A comprehensive study of a less harmful functionalization of multiwalled carbon nanotubes (MWCNT) was performed. The influence of ultrasonic cavitation and solid/liquid interface was indirectly evaluated by statistical characterization of MWCNT aspect ratio and degree of functionalization. MWCNT aspect ratio was determined through hundreds of electron microscopy images. Degree of functionalization of MWCNT was characterized by elemental analysis and thermogravimetry. Distribution of different oxygen-containing functional groups was assessed by potentiometric titration. MWCNT aqueous dispersions were evaluated by electrophoretic mobility and dynamic light scattering. An acid volume over 90% lower than usually reported in literature guaranteed MWCNTs with significantly larger aspect ratio, higher proportion of carboxylic groups and a more negative zeta potential in aqueous suspension. These results can be related to a more localized ultrasonic cavitation in MWCNTs/acid interface for reduced liquid volumes. This distinguished influence of ultrasonic cavitation may be a valuable contribution to more eco-friendly processes with nanomaterials.

Single-walled carbon nanotubes are oxidized in the presence of H2SO4/HNO3 mixtures containing distinct concentrations of the nitronium ion, [NO2+]. The spectroscopic analyses of the final samples suggest a higher structural disorder in the oxidized systems with increasing [NO2+]. This is due to a considerable oxygen amount on the tube surface, reaching up to 30%, depending on the reaction time and [NO2+]. Interestingly, if long reaction time is considered, the oxygen amount on the tube surface is maximum for low [NO2+] and reduces slightly for larger [NO2+]. On the other hand, the oxidation process occurs gradually at 4 h, allowing a fine control of the oxidation process. Therefore, if fine tuning of the oxidation degree is desirable, the reaction must be conducted during short time (4 h) using increasing [NO2+] as those obtained from 2:1, 2.5:1 and 3:1 H2SO4/HNO3 acid mixtures to produce increasing content of functionalization.

The introduction of oxygen groups in carbon nanotubes is considered crucial for many applications. However, there is a lack of controlled functionalization methods which ensure nanotubes with specific property values according to each interest. In this work, acid treatments of multiwalled carbon nanotubes (MWCNTs) employing an optimized ultrasound process with moderate heating and stirring were studied by means of a factorial design. The functionalized nanotubes were characterized by thermogravimetry, elemental analysis, Raman spectroscopy, electron microscopy and water stability tests. Statistic models were fitted for the degree of functionalization and length reduction of MWCNTs. Temperature was identified as a key parameter to produce more functionalized MWCNTs with less structural damage. The properties of the functionalized MWCNTs can be tailored by the choice of parameters exploited in the statistical models developed to enable different end-use requests, such as for polymeric composites or bio-related applications, which is the original contribution of this work.

Few-layered graphene oxide (GO) was prepared using a fast and energy-saving method by microwave-assisted acid technique. The oxygenated groups existing on the GO surface were determined using UV-Vis, X-ray photoelectron and Fourier-transform infrared spectroscopies. An oxygenated group percentage of 30% in mass for the GO was observed by thermogravimetric analysis. The reduced few-layered graphene oxide (rGO) film annealed at 110 °C deposited onto a silicon/silica wafer showed expanded graphite-like structure with 0.70 nm between the rGO sheets, as determined by X-ray diffraction. This rGO film exhibited a relatively high electrical conductivity value of 7.36 × 102 S m-1 confirming the good restoration of the π-conjugated system. The prepared GO sample exhibited good stability in water from pH 4 to 12, as determined by its zeta potential, and contained 5 to 9 layers, as determined by atomic force microscopy (AFM) and transmission electron microscopy (TEM).

Este trabalho apresenta uma caracterização de sistemas epoxídicos a base do éter diglicidílico do bisfenol A (DGEBA), curado com dois co-monômeros do tipo amina cicloalifática - piperidina (Pip) e 4,4'-diamino-3,3'-dimetildiciclohexilmetano (3DCM) - antes e após a aplicação de irradiação com raios gama. Variações nas propriedades mecânicas e térmicas foram investigadas através de medidas do módulo elástico, da temperatura de transição vítrea e do perfil de degradação dos materiais. Foi possível observar que uma dose de irradiação de 50 kGy provoca variações sutis em propriedades como rigidez e estabilidade, que são relevantes do ponto de vista fundamental. Este trabalho permite afirmar que as variações de propriedades observadas não implicam em impacto negativo na utilização destes sistemas como biomaterial na área médica, considerando a etapa de esterilização por radiação de que são objeto.

Two epoxy polymers based on diglycidyl ether of bisphenol A (DGEBA), cured with piperidine (Pip) and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane (3DCM), were characterized before and after treatment with γ irradiation. The changes in the mechanical and thermal properties were studied by elastic modulus, glass transition temperature and degradation temperature measurements. A dose of 50 kGy of irradiation caused subtle variations in properties such as rigidity and stability, which are relevant from the fundamental point of view. The variations do not imply on negative impact when considering the stage of sterilization during the use of these systems as a biomaterial in the medical area.

