Orientation of carbon nanotubes in polypropylene melt

The correlation between shear stress and the orientation of single‐walled carbon nanotubes (SWCNTs) in an SWCNT/polypropylene composite during the melt process was investigated. Highly oriented composite fibers were produced by extruding the polypropylene melt using a capillary rheometer. The experimental range of shear rates covered those of common polymer melt‐shaping processes. The effect of functionalization of the SWCNTs on orientation was also investigated. Polarized Raman spectroscopy was used to analyze the orientation of the SWCNTs. A high degree of SWCNT orientation was observed under high shear stress, and the functionalized SWCNTs induced a higher degree of orientation than did pristine SWCNTs. The existence of a critical shear stress was observed for the orientation of the SWCNTs, and their orientation was found to occur more efficiently above this critical shear stress. The crystallization temperature and heat of fusion were characterized using a differential scanning calorimeter, and both parameters were observed to increase with the incorporation of SWCNTs. © 2012 Society of Chemical Industry     

Mechanical properties of surface-functionalized SWCNT/epoxy composites

Well-dispersed epoxy/single-walled carbon nanotube (epoxy/SWCNT) composites were prepared by oxidization and functionalization of the SWCNT surfaces using polyamidoamine generation-0 (PAMAM-0) dendrimer. For comparison purposes, neat epoxy, epoxy/PAMAM-0 and epoxy/pristine-SWCNTs were also prepared. The morphology and mechanical properties of the above composite systems were investigated and correlated with the surface characteristics of SWCNTs. It is found that surface functionalization can effectively improve the dispersion and adhesion of SWCNTs in epoxy. This leads to enhancement in mechanical properties of epoxy, but the improvement is not as significant as expected. It is also found that surface functionalization agent will have an undesirable effect on the physical and mechanical properties of epoxy/SWCNT composites. Issues regarding optimization of mechanical properties of epoxy/SWCNT composites are discussed.     

Effect of silane functionalization of montmorillonite on epoxy/montmorillonite nanocomposite

Mechanical and dynamic mechanical properties of various montmorillonite (MMT)/epoxy nanocomposites were investigated. 3-aminopropyltriethoxysilane functionalized MMT was compared with commercial pristine MMT and ammonium salt substituted MMT. Qualitative evidence of silane functionalization was confirmed by FT-IR. XRD and TEM were used to characterize the degree of intercalation of MMT in epoxy nanocomposite. Tensile stress and elongation of MMT/epoxy nanocomposite were improved significantly by the silane functionalization of MMT. Dynamic mechanical analysis showed that silane functionalization of MMT resulted in active interactions between MMT and epoxy.     

Evidence of sidewall covalent functionalization of single-walled carbon nanotubes and its advantages for composite processing

Single-walled carbon nanotubes (SWCNTs) were functionalized in a three-step procedure. The first step is a radical reaction creating a covalent bond between the carbon nanotube surface and grafted p-methoxyphenyl functional groups. In a second step, a deprotection of the methoxy functions generates free alcohol groups and in the final step an esterification is done in order to install a double bond for further polymerization. Evidence that functionalization has actually occurred on the SWCNT sidewalls is furnished through investigations involving several complementary techniques (visual dispersion tests, transmission electron microscopy, thermal gravimetric analysis and adsorption volumetry). We show that surface properties of SWCNTs are changed throughout the chemical treatments and that the obtained level of functionalization is low. Incorporation of functionalized SWCNTs in a polymer (poly(methyl methacrylate)) matrix was done through an in situ polymerization process. Observations of the obtained composites using scanning and transmission electron microscopy illustrate that interactions between the SWCNT surface and the polymer matrix are improved.     

