ABSTRACT Martensitic stainless steels can be used in different applications such as surgical instruments where a good wear and corrosion resistance are required. Surface modification treatments such as nitriding improve the mechanical properties of these steels, however; they affect the corrosion resistance. For this reason, the DLC (Diamond Like Carbon) coatings deposition can be convenient. The wear and corrosion behaviour was studied in duplex samples (nitrided and PACVD coated) and they were compared with nitrided and only coated samples and with those without treatment, only heat treated (quench and tempering). The coatings were analyzed by Raman spectroscopy and EDS. Pin on disk tests were performed and the adhesion was evaluated using Scratch Test and Rockwell C Indentation. The nanohardness was measured with a Berkovich indenter. The corrosion tests for surgical instruments (according to the Standard ASTM F 1089 -02) and Spray Salt Fog tests were carried out. In the DLC coatings, the ID/IG ratio was 0.8 and the hydrogen content was calculated and resulted to be about 20 %. The coating thickness was 2 µm and the hardness reached 24 GPa. The nitrided layer thickness was 10 µm. The duplex and coated samples presented low friction coefficient and the wear volume loss was undetectable. The coatings had good corrosion behaviour in the corrosion tests. Nevertheless, the nitrided sample presented a corroded region in the copper sulfate and boil tests. The duplex samples had better adhesion than the coated samples in scratch test and indentation Rockwell C.

RESUMEN Los aceros inoxidables martensíticos como el AISI 420 tienen múltiples aplicaciones, entre ellas instrumentos quirúrgicos, donde se requiere buena resistencia al desgaste y a la corrosión. Los tratamientos de modificación superficial, como la nitruración iónica, permiten mejorar las propiedades mecánicas de estos aceros pero afectan su resistencia a la corrosión. Por esta razón, un tratamiento posterior de deposición de recubrimiento tipo DLC (“Diamond Like Carbon”, carbono símil diamante) puede ser conveniente. En este trabajo se estudió el comportamiento al desgaste y a la corrosión de muestras dúplex (nitruradas y recubiertas por PACVD) y se compararon con muestras nitruradas, sólo recubiertas, nitruradas y sólo templadas y revenidas. Se analizaron los recubrimientos con espectroscopia Raman y EDS. Se realizaron ensayos de desgaste tipo “pin on disk” y se evaluó la adhesión mediante ensayos de Scratch Test e indentación Rockwell C. Se midió nanodureza con indentador Berkovich. Se llevaron a cabo los ensayos propuestos para instrumentos quirúrgicos en la Norma F 1089-02 (prueba de agua hirviendo y de hisopado con sulfato de cobre) y ensayos de niebla salina. Estos recubrimientos tienen una relación ID/IG de 0,8 y bajo contenido de hidrógeno aproximadamente del 20 %. El espesor de los recubrimientos fue de 2 µm y la dureza alcanzó 24 GPa. La capa nitrurada tuvo un espesor de 10 µm. Las muestras dúplex y recubierta presentaron bajo coeficiente de fricción y el volumen desgastado fue indetectable. Además, tuvieron buen comportamiento a la corrosión en el ensayo de niebla salina y en los ensayos propuestos en la Norma ASTM F 1089-02. No obstante, la muestra sólo nitrurada presentó una región corroída en el ensayo de sulfato de cobre y en el de agua hirviendo. La muestra dúplex presentó mejor adhesión que la muestra sólo recubierta en los ensayos de Scratch Test y de indentación Rockwell C.

ABSTRACT The adsorption of Violet Remazol 5R (VR 5) on wood sawdust modified with succinic anhydride (SSA) as a function of contact time, pH, and initial dye concentrations was investigated using a batch technique under ambient conditions. The SSA obtained was confirmed by IR spectroscopy, thermogravimetry and 13C NMR, and degrees of substitution (DS) were calculated. A study on the effect of the pH on the adsorption of VR 5 showed that the optimum pH was 2.0. The interactions were assayed with respect to the pseudo-first-order and pseudo-second-order kinetic models, and were found to follow closely the pseudo-second-order. The isotherm was adjusted to the Langmuir, the Freundlich and the Temkin sorption models. SSA is a promising material for the removal of dye textile from aqueous solutions, and under conditions studied the removal percentage achieved was 51.7%.

