Alejandro Ansón-Casaos

Solvent-Free Preparation of High-Toughness Epoxy−SWNT Composite Materials

Multicomponent nanocomposite materials based on a high-performance epoxy system and single-walled carbon nanotubes (SWNTs) have been prepared. The noncovalent wrapping of nitric acid-treated SWNTs with a PEO-based amphiphilic block copolymer leads to a highly disaggregated filler with a boosted miscibility in the epoxy matrix, allowing its dispersion without organic solvents. Although direct dispersion of acid-treated SWNTs results in modestly improved epoxy matrix mechanical properties, the incorporation of wrapped SWNTs produces a huge increase in toughness (276% improvement at 0.5 wt % loading) and impact strength (193% at 0.5 wt % loading) with no detrimental effect on the elastic properties. A synergistic effect between SWNTs and the block copolymer is revealed on the basis of tensile and impact strength results. Atomic force microscopy has been applied, obtaining stiffness mappings that identify nanostructure features responsible of the dynamic mechanical behavior. The electrical percolation threshold is greatly reduced, from 0.31 to 0.03 wt % SWNTs when block copolymer-wrapped SWNTs are used, and all the measured conductivity values increased up to a maximum of 7 orders of magnitude with respect to the baseline matrix (1 wt % wrapped-SWNTs loading). This approach provides an efficient way to disperse barely dispersible SWNTs without solvents into an epoxy matrix, and to generate substantial improvements with small amounts of SWNTs.

Covalent functionalization of MWCNTs with poly(p-phenylene sulphide) oligomers: a route to the efficient integration through a chemical approach

We report a new strategy to obtain high performance polymer-grafted multi-walled carbon nanotubes (MWCNTs). Chlorophenyl-functionalized MWCNTs, obtained through the in situ generation and reaction of diazonium compounds, were subjected to polymerization in the presence of Na2S and 1,4-dichlorobenzene in order to yield MWCNTs covalently functionalized with poly(p-phenylene sulfide) (PPS) oligomers. The MWCNT functionalization and the PPS oligomeric chain growth can be controlled throughout accessible experimental variables, including the possibility to carry out the whole process in a one-pot reaction. This represents an efficient and facile route to develop covalently grafted MWCNTs beyond those reported so far for the same polymer. These materials are promising fillers for the production of high performance PPS-based composite materials, due to the improvement of the filler–matrix compatibility. The manufacturing and characterization of some test samples show that oligomer-grafted MWCNTs induce the suppression of the intrinsic confinement effect imposed by the nanofiller, as for the observation of an increase in the PPS crystallinity. An outstanding increase in the PPS thermal stability and mechanical properties is also observed, as compared to bare MWCNTs, while leaving the electrical properties unharmed.

Influence of air oxidation on the surfactant-assisted purification of single-walled carbon nanotubes.

Arc discharge single-walled carbon nanotube (SWCNT) soot was treated under different experimental conditions including gas- and liquid-phase oxidation, heat treatment in an inert gas, and hydrogen gasification. Afterward, the samples were dispersed in a surfactant and centrifuged at a moderately high speed. Near-infrared spectra of all the dispersions were compared with that of raw SWCNT soot. The relative intensity of SWCNT characteristic spectral bands strongly increased for air-oxidized samples after centrifugation, while it did not substantially change for samples oxidized with nitric acid or reduced with hydrogen. The relative SWCNT spectral intensity was associated to the sample purity through the so-called purity index, which was calculated from the S(22) band transition of semiconducting SWCNTs. Air-oxidized samples experienced a 7-fold increase in the purity index during centrifugation, while it increased by only 2-3 times for nonoxidized samples. Air oxidation specifically improves the preferential stability of SWCNTs over carbonaceous impurities in the dispersions, leading to the highest purity index values reported so far.