Low degree of functionalization of Single-Walled Carbon Nanotubes probed by highly sensitive characterization techniques

Single-Walled Carbon Nanotubes (SWCNTs) were functionalized using a one-step radical addition procedure leading to a desired low functionalization degree. Based on well chosen techniques, the characterization of the functionalized samples allows having a good feedback on the functionalization process. We were able to determine the functionalization level and the nature of the bonds between the SWCNT surface and the functional groups. By means of a TGA–mass spectrometry coupling technique, the mechanisms of detachment upon heating were used to determine the nature of the grafted functional groups. In addition to the expected groups, unexpected groups were covalently grafted on the sample surface. Based on inert gas adsorption properties, we show that the functional groups are unambiguously grafted on the SWCNT sidewalls.     

The influence of single-walled carbon nanotube functionalization on the electronic properties of their polyaniline composites

The “in situ” preparation and characterization of composites of polyaniline (PANI) and single-walled carbon nanotubes (SWCNTs) are reported. To improve the dispersion and compatibility with the polymer matrix the raw SWCNTs were modified following different routes. SWCNTs oxidized by chemical or thermal treatments (nitric acid and air oxidation, respectively) were subjected to covalent functionalization with octadecylamine (ODA). SWCNT/PANI composites were prepared either from just oxidized SWCNTs, or from ODA functionalized SWCNTs. Temperature-programmed desorption, elemental analyses, ultraviolet-visible (UV-vis), UV-vis with near infrared and Raman spectroscopy, X-ray diffraction, scanning and transmission electron microscopy and conductivity measurements were used to characterize the functionalized SWCNT materials, dispersions and composites. The PANI composite prepared from air oxidized SWCNTs showed the best electrical conductivity indicating a better interaction with polyaniline than ODA functionalised SWCNTs. The improvement of conductivity is attributed to the doping effect or charge transfer of quinoide rings from PANI to SWCNTs.     

Surfactant-free assembling of functionalized single-walled carbon nanotube buckypapers

The electrical and textural properties of single-walled carbon nanotube buckypapers were tunned through chemical functionalization processes. Single-walled carbon nanotubes (SWCNTs) were covalently functionalized with three different chemical groups: Carboxylic acids (-COOH), benzylamine (-Ph-CH₂-NH₂), and perfluorooctylaniline (-Ph-(CF₂)₇-CF₃). Functionalized SWCNTs were dispersed in water or dimethylformamide (DMF) by sonication treatments without the addition of surfactants or polymers. Carbon nanotube sheets (buckypapers) were prepared by vacuum filtration of the functionalized SWCNT dispersions. The electrical conductivity, textural properties, and processability of the functionalized buckypapers were studied in terms of SWCNT purity, functionalization, and assembling conditions. Carboxylated buckypapers demonstrated very low specific surface areas (< 1 m²/g) and roughness factor (R_a = 14 nm), while aminated and fluorinated buckypapers exhibited roughness factors of around 70 nm and specific surface areas of 160-180 m²/g. Electrical conductivity for carboxylated buckypapers was higher than for as-grown SWCNTs, but for aminated and fluorinated SWCNTs it was lower than for as-grown SWCNTs. This could be interpreted as a chemical inhibition of metallic SWCNTs due to the specificity of the diazonium salts reaction used to prepare the aminated and fluorinated SWCNTs. The utilization of high purity as-grown SWCNTs positively influenced the mechanical characteristics and the electrical conductivity of functionalized buckypapers.     

The synthesis of covalent bonded single‐walled carbon nanotube/polyvinylimidazole composites by in situ polymerization and their physical characterization

