Alejandro Ansón

Sensitivity of single wall carbon nanotubes to oxidative processing: structural modification, intercalation and functionalisation

Abstract The effect of oxidation on modification of single wall carbon nanotubes (SWCNTs) through successive purification steps has been studied. The efficient elimination of metal impurities has been followed by induced coupled plasma spectroscopy. Upon acid treatment, Raman spectroscopy clearly proofed that HNO3 molecules were intercalated into the bundles of SWCNTs. At the same time, SWCNTs also have suffered a high degree of degradation and defects were introduced. The subsequent thermal processes led to the removal of further defect carbon materials and to the almost complete de-intercalation of the HNO3 molecules. Changes in the structure of the SWCNT bundles have been observed by transmission electron microscopy. While bundles tend to separate upon acid treatment, after the complete purification process, the remaining SWCNTs tend to form thick bundles again. The existence of functional groups in the raw single wall carbon nanotubes material and their modification and almost complete removal after the final annealing step has been studied by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and temperature programmed desorption. Nitrogen adsorption isotherms analysed according to Brunauer–Emmet–Teller showed important changes in the pore volume and surface area through the purification steps.

Single-Walled Carbon Nanotubes as Electrodes in Supercapacitors

7 pages.-- PACS: 82.47.Uv; 82.45.Fk; 85.35.Kt; 68.43.Mn; 82.45.Yz; 82.45.Gj; 81.40.Gh; 78.30.Na

Modifications of single-wall carbon nanotubes upon oxidative purification treatments

A systematic characterization of single-wall carbon nanotube (SWCNT) material after successive purification steps, including reflux treatment with nitric acid, air oxidation, and annealing, has been performed. Inductively coupled plasma–optical emission spectroscopy shows that a considerable reduction of the metal impurities by up to 95% can be obtained by the nitric acid reflux treatment. During this process, Raman spectroscopy clearly proves that HNO3 molecules are intercalated into the bundles of SWCNTs. At the same time, SWCNTs have suffered a high degree of degradation and defects are being introduced. The subsequent thermal processes lead to the removal of further defect carbon materials and to the almost complete de-intercalation of the HNO3 molecules. Transmission electron microscopy reveals that the remaining SWCNT bundles tend to form thick bundles. Thus the applied purification process results in a high-purity SWCNT material with a drastically reduced content of metal nanoparticles and composed of large bundles of SWCNTs.

The influence of a compatibilizer on the thermal and dynamic mechanical properties of PEEK/carbon nanotube composites

The effect of polyetherimide (PEI) as a compatibilizing agent on the morphology, thermal, electrical and dynamic mechanical properties of poly(ether ether ketone) (PEEK)/single-walled carbon nanotube (SWCNT) nanocomposites, has been investigated for different CNT loadings. After a pre-processing step based on ball milling and pre-mixing under mechanical treatment in ethanol, the samples were prepared by melt extrusion. A more homogeneous distribution of the CNTs throughout the matrix is found for composites containing PEI, as revealed by scanning electron microscopy. Thermogravimetric analysis demonstrates an increase in the matrix degradation temperatures under dry air and nitrogen atmospheres with the addition of SWCNTs; the level of thermal stability of these nanocomposites is maintained when PEI is incorporated. Both differential scanning calorimetry and synchrotron x-ray scattering studies indicate a slight decrease in the crystallization temperatures of the compatibilized samples, and suggest the existence of reorganization phenomena during the heating, which are favoured in the composites incorporating the compatibilizer, due to their smaller crystal size. Dynamic mechanical studies show an increase in the glass transition temperature of the nanocomposites upon the addition of PEI. Furthermore, the presence of PEI causes an enhancement in the storage modulus, and hence in the rigidity of these systems, attributed to an improved interfacial adhesion between the reinforcement and the matrix. The electrical and thermal conductivities of these composites decrease with the incorporation of PEI. Overall, the compatibilized samples exhibit improved properties and are promising for their use in industrial applications.

Carbon Nanotube Effect on Polyaniline Morphology in Water Dispersible Composites

A straightforward, template-free chemical oxidative polymerization of aniline was used to prepare nanofibrillar polyaniline (nf-PANI) and a set of corresponding composites with multiwall carbon nanotubes (MWNTs). All the products showed remarkable water dispersibility since they are formed by hydrophilic particles of nanometric size. A comparative study performed on composites in a wide range of MWNT loadings has led to two main conclusions: on one hand, the presence of MWNTs affects neither the chemical structure nor the crystallinity of polyaniline. On the other hand, even small amounts of MWNTs have a significant effect on the morphology of polyaniline in composites. This effect is noticeable not only in electron microscopy images but also in the UV-vis absorbance of water dispersions and electrical conductivity behavior in the solid state. Competition between nucleation sites during polymerization is proposed as an explanation for these phenomena.

Hydrogen adsorption on a single-walled carbon nanotube material: a comparative study of three different adsorption techniques

Hydrogen adsorption measurements on mixed carbon material containing single-walled carbon nanotubes (SWNTs) obtained by the electric-arc method were carried out by three different techniques: a volumetric system, a gravimetric system and an electrochemical method. The found H2 gas adsorption capacity (volumetric and gravimetric) is very low, around 0.01 wt% at room temperature and pressure, increasing to 0.1 wt% at 20 bar. Electrochemical measurements show a slightly higher capacity (0.1–0.3 wt%) than volumetric and gravimetric data. The results obtained by the three different techniques are compatible within each other and they are also in good agreement with other previously reported data from different researchers.

Grafting of a hydroxylated poly(ether ether ketone) to the surface of single-walled carbon nanotubes

A hydroxylated poly(ether ether ketone) (HPEEK) derivative has been covalently grafted onto the surface of acid-treated single-walled carbon nanotubes (SWCNTs) following two different esterification approaches. The hydroxylation degree of the HPEEK and the extent of the grafting reactions were determined by thermogravimetric analysis. Microscopic observations revealed an increase in the bundle diameter of the SWCNTs and the heterogeneous composition of the synthesized samples. Infrared, nuclear magnetic resonance and X-ray photoelectron spectra corroborated the grafting success, showing the appearance of signals associated with the ester group. The polymer-grafted SWCNTs display higher decomposition temperatures and a wider range of thermal degradation than the HPEEK. The esterification decreases the crystallization and melting temperature as well as the crystallinity of the HPEEK. The semicrystalline nature of the grafted samples was confirmed by X-ray diffraction analysis, which reveals a diminution in the crystal size of the polymer. Dynamic mechanical studies show an exceptional increase in the storage modulus and glass transition temperature of the polymer by the attachment to the SWCNTs. Slightly better thermal and mechanical properties are observed for the sample with the higher esterification degree. The HPEEK-grafted SWCNTs can be used as fillers to prepare PEEK nanocomposites with enhanced performance.