Epoxy composites with covalently anchored amino-functionalized SWNTs: towards the tailoring of physical properties through targeted functionalization

Functionalization of single-walled carbon nanotubes (SWNTs) with covalently grafted amine moieties provides reactive fillers with potential for covalent anchoring to an epoxy matrix. Manufacturing and characterization of a high performance epoxy system reinforced with as-grown and aminated SWNTs are presented through four different approaches. Epoxy composite materials incorporating SWNTs aminated through sidewall addition reactions present enhanced mechanical, thermal and electrical properties, beyond the effect of unfunctionalized SWNTs. The functionalization pathways studied here lead to a composite with specific improvements in some of the physical properties of the epoxy matrix, which enables the tailored design of the composites properties through functionalization. The aminationviadiazonium reaction with 4-aminobenzylamine is especially effective in enhancing the tensile and impact properties of the epoxy composites (44% improvement in impact strength at 0.1 wt% loading) and leads to the highest increase in elastic modulus reported so far for the integration of aminated nanotubes into epoxy resin. Composites incorporating aminated SWNTs throughout the 1,3-dipolar cycloaddition reaction stand out for their thermo-oxidative stability and thermomechanical properties. The incorporation of as-produced arc-discharge SWNTs into the TGAP/DDS epoxy matrix leads to composite materials with the highest electrical conductivity among all the studied samples.

Reactive fillers based on SWCNTs functionalized with matrix-based moieties for the production of epoxy composites with superior and tunable properties

Composite materials based on epoxy matrix and single-walled carbon nanotubes (SWCNTs) are able to exhibit outstanding improvements in physical properties when using a tailored covalent functionalization with matrix-based moieties containing terminal amines or epoxide rings. The proper choice of grafted moiety and integration protocol makes it feasible to tune the composite physical properties. At 0.5 wt% SWCNT loading, these composites exhibit up to 65% improvement in storage modulus, 91% improvement in tensile strength, and 65% improvement in toughness. A 15 °C increase in the glass transition temperature relative to the parent matrix was also achieved. This suggests that a highly improved interfacial bonding between matrix and filler, coupled to improved dispersion, are achieved. The degradation temperatures show an upshift in the range of 40-60 °C, which indicates superior thermal performance. Electrical conductivity ranges from ~10(-13) to ~10(-3) S cm(-1), which also shows the possibility of tuning the insulating or conductive behaviour of the composites. The chemical affinity of the functionalization moieties with the matrix and the unchanged molecular structure at the SWCNT/matrix interface are responsible for such improvements.

Electrochemical sensing of guanine, adenine and 8-hydroxy-2′-deoxyguanosine at glassy carbon modified with single-walled carbon nanotubes covalently functionalized with lysine

This work reports the synthesis and characterization of single-walled carbon nanotubes (SWCNT) covalently functionalized with L-lysine (Lys) and the analytical performance of glassy carbon electrodes (GCE) modified with a dispersion of SWCNT-Lys (GCE/SWCNT-Lys) for the highly sensitive quantification of guanine, adenine and 8-hydroxy-2′-deoxyguanosine. Detection limits of 75, 195 and 97 nM were obtained for guanine, adenine and 8-hydroxy-2′-deoxyguanosine, respectively by voltammetric adsorptive stripping with medium exchange. GCE/SWCNT-Lys was successfully used for the detection of adenine and guanine oxidation after adsorption of salmon sperm-double stranded DNA. A clear definition of 8-hydroxy-2′-deoxyguanosine oxidation signal is observed even in the presence of large excess of guanine, adenine or salmon sperm-double stranded DNA.

Peptide-based biomaterials. Linking L-tyrosine and poly L-tyrosine to graphene oxide nanoribbons

Peptide-based biomaterials are being studied actively in a variety of applications in materials science and biointerface engineering. Likewise, there has been ongoing exploration over the last few decades into the potential biological applications of carbon nanomaterials, motivated by their size, shape, structure and their unique physical and chemical properties. In recent years, the functionalization of carbon nanotubes and graphene has led to the preparation of bioactive carbon nanomaterials that are being used in biomedicine as structural elements and in gene therapy and biosensing. The present study proposes different strategies for the bonding of l-tyrosine and the homopolypeptide poly-l-tyrosine to graphene oxide nanoribbons (GONRs). The covalent attachment of l-tyrosine was undertaken by amidation of the α-amine group of tyrosine with the existing carboxylic groups in GONR and by means of esterification through phenol nucleophiles contained in their side chains. In both cases use was made of protective groups to address the functionalization with the desired reactive groups. The linking of GONRs to the PTyr was attempted according to two different strategies: either by ester bonding of commercial PTyr through its phenol side groups or by in situ ring-opening polymerization of an N-carboxyanhydride tyrosine derivative (NCA-Tyr) with Tyr-functionalized GONRs. These biofunctionalized nanomaterials were characterized by Raman and infrared spectroscopies, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, fluorescence and electrochemical techniques. On the basis of their properties, prospects for the potential utilization of the prepared hybrid nanomaterials in different applications are also given.