Single‐walled carbon nanotube (SWCNT) polyvinylimidazole (PVI) composites have been prepared by in situ emulsion polymerization. Dispersion of raw SWCNTs in the PVI matrix was improved by surface modification of the SWCNTs using nitric acid treatment and air oxidation. The carbonyl‐terminated SWCNTs were covalently bonded to PVI by in situ polymerization and the SWCNT/PVI composite was thus obtained. The morphological and structural characterizations of the surface‐functionalized SWCNTs and SWCNT/PVI composites were carried out by Fourier transform infrared spectroscopy, X‐ray diffraction, conductivity measurements, scanning, and transmission electron microscopy. Thermograms of the materials were determined by the differential scanning calorimetry technique. The characterization results indicate that PVI was covalently bonded to SWCNTs and a new material was then obtained. The functionalized SWCNTs showed homogenous dispersion in the composites, whereas purified SWCNT resulted in poor dispersion and nanotube agglomeration. SWCNT/PVI composites exhibited chemical stability enhancement in many common solvents. I–V curves of the samples exhibit an ohmic character. Conductivity values for pure SWCNTs, pure PVI and SWCNT/PVI composite were measured to be 3.47, 2.11 × 10⁻⁹, and 2.3 × 10⁻³ S/m, respectively. Because of resonance, a large dielectric constant is obtained for SWCNT/PVI composite, which is not observed for ordinary materials. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

An easy method for direct metal coordination reaction on unoxidized single-walled carbon nanotubes

The transition metal copper (II) ion (Cu²⁺) was effectively coordinated with a single-walled carbon nanotube (SWCNT) to produce a SWCNT–Cu²⁺ complex by a metal coordination reaction. Since the complex was very reactive towards the carboxylic acid group, the chemical functionalization of SWCNTs was easy to accomplish. This approach was used to functionalize the surface of the SWCNTs with stearic acid or ethylenediaminetetraacetic acid for tuning of the relative hydrophobicity and hydrophilicity of the surface, respectively. The mild reaction conditions used for metal coordination of the SWCNTs minimized the defects that result from chemical modification of SWCNT. Thus, the electrical properties of unmodified SWCNTs were preserved. Various analytical techniques, including Fourier transform infrared spectroscopy, thermal gravimetric analysis, ultraviolet–visible spectroscopy, and water sorption isotherm measurements, were used to characterize the surface properties of the functionalized SWCNTs. Functionalization of SWCNTs by metal coordination reaction effectively modified the SWCNT surface, while conserving the excellent physical properties of the SWCNTs. The surface properties of the SWCNTs were easily tuned by introduction of the functional groups required for specific applications.     

Ionomer covalent functionalization of single‐walled carbon nanotubes by radical polymerization of zirconium acrylate

A facile and efficient covalent functionalization of single‐walled carbon nanotubes (SWCNTs) via peroxide‐mediated free radical covalent attachment and polymerization of zirconium acrylate is reported. The resulting covalently functionalized SWCNTs exhibit improved solubility in organic solvents. The covalently functionalized SWCNTs are characterized by cross polarization magic angle spinning ¹³C NMR, differential scanning calorimetry, thermogravimetric analysis, x‐ray diffraction, Raman, and infrared spectroscopy. Infrared spectroscopy reveals that carboxylate groups of covalently attached ionomers chelate with zirconium ions and the participating carboxylate groups may be from different ionomer chains leading to cross‐linking the chains. The SWCNT topology, ionic clustering, and π‐electron clouds were explored by transmission electron microscopy. © 2014 American Institute of Chemical Engineers AIChE J, 60: 820–828, 2014     

Influence of shear in the crystallization of polyethylene in the presence of SWCNTs

It is well accepted that due to epitaxy matching, carbon nanotubes are good nucleating agent for linear polyethylene. We demonstrate that not only in the quiescent conditions but also at the relatively low shear rates the presence of single-walled carbon nanotube (SWCNT) accelerates the crystallization kinetics of polyethylene (PE). The influence of SWCNTs on the crystallization kinetics in the quiescent condition is followed with the help of rheological and differential scanning calorimetry studies. The influence of flow on the stretch of the polymer chain is probed using time-resolved small-angle X-ray scattering (SAXS) and is verified with the Deborah number. SAXS data indicates that the strong shearing conditions (shear rate > 50/s for 1 s) are requisite to form shish-kebab structure in the neat polymer. However, for the low shear (shear rate < 50/s for 1 s), the shish-kebab structure that arises due to chain orientation is enhanced in the presence of SWCNTs. The development of oriented structures in SWCNT/PE composites and their absence in the neat polymer under low shear rate indicates that the presence of SWCNTs plays a significant role in the chain orientation. Overall, the results manifest the influence of SWCNTs on chain relaxation of the polymer.     