Natural lignocellulosic fiber epicarp extracted from the babassu coconut (Orbignya speciosa) was chemically modified through reaction with molten maleic anhydride without solvent, with incorporation of 189.34 mg g-1 of carboxylic acid groups into the biopolymer structure. The success of this reaction was also confirmed by the presence of carboxylic acid bands at 1741 and 1164 cm-1 in the infrared spectrum. Identically, the same group is observed through 13C NMR CP/MAS in the solid state, via high field signals in the 167 pm region. Both the precursor and the immobilized maleated biopolymers presented nearly the same thermal stability and similar crystallinity to cellulose. However, the pendant carboxylic groups have the ability to remove copper with maximum sorption through a batchwise process at pH 6.0, as expected from the point of zero charge, determined to be 6.45. The sorption kinetic data were fitted to pseudo-first order, pseudo-second order, Elovich-chemisorption and intra-particle diffusion models and the equilibrium data were fitted to the Langmuir, the Freundlich and Tenkim isotherm models. Taking into account a statistical error function and determination coefficients, the data were fit to the pseudo-first and pseudo-second order kinetic and Langmuir isotherm models, with a maximum sorption capacity of copper ions of 55.09 mg g-1. This value suggests the application of this biopolymer with incorporated carboxylate groups as a favorable agent for copper removal from appropriate systems.

Os componentes mesocarpo e epicarpo do coco babaçu foram utilizados como novos biossorventes alternativos para remoção do corante têxtil ftalocianina de cobre de soluções aquosas. Esses biopolímeros foram caracterizados por análise elementar, RMN de 13C no estado sólido, espectroscopia de absorção na região do infravermelho, análise termogravimétrica e difratometria de raios X. Os resultados mostraram que a composição do mesocarpo e do epicarpo é similar à de outros materiais lignocelulósicos e que ambos os componentes são efetivos na remoção do corante têxtil Turqueza Remazol. O modelo cinético de pseudo-segunda ordem resultou no melhor coeficiente de correlação tanto para o epicarpo quanto para o mesocarpo (R² = 0,999), com constantes de velocidade de sorção, k2, de 0,31 e 1,43 g mg-1 min-1, respectivamente. Os modelos de Langmuir e Freundlich foram empregados para analisar os dados experimentais em sua forma linearizada. O segundo modelo apresentou melhor adequação para a adsorção do corante Turqueza Remazol com sorção máxima de 1,44 e 2,38 mg g-1 a pH 6,0 para mesocarpo e epicarpo, respectivamente.

The mesocarp and epicarp components of the babassu palm tree were applied as novel alternative biosorbents for copper phtalocyanine textile dye removal from aqueous solutions. The natural biopolymers were characterized by elemental analyses, solid state 13C NMR, infrared spectroscopy, thermogravimetric analysis and X-ray diffractometry. Results demonstrated that the compositions of the mesocarp and epicarp are similar to those of other lignocellulosic materials, and that they were very effective for removal of the textile dye Turquoise Remazol. A pseudo second-order kinetic model resulted in the best fit with experimental data for both epicarp and mesocarp (R² = 0.999), providing rate constants of sorption, k2, of 0.31 and 1.43 g mg-1 min-1, respectively. The Langmuir and Freundlich isotherm models were employed for adsorption analysis of the experimental data in their linearized forms. The second model resulted in the better fit for Turquoise Remazol dye, which presented maximum adsorption of 1.44 and 2.38 mg g-1 at pH 6.0 for mesocarp and epicarp, respectively.

