and surface morphology of the LPS‐grafted MWNTs were studied by Fourier transform infrared spectroscopy, thermogravimetric analysis, energy‐dispersive spectroscopy, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of diaminobenzoyl‐functionalized multiwalled carbon nanotubes on the nonisothermal curing kinetics,dynamic mechanical properties,and thermal conductivity of epoxy–anhydride composites

To obtain advanced materials with a high thermal dissipation, the addition of multiwalled carbon nanotubes containing diverse functionality groups, that is, as‐received multiwalled carbon nanotubes (AS‐MWCNTs) and diaminobenzoyl multiwalled carbon nanotubes (DA‐MWCNTs), to epoxy–anhydride composites was accomplished. According to nonisothermal differential scanning calorimetry analysis, the reactive functional groups present on the surfaces of the AS‐MWCNTs and DA‐MWCNTs accelerated the nucleophilic addition reaction of epoxy composites. Because of the difference in the reactivities of these functional groups toward epoxy groups, the distinction of fractional conversion and the reaction rate of the curing process were remarkably evident at the early stage. A suitable kinetic model was effectively elucidated with the Málek approach. The curing kinetics could best be described by a two‐parameter autocatalytic model as a truncated ?esták–Berggren model. The DA‐MWCNTs achieved effective load transfer and active heat conductive pathways; this resulted in good dynamic mechanical and thermal properties. As a result, the diglycidyl ether of bisphenol A/DA‐MWCNTs constituted an effective system with enhanced heat dissipation of materials for electronic applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43567.     

Nonisothermal crystallization kinetics of carbon nanotubes containing segmented polyurethane elastomer

Nanocomposites of the segmented polyurethane (SPU) elastomer with different concentrations of multiwall carbon nanotubes (MWCNTs) have been prepared. Scanning electron microscopy has been used to visualize the surface morphology and distribution of the nanotubes inside the matrix. Differential scanning calorimetry has been utilized to investigate the effects of MWCNTs on the crystallization characteristics of the SPU by collecting data at four cooling rates namely 5, 10, 15, and 20°C/min in the temperature range between 200°C to ambient. The results reveal that MWCNTs act as effective nucleating agent for crystallization of the hard segment of SPU and advance the onset and peak temperatures of crystallization by 38 and 23°C, respectively. The associated enthalpy and extent of crystallization are also increased by 34%. Different crystallization kinetic parameters have been calculated using both modified Avrami and combined Ozawa‐Avrami models to suggest a three dimensional growth of crystallization of SPU and its nanocomposites. The activation energy has been calculated using Kissinger method, which indicates that activation energy decreases with increasing concentration of MWCNTs. The calorimetric results have further been correlated with thermomechanical analysis and glass transition temperature of the nanocomposites corresponding to soft segment is found to increase by 20°C. POLYM. ENG. SCI., 56:1248–1258, 2016. © 2016 Society of Plastics Engineers     

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