Modifying the electronic properties of single-walled carbon nanotubes using designed surfactant peptides

The electronic properties of carbon nanotubes can be altered significantly by modifying the nanotube surface. In this study, single-walled carbon nanotubes (SWCNTs) were functionalized noncovalently using designed surfactant peptides, and the resultant SWCNT electronic properties were investigated. These peptides have a common amino acid sequence of X(Valine)(5)(Lysine)(2), where X indicates an aromatic amino acid containing either an electron-donating or electron-withdrawing functional group (i.e. p-amino-phenylalanine or p-cyano-phenylalanine). Circular dichroism spectra showed that the surfactant peptides primarily have random coil structures in an aqueous medium, both alone and in the presence of SWCNTs, simplifying analysis of the peptide/SWCNT interaction. The ability of the surfactant peptides to disperse individual SWCNTs in solution was verified using atomic force microscopy and ultraviolet-visible-near-infrared spectroscopy. The electronic properties of the surfactant peptide/SWCNT composites were examined using the observed nanotube Raman tangential band shifts and the observed additional features near the Fermi level in the scanning tunneling spectroscopy dI/dV spectra. The results revealed that SWCNTs functionalized with surfactant peptides containing electron-donor or electron-acceptor functional groups showed n-doped or p-doped altered electronic properties, respectively. This work unveils a facile and versatile approach to modify the intrinsic electronic properties of SWCNTs using a simple peptide structure, which is easily adaptable to obtain peptide/SWCNT composites for the design of tunable nanoscale electronic devices.     

ECAE加工对PP/MMT复合材料结构和性能的影响

研究了聚丙烯/蒙脱土(PP/MMT)复合材料经等通道转角挤压(ECAE)加工后的结构与性能,并探讨了MMT的变形和分散机理。结果表明,ECAE加工的巨大剪切力不仅能使PP/MMT复合材料的基体产生取向,而且还可使团聚的MMT粒子在基体中变形、取向、分散和尺寸减小,且二次ECAE加工对MMT粒子的分散效果更加显著;PP/MMT复合材料经一次ECAE加工后试样的缺口冲击强度有所提高,而经二次ECAE加工后试样的冲击强度显著提高,其中含2%MMT的ECAE-PP/MMT-A试样的缺口冲击强度达到了93.1kJ/m2,为纯PP的19倍。     

Optical absorption response of chemically modified single-walled carbon nanotubes upon ultracentrifugation in various dispersants

Arc discharge single-walled carbon nanotubes (SWCNTs) were modified through different oxidative treatments and functionalization reactions. The modified SWCNT powders were dispersed in four different aqueous media and purified by ultracentrifugation. Extinction coefficients of the modified SWCNTs depended on the SWCNT type but did not depend on the dispersion medium. According to visible/near infrared spectroscopy, the purity of all the modified SWCNT dispersions substantially improved after ultracentrifugation; however, the spectrum profile, the degree of purity and the centrifugation yield were influenced by the SWCNT type, the surface functional groups and the dispersion medium. Semi-quantitative purity indexes calculated from optical absorption spectra were supported by transmission electron microscopy observations. Contents in metal impurities were analyzed by energy dispersive X-ray spectroscopy. SWCNT samples processed by oxidative acid treatments and ultracentrifugation showed metal contents of lower than 0.5 wt%.     

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     

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.     