Uma amostra natural de esmectita oriunda do estado do Piauí, Brasil, foi organofuncionalizada com 3-mercaptopropiltrimethoxissilano e 3-aminopropiltriethoxissilano. O espaçamento basal da argila natural é de 0,99 nm e área superficial 48 m² g-1. Houve um aumento no espaçamento basal para 1,84 e 2,01 nm e o aumento da área específica para 781 e 795 m² g-1 para as argilas quimicamente modificadas, respectivamente. A argila natural e a argila quimicamente modificada adsorveram cátions mercúrio em solução aquosa em pH 3,0 e 298 ± 1 K. Os modelos de isotermas de adsorção de Langmuir, Redlich-Peterson e Toth foram aplicados para ajuste dos dados experimentais com aproximação não linear. Para as interações cátion/centros básicos para cada esmectita na interface sólido/líquido foi utilizada metodologia calorimétrica e foram obtidas as constantes de equilíbrio e os efeitos térmicos exotérmicos. Considerando o número interativo de moles para cada cátion e as constantes de equilíbrio, a entalpia, "intHº (-11,98 a -13,93 kJ mol-1) e a energia livre de Gibbs negativa, "intGº (-22,4 ± 0,1 a -23,9 ± 0,1 kJ mol-1) foram calculadas, o que permitiram a determinação da entropia positiva "intSº (51 ± 01 a 55 ± 2 J K-1 mol-1). As interações cátion/centros básicos são de natureza espontânea como demonstram os valores de energia livre de Gibbs, dando o conjunto de dados favoráveis como expressam a entalpia exotérmica e a entropia positiva, mostrando que a esmectita natural e as quimicamente modificadas têm habilidade em complexar mercúrio. Logo, esses materiais são úteis na remoção de mercúrio em um ecossistema.

A natural smectite clay sample from Piauí State, Brazil, was organofunctionalized with 3-mercaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane silyating agents. The basal spacing of 0.99 nm and surface area of 48 m² g-1 for natural clay increased to 1.84 and 2.01 nm, and 781 and 795 m² g-1 for modified clays, respectively. The natural and chemically immobilized clay samples adsorb mercury cations from aqueous solutions at pH 3.0 at 298 ± 1 K. The Langmuir, Redlich-Peterson and Toth adsorption isotherm models were applied to fit the experimental data with a nonlinear approach. From the cation/basic center interactions for each smectite at the solid-liquid interface, by using calorimetry methodology, the equilibrium constant and exothermic thermal effects were obtained. By considering the net interactive number of moles for each cation and the equilibrium constant, the enthalpy, "intHº (-11.98 to -13.93 kJ mol-1) and negative free Gibbs energy, "intGº (-22.4 ± 0.1 to -23.9 ± 0.1 kJ mol-1) were calculated. These values enabled the determination of positive entropy, "intSº (51 ± 01 to 55 ± 2 J K-1 mol-1). The cation-basic center interactions are spontaneous in nature as demonstrated from favorable enthalpic and entropic results. Natural and anchored smectites have the ability to complex mercury, acting as useful materials for removal of this hazardous metal from an ecosystem.

Amostras de caulinita oriundas da região do Rio Capim, estado do Pará, Brasil, foram intercaladas com dimetilsulfóxido - DMSO. As amostras de caulinita naturais e intercaladas foram utilizadas em processo de adsorção com Zn(II) em meio aquoso em pH 5,0 e temperatura controlada de 298 ± 1K. As propriedades físico-químicas das amostras de caulinita foram otimizadas pelo processo de intercalação, como: área superficial de 14,74 para 91,72 m²g-1 (A1) e diâmetro de poros de 2,79 para 10,72 nm (A1). A análise dos resultados experimentais de adsorção foi feita pelos modelos de Langmuir, Temkin e Freundlich. O modelo de Langmuir apresentou melhor aproximação com os dados experimentais de adsorção. Estes resultados foram bem representados pelo modelo cinético de segunda ordem de Lagergren, com a taxa constante K2 no intervalo de 4,76x10-3 a 11,81x10-3 g(mmol.min)-1 (A2). O processo de adsorção foi considerado rápido alcançando o equilíbrio em 180 min.