Study of neuron survival on polypyrrole‐embedded single‐walled carbon nanotube substrates for long‐term growth conditions

Cultures of primary embryonic rat brain hippocampus neurons with supporting glia cells were carried out on different substrates containing polypyrrole (PPy) and/or single-walled carbon nanotubes (SWCNTs). Neuron adhesion, neurites and dendrites branching elongation, and development of neuron networks on substrates were followed by phase-contrast optical microscopy and quantified to state cell survival and proliferation. Suspensions of as-grown and purified SWCNTs were sprayed on a glass coverslips and PPy/SWCNTs were deposited by potentiodynamic electrochemical deposition. Cell neurotoxicity revealed by neuron death was very high for purified SWCNTs substrates in good agreement with [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] (MTT) test showing lower viability on SWCNTs containing substrates compared with PPy-substrates and control samples probably due to the metal content and the carboxylic groups introduced during the purification. It is interesting to highlight that neurons grown on PPy-substrates adhere developing neurites and branching dendrites earlier even than on control cultures. On subsequent days the neurons are able to adapt to nanotube substrates developing neuron networks for 14-day cultures with similar patterns of complexity for control, PPy and PPy/SWCNT substrates. PPy/SWCNT substrates show a lower impedance value at frequencies under 1 Hz. We have come to the conclusion that glia cells and PPy added to the culture medium and substrates respectively, improve in some degree nanotube biocompatibility, cell adhesion and hence cell viability.

Piezoresistive response of Pluronic-wrapped single-wall carbon nanotube–epoxy composites

This article reports on the piezoresistive behaviour of polymer-based nanocomposites, which are composed of epoxy resins and Pluronic-wrapped carbon nanotubes. The samples were prepared with carbon nanotube concentrations up to 1 wt.%. Good carbon nanotube dispersion was achieved due to the Pluronic wrapping of the carbon nanotube, as confirmed by electron and atomic force microscopies. The correlation between the electrical resistivity and mechanical strain was obtained for varying mechanical deformation. The electrical response is linear for small strains, and the values of the gauge factor are ∼2.6. The small variations of the signal over 32 cycles, the time response to deformations from 0.1 to 50 mm min−1 and the stable temperature behaviour up to 60°C show the viability of these materials to be used as piezoresistive sensors.

SWCNTs AS ELECTRON WITHDRAWERS IN NANOCRYSTALLINE ANATASE PHOTOCATALYSTS

Single-walled carbon nanotube (SWCNT)/anatase TiO2 composite materials were prepared by successive sol–gel and hydrothermal processes. The composites contained thin SWCNT bundles embedded in aggregates of ~ 12 nm anatase crystallites. A series of SWCNT/TiO2 photocatalysts was prepared with various SWCNT contents; a SWCNT content of ~ 8 wt.% was found to be optimal for methylene blue (MB) degradation under combined UV/visible radiation. The optimized SWCNT/TiO2 composite demonstrated substantially higher photocatalytic activity than pure nanocrystalline anatase (5.2 times) and Degussa P-25 TiO2 powder (2.7 times). The MB degradation and mineralization processes were separately evaluated and complete decomposition of MB was shown to take place. The presence of SWCNTs caused an increase in the visible light absorbance of TiO2; however, SWCNT/TiO2 composites did not show any photocatalytic activity when the UV part of the UV/visible light source was filtered. Therefore SWCNTs worked as acceptors for the TiO2 photoexcited electrons, but did not act as sensitizers for TiO2.