Nebulization of single-walled carbon nanotubes for respiratory toxicity studies

An ultrafine aerosol consisting of airborne single-walled carbon nanotubes (SWCNTs) was produced by nebulizing functionalized SWCNTs in methanol. Prior to atomization, purified SWCNTs were functionalized with aryl sulfonate groups via a Birch reaction. The functionalized SWCNTs were then dispersed in methanol and nebulized using a TSI-3076 constant output atomizer. Atomic force microscopy of a mica plate placed in the flow revealed both individual and bundled SWCNTs. We anticipate that this method for producing ultrafine mists of SWCNTs will enable respiratory toxicity studies of inhaled ultrafine SWCNT particulate.     

Raman spectroscopic evidence for interfacial interactions in poly(bithiophene)/single-walled carbon nanotube composites

Electrochemical polymerization of 2,2′-bithiophene (BTh) on single-walled carbon nanotube (SWCNT) films has been studied by Raman scattering and infrared absorption spectroscopy. Covalent functionalization of SWCNTs with poly(bithiophene) (PBTh) in its un-doped and doped states is demonstrated. The occurrence of a charge transfer process at the interface of PBTh and SWCNTs, is shown by: (i) an up-shift of the Raman lines associated with the radial breathing modes of SWCNTs that reveals both a doping process and an additional twisting together as a rope with the conducting polymer as binding agent; (ii) a new Raman band in the range 1430-1450 cm⁻¹ indicating the functionalization of SWCNTs with PBTh in doped and un-doped states; (iii) strong absorption bands situated in the interval 600-800 cm⁻¹ resulting from steric hindrance produced by the nanotube binding to the polymeric chain. Treatment of the PBTh/SWCNT composite with aqueous NH₄OH solution forms un-doped PBTh covalently functionalized SWCNTs. At the resonant excitation of the metallic tubes, an additionally enhanced Raman process is generated by plasmon excitation in the metallic nanotubes. It is evidenced by a particular behavior in the Stokes and anti-Stokes branch of the PBTh Raman line at 1450 cm⁻¹.     

Single-electron transfer living radical copolymerization of SWCNT-g-PMMA via graft from approach

The sidewall functionalization of single-walled carbon nanotubes (SWCNTs) was established by poly (methyl methacrylate) (PMMA) using controlled radical polymerization (CRP) method. A bromide functionalized SWCNT (SWCNT-Br) has been used as an initiator for the synthesis of SWCNT-graft-PMMA (SWCNT-g-PMMA). The efficiency of the sacrificial initiator (S) was monitored during the polymerization process. The obtained polymers possess a uniform distribution of molecular weight with a lower polydispersity index of 1.36. The SWCNTs-based initiator acts as an efficient medium for the controlled growth of polymer on the SWCNTs surfaces. The presence of bimodal gel permeation chromatographic (GPC) curve for the SWCNT-g-PMMA(S) obtained through sacrificial initiator (S) confirms uncontrolled behavior. However, the clear sharp peak for SWCNT-g-PMMA obtained without sacrificial initiator shows its well-controlled process of polymerization, which acts as a mimic to bone cement. The efficiency of the functionalization of SWCNT and the controlled formation of SWCNT-g-PMMA composites were characterized by TGA, Raman, TEM, NMR, XPS and dispersion measurements.     

Selective deposition of semiconducting single-walled carbon nanotubes onto amino-silane modified indium tin-oxide surface for the development of poly(3-hexylthiophene)/carbon-nanotube photovoltaic heterojunctions

A method is described to obtain separation of single-walled carbon nanotubes (SWCNTs) on an indium tin-oxide (ITO) substrate by modifying the conducting surface of ITO with amino-silane functional groups. Scanning electron microscopy confirmed that the amino-silane functionalization of the substrate is a critical parameter for the immobilization of separated nanotubes. In particular spin coating the SWCNT solution onto the amino-silane modified ITO surface results in a lower nanotube density with respect to the reference sample obtained on pure ITO together with the immobilization of semiconducting carbon nanotubes onto the substrate. The possibility of using these SWCNT thin films to obtain polymer/nanotube heterojunctions for the development of organic solar cells is considered.