Abstract In this study we evaluated the use of eucalyptus lignin as a stabilizer in combination with other stabilizers in a vulcanized elastomeric based on natural rubber. The stabilizers tested were 6PPD (N-1,3-dimethyl-butyl-N'-phenyl-p-phenylenediamine), TMQ (oligomerized 2,2,4-trimethylquinoline), paraffin wax and eucalyptus lignin. At predetermined time intervals, samples were taken from aging conditions and the mechanical properties and additive content were determined. The sample with a combination of wax and lignin in the same formulation showed the greatest resistance to oxidative degradation. In samples with only one stabilizer, the migration test indicated greater diffusion of lignin to the surface. Samples exposed to thermo-oxidative aging showed greater loss in the mechanical properties of tear strength and 6PPD consumption. In the accelerated aging with ozone, all showed a behavior more resistant to aging. We concluded that lignin can be used as a substitute for synthetic stabilizers, without impairing the performance of natural rubber compounds.

Abstract In this work, NRL films were enriched with red propolis and silver nanoparticles with the aim of obtaining dressings with bactericide properties. To improve the properties of these materials, plasma treatment was also applied to the films. Cytotoxic effects were evaluated by MTT and agar diffusion assays on secondary and stem cells. Determination of cell behavior on the films were assessed by EDS and FEG-SEM. In general, the plasma modified NRL films presented hydrophilic character, favorable condition for biomedical applications. RBS results showed that silver is probably in nanoparticulate form. MTT assays revealed that non-cytotoxic effects were observed for all the samples extracts. Either the plasma treatment or silver deposition were effective in sterilizing the samples and modifying their surfaces. It was demonstrated in this in vitro study that ADSCs associated with NRL films enriched with propolis should be considered promising for application in the healing of occlusive wounds.

This research aimed to evaluate the ideal proportion of two stabilizers in elastomeric compositions indicated for tire sidewall. The stabilizers applied in different proportions were N-1,3-dimethyl-butyl-N'-phenyl-p-phenylenediamine (6PPD) and oligomerized 2,2,4-trimethyl-quinoline (TMQ). Nine compositions were prepared with 0.5, 1.5 and 2.5 phr of 6PPD combined with 0.5, 1.0 and 1.5 phr of TMQ. The compounds were exposed to accelerated aging processes, including thermo-oxidative, photochemical and ozone chamber. Also, the samples were aged in the environment for 440 days. At regular intervals, the samples were evaluated. Gas chromatography was used to quantify the content of 6PPD. Overall, the samples exposed to thermo-oxidative aging showed the greatest loss of mechanical properties (tear and tensile strength) as well as the 6PPD content. From the mechanical strength results, it was possible to conclude that the best combination of stabilizers was 2.5 phr of 6PPD and 1.0 of TMQ.

The aim of this study was to prepare and characterize a hybrid layered material (organoclay) with a Na-montmorillonite and the triethylene glycol mono-n-decyl ether (C10E3) nonionic surfactant which forms a lamellar phase at room temperature. The synthesized organoclay was characterized by complementary techniques (Fourier transform infrared spectroscopy and X-ray diffraction). Experiments in conjunction with electron density analysis showed that a bilayer or membrane of C10E3 was intercalated within the interlayer space of a naturally exchanged Na-montmorillonite. The intercalation of a bilayer of C10E3 in a clay mineral offers new perspectives for the manufacturing of nanomaterials. While showing a hydrophobic surface and a large interlayer space value, the resulting organoclay preserves the compensating cations within the interlayer space allowing one to perform ion exchanges, making easier the intercalation of further organic molecules of important size with functional properties or for environmental purposes.

This paper describes the adsorption of 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) from aqueous solution by decomposed peat. The peat presented a good adsorption process, close to 76.2% for E2 removal and approximately 55.0% for EE2. Moreover, the results indicated a probable multi-layered process. Adsorption isotherms were well fitted by Freundlich model. The data were evaluated considering the pseudo-first-order and pseudo-second-order approaches, being the second more significant mechanism in the rate-controlling step. Thermodynamic data revealed that hormones adsorption onto peat is spontaneous under the employed experimental conditions. The results confirmed the potential of this adsorbent to be employed for effluents treatment.

Os valores de acidez carboxílica (CA), fenólica (PhA) e total (TA) de um conjunto de cinco amostras padrão da Sociedade Internacional de Substâncias Húmicas (IHSS) e de quatro compostos modelo foram determinados pelo método de titulação potenciométrica. Os dados das curvas de titulação foram tratados pelo programa BEST7 assim como pela equação de Henderson-Hasselbalch modificada (MHHM) e os parâmetros obtidos mostraram-se extremamente dependentes do modelo matemático aplicado. Para as amostras de substâncias húmicas (SH), a aplicação da MHHM resultou em uma alta CA e uma baixa PhA, sendo o resultado praticamente oposto quando o programa BEST7 foi empregado. No caso dos compostos modelo entretanto, os valores de acidez convergiram aos valores esperados (teóricos) independente do modelo aplicado. Para investigar as razões das discrepâncias, variações na condução das titulações (p.e., titulação rápida ou lenta) também foram consideradas. O conjunto de informações mostrou que a determinação da acidez de SH por titulação potenciométrica é extremamente dependente do modelo matemático, assim como das condições experimentais aplicadas.