A influência de modificação química (por tratamento ácido seguido de funcionalização com trietilenotetramina, TETA) sobre a superfície de nanotubos de carbono de paredes múltiplas (MWCNT) foi estudada qualitativa e quantitativamente. A análise termogravimétrica (TGA) mostrou que, no caso do nanotubo funcionalizado com amina, 29% de perda de massa pode ser atribuída a -C(=O)TETA e grupos funcionais residuais que contêm oxigênio. A espectroscopia de fotoelétrons excitados por raios X (XPS) foi utilizada para observar as funções aminadas e oxigenadas ligadas covalentemente à superfície do nanotubo. As imagens de microscopia de força elétrica (EFM) indicaram que, à medida que se modifica a química superficial dos nanotubos em presença de ar, estes mostram respostas diferentes em função do potencial da ponta. Deslocamentos nos sinais de fase de EFM decrescem quando se modifica a superfície dos tubos com grupos funcionais contendo oxigênio e amina. Em atmosfera seca e inerte de N2, as três diferentes superfícies mostraram a mesma resposta à EFM. Além disso, o caráter hidrofílico dos "buckypapers" cresceu na ordem MWCNT < MWCNT-aminado < MWCNT-oxidado.

The influence of chemical modification by acid treatment followed by triethylenetetramine (TETA) functionalization on the surface of multi-walled carbon nanotubes (MWCNT) was evaluated, both qualitative and quantitatively. Thermogravimetric analysis (TGA) showed that, in the case of amine-functionalized nanotubes, 29% of mass loss can be attributed to -C(=O)TETA and residual oxygen-containing functional groups. X-ray photoelectron spectroscopy (XPS) was used to observe the oxygenated and aminated functions covalently linked to the nanotube surface. Electric force microscopy (EFM) images indicated that the nanotubes with diverse surface chemistry showed distinct responses to the tip potential in the presence of air. Shifts in EFM phase images decreased when the nanotube surface was modified with oxygen and amine-containing functional groups. In dry and inert N2 atmosphere, however, the three different surfaces showed the same response to EFM. In addition, the hydrophilic character of the buckypapers increased in the order MWCNT < aminated-MWCNT < oxidized-MWCNT.

Multi-walled carbon nanotubes (MWCNTs) functionalized with amine and carboxyl groups were used to prepare polyurethane/MWCNT nanocomposites in two distinct concentrations: a lower value of 1 mass% (spray coating) and a higher one of ~50 mass% (buckypaper based). The MWCNT-NH2 sample contained only 0.5 mass% of amine groups, whereas MWCNT-COOH contained 5 mass% of carboxyl groups. The MWCNT functionalized with low amine group content showed improved thermal properties when compared to neat thermoplastic polyurethane (TPU) and MWCNT-COOH based nanocomposites. The electrical conductivity of the polyurethane elastomer was greatly increased from 10-12 to ~10-5 S cm-1in the 1 mass% nanotube composite and to 7 S cm-1for the MWCNT-NH2 buckypaper-based nanocomposite. Furthermore, the relative high content of functional groups in the MWCNT-COOH sample, which disrupt the sp²structure in the nanotube walls, led to inferior properties; for instance the conductivity of the buckypaper based composite is one order of magnitude lower when using MWCNT-COOH in comparison with the MWCNT-NH2. These results show the range of property design possibilities available with the elastomeric polyurethane nanocomposite by tailoring the functional group content and the carbon nanotube load.

Polyurethane/multi-walled carbon nanotube (MWCNT) nanocomposites have been prepared with nanotube concentrations between 0.01 wt% and 1 wt%. MWCNT as-synthesized samples with ~74 nm diameter and ~7 μm length were introduced by solution processing in the polyurethane matrix. Scanning electron microscopy (SEM) images demonstrated good dispersion and adhesion of the CNTs to the polymeric matrix. The C=O stretching band showed evidence of perturbation of the hydrogen interaction between urethanic moieties in the nanocomposites as compared to pure TPU. Differential scanning calorimetry and positron anihilation lifetime spectroscopy measurements allowed the detection of glass transition displacement with carbon nanotube addition. Furthermore, the electrical conductivity of the nanocomposites was significantly increased with the addition of CNT.

Polímeros condutores iônicos ou eletrólitos poliméricos constituídos por um sistema de sal dissolvido em uma matriz polimérica sólida são materiais que apresentam interesse científico e potencial tecnológico. A dissolução de sais em uma matriz polimérica amorfa ou semicristalina sólida leva a estudos sobre intrigantes aspectos estruturais, que podem ser abordados por técnicas físico-químicas diversas tais como RMN, Raman e Espectroscopia de Vida Média de Pósitrons. Os estudos estruturais são correlacionados com propriedades eletroquímicas visando à utilização desses materiais em dispositivos tais como baterias, supercapacitores e células solares. Grupos brasileiros têm gradativamente ampliado os estudos e aplicações de eletrólitos poliméricos sólidos.

Ionic conducting polymers or polymer electrolytes prepared with the addition of a soluble salt in a solid polymeric matrix are very important materials, associated with an intense research activity and technological efforts. Structural studies in a system of salt dissolved in an amorphous or semicrystalline solid polymeric matrix can be done with various techniques, such as NMR, Raman and Positron Annihilation Spectroscopy. The structural studies are correlated with electrochemical properties in order to evaluate these materials for applications in batteries, supercapacitors and solar cells. Brazilian researchers are contributing to the fundamental research and development of new applications of polymeric electrolytes.