The kaolinite clay samples from Capim River region, Pará state, Brazil, were intercalated with dimethylsulfoxide - DMSO. The natural and intercalated kaolinite were used in adsorption process with Zn(II) in aqueous medium at pH 5.0 and controlled temperature of 298 ± 1K. The physical-chemical properties of kaolinite samples were optimized for the intercalation process, such as: specific area of 14.74 to 91.72 m²g-1 (A1) and pore diameter of 2.79 to 10.72 nm (A1). The adsorption experimental results were analyzed for Langmuir, Temkin and Freundlich models, the Langmuir model has been presented best approximation with experimental adsorption isotherms data. These results best fitted the second order kinetic of Lagergren model with rate constant K2, in the range of 4.76x10-3 to 11.81x10-3 g(mmol.min)-1 (A2). The adsorption process was very fast and equilibrium was approached within 180 min.

Amostra de esmectita pertencente a Serra de Maicuru (Estado do Pará, Norte do Brasil, região amazônica) foi pilarizada com Al13, A Argila pilarizada com alumínio (Al-PILC) foi caracterizada por DRX, MEV e EDS. Para a análise textural foram utilizadas isotermas de adsorção-desorção utilizando o nitrogênio. Este artigo é dirigido ao estudo da adsorção de metais pesados. A adsorção dos íons de Cu2+, Ni2+e Co2+ foi realizadas com a matriz Al-PILC em temperatura ambiente com soluções aquosas contendo os íons metálicos. Os modelos de adsorção adotados foram os de Langmuir, Freundlich e Temkin que foram aplicados aos valores obtidos experimentalmente com regressão linear. A equação de Langmuir foi o melhor modelo de linearização com r = 0,999. A equação de Freundlich apresentou limitações em altas concentrações, mas foram obtidos valores (Kf e n) bastante aceitáveis utilizando este modelo. Os parâmetros foram utilizados para calcular a quantidade de Nf em função de Cs.

Smectite sample from the Serra de Maicuru area (Pará state, northern Brazil, Amazon region) were used for the pillaring process with Al13. Aluminum pillared clay (Al-PILC) was characterized by XRD, SEM and EDS. the textural analysis using nitrogen adsorption-desorption isotherms. The aim of this paper is to study in how Al-PILC adsorb heavy metals. The adsorption of Cu2+, Ni2+, Co2+ ions from aqueous solution in room temperature by Al-PILC have been carried out. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data, with the first model well adjusted with r = 0.999. The one-surface Langmuir equation provided the best fit to the data. The Freundlich equation presented limitations in rises concentrations, but acceptable values of parameters were obtained (Kf and n) with the use of the three models. The parameters were used to calculate the amount adsorbed Nf, a function constant Cs.

Amostras de esmectitas oriundas do estado do Pará, região amazônica, Brasil, foram usadas em processo de pilarização no presente estudo. As matrizes pilarizadas e natural foram caracterizadas usando DRX e analise textural usando isotermas de adsorção-desorção de nitrogênio. Os íons de intercalação (Al13, Ti, Zr) foram obtidos através de reações químicas com soluções de AlCl(3)6H2O/ NaOH, etoxido de titânio/HCl, acetato de zircônio / HCl. Os resultados obtidos com o processo de pilarização apresentaram aumento do espaçamento basal de 15,6 para 20, 64 Å e área superficial de 44 para 358 m²/g (Zr-PILC). A estabilidade térmica da argila natural foi melhorada com o processo de pilarização. O material resultante foi submetido a um processo catalítico de decomposição do óleo de andiroba em um reator de leito fixo a 673 ± 1 K. A atividade catalítica foi determinada pelo produto de decomposição resultante da reação química. Os parâmetros físico-químicos foram obtidos usando DRX, FTIR e análise textural. As argilas pilarizadas apresentaram alta acidez de Brønsted, com alta concentração de hidrocarbonetos aromáticos e baixa concentração de hidrocarbonetos alifáticos.