Carboxylic (CA), phenolic (PhA) and total (TA) acidity contents of five International Humic Substances Society (IHSS) standards and four model compounds were determined via the potentiometric titration method. Titration curves were scrutinized both by the BEST7 algorithm and the modified Henderson-Hasselbalch model (MHHM). In the case of IHSS samples, the fitting data depended on the analytical procedure undertaken. Whilst high CA and low PhA were usually recorded using the MHHM, the opposite trend was observed employing the BEST7 algorithm. In contrast, in the case of model compounds the acidity values matched well with theoretical data regardless of the procedure. In order to better understand the reasons for such discrepancies changes in the titrations procedure (e.g.: fast or slow) were also considered. General data strongly suggest that acidity determination of humic substances (HS) by potentiometric methods is extremely dependent on both the choice of mathematical model to fit experimental data points as well as the experimental conditions employed.

A reciclagem de elastômeros vulcanizados tem sido um problema para as empresas geradoras de resíduos elastoméricos, e ao mesmo tempo um amplo campo de estudo para pesquisadores da área. Diante da possibilidade de recuperação desses resíduos, deu-se início a este trabalho, relacionado à incorporação de pó de pneu de automóvel (STR-r) como uma carga, em uma formulação típica para banda de rodagem de pneu de motocicleta (formulação base - FB). O estudo teve início com a caracterização do STR-r, com base na análise granulométrica, análise termogravimétrica (TG) e calorimetria exploratória diferencial (DSC). A incorporação do STR-r na FB foi realizada em misturador aberto, nas proporções de 5 a 20 phr. Foram calculados os parâmetros reométricos de vulcanização e determinadas as propriedades mecânicas como resiliência, dureza (Shore A), resistência à abrasão, à tração e ao rasgamento dos compósitos preparados. Os resultados foram comparados aos da FB de um processo produtivo de uma empresa de pneus para motocicleta. A partir da análise dos resultados dos diferentes compósitos, foi escolhida a formulação com 10 phr de STR-r para ser produzida em escala industrial, ou seja, em misturador fechado, tipo Banbury. Os cálculos do custo de produção foram realizados com o objetivo de avaliar a viabilidade econômica deste desenvolvimento.

The recycling of vulcanized elastomers represents a problem for companies generating elastomeric residues and has become a wide field of study for researchers in this area. This study addresses the possible use of these residues and investigates an alternative for their recovery through incorporation of tread powder of cars tires (STR-r) as a filler into a typical formulation for motorcycle tire tread (base formulation - BF). The study began with the characterization of the STR-r, based on granulometric, thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses. The incorporation of STR-r into BF was carried out in an open mixer, in the proportions of 5 to 20 phr. The rheometric parameters of the vulcanization and the mechanical properties of the composites prepared, such as elongation at break, hardness (Shore A), abrasion resistance, tensile and tear strength, were determined. The results were compared with those of BF used in the production process of a motorcycle tire company. Following the analysis of the results for the different composites, the formulation with 10 phr of STR-r was selected to be produced on an industrial scale, that is, in a closed Banbury-type mixer. The calculation of the production cost was carried out in order to evaluate the economic viability of this recycling option.

Seis amostras de ácidos fúlvicos (AF) e húmicos (AH) estuarinos foram fracionadas por meio de cromatografia líquida de alta performance em fase reversa, num gradiente de polaridade água -> acetonitrila, com detecção por fluorescência. Diferenças entre os cromatogramas mostraram que os AH contêm mais componentes hidrofóbicos que os AF. Os espectros de fluorescência tridimensional das frações foram bastante similares entre si e também ao da amostra original, indicando que, apesar das polaridades distintas, a complexidade e as principais características do material original se mantêm. Um mesmo grupo de fluoróforos parece ser responsável pelas características de fluorescência, dos dois tipos de substâncias húmicas. Um deslocamento batocrômico dos espectros de emissão das soluções originais, com relação àqueles das frações, foi atribuído a uma maior proximidade destes fluoróforos, possivelmente devido à formação de agregados. Em geral, os resultados confirmam o conceito de que as "macromoléculas" húmicas consistem de associações de estruturas menores com características químicas semelhantes.

Six estuarine fulvic (FA) and humic acids (HA) were fractionated with reversed-phase high performance liquid chromatography in a water/acetonitrile gradient, with fluorescence detection. Differences between FA and HA chromatograms pointed to a higher incidence of hydrophobic components in the latter. Excitation-emission matrix fluorescence diagrams of most fractions were similar to those of the bulk samples indicating that, in spite of their distinct polarities, the complexity and main spectral characteristics of the materials persisted. A primary group of fluorophores, which are present in most of the fractions, seems to be at the origin of the fluorescence properties of both kinds of HS. A bathochromic shift of the bulk solutions spectra in relation to the fraction emissions was attributed to a greater proximity of these fluorophores, possibly due to the formation of aggregates. Generally, the results reinforced concepts that humic macromolecules consist of assemblages of structurally similar building blocks.