Smectite-bearing clay samples from Pará state, Amazon region, Brazil, were used for pillaring process in the present study. The natural and pillarized matrices were characterized using XRD and textural analysis using nitrogen adsorption-desorption isotherms. The ions of intercalation (Al13, Ti, Zr) were obtained through chemical reactions of AlCl(3)6H2O/ NaOH, titanium ethoxide /HCl, zirconium acetate /HCl solutions. The Results showed that the pillarization process increases the basal spacing of the natural clay from 15.6 to 20.64 Å and the superficial area from 44 to 358 m²/g (Zr-PILC). The thermal stability of the natural clay was improved by the pillaring procedure. The resulting materials were submitted to catalytic process of decomposition of andiroba oil in a fix bed reactor at 673 ± 1 K. The catalytic activity was determined by the product composition resulting from the chemical reactions. The physicochemical parameters of the catalysts were obtained using XRD, FTIR and textural analysis. The pillared clays showed higher Brønsted acidity, with higher concentration in aromatic hydrocarbons and small concentration of aliphatic hydrocarbons.

Amostras de argila esmectítica provenientes do município de Serra Madureira no Estado do Acre foram utilizadas no processo de pilarização. As matrizes natural e pilarizada foram caracterizadas por difração de raios X, espectroscopia no infravermelho com transformada de Fourier, análises térmicas diferencial e gravimétrica, microscopia eletrônica de varredura, espectroscopia de raios X por energia dispersiva e análise textural. As soluções pilarizantes de titânio, Ti(OC2H5)4 e TiCl4, foram analisadas por espectroscopia no infravermelho com transformada de Fourier. O íon intercalante foi obtido através da reação química entre as soluções de Ti(OC2H5)4 e HCl na proporção aproximada de HCl/Ti=1 e soluções de TiCl4 em reação com etanol com relação Ti/argila= 25 mmol Ti/g. A intercalação da notronita foi efetuada utilizando-se de dois métodos: com a solução de acido clorídrico incorporada paulatinamente na solução de etóxido de titânio, e utilizando o cloreto de titânio em solução de etanol, com vigorosa agitação a 25 ºC durante 3 h e com calcinação a 450 ºC e 600 ºC. Os resultados de difração de raios X do processo de pilarização mostraram alterações no espaçamento basal de 15,30 Å para 18,76 Å, e na área de superfície específica de 44,37 m²/g para 188,72 m²/g. A estabilidade térmica da argila natural foi otimizada com o processo de pilarização.

Smectite clays of the State of Acre, Brazil, were used for the pillarization process. The natural and pillarized matrices were characterized by X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), thermal analysis, scanning electron microscopy, energy dispersive spectroscopy and textural analysis. The titanium pillarized solutions Ti(OC2H5)4 and TiCl4 were analyzed by FTIR. The intercalation ion was obtained by reacting Ti(OC2H5)4 with HCl (HCl/Ti ~ 1) and TiCl4 with ethanol (Ti/clay ~ 25 mmol Ti/g). The notronite intercalation was carried out using two methods: with dropwise hydrochloric acid in titanium ethoxide solution, and using titanium tetrachloride, kept under vigorous stirring at 25 °C for 3 h and calcination at 450 °C and 600 °C. The X-ray diffraction results of the pillarization process show an increase (15.30 Å to 18.76 Å) in the basal spacing of the natural clay and in the specific surface area (44.37 m²/g to 188.72 m²/g) The thermal stability of the natural clay was improved by the pillarization procedure.

As amostras de esmectita do estado do Pará, Amazônia, Brasil foram caracterizadas utilizando XRD, 27Al MAS NMR, FTIR e análise textural por curvas isotérmicas de adsorção-dessorção de nitrogênio. Na produção das argilas pilarizadas foi usado como íon intercalante, o Al13 (o íon de keggin), obtido pela reação das soluções AlC(l3)6H2O/NaOH, com razão molar OH/Al=2. Foram adotadas as proporções (Al/Argila): 5, 10, 20 e 25 meq/g de argila, com intercalação em 25 ºC, durante as 3 h e calcinada a 450 ºC (temperatura adequada da calcinação). O resultado mostrou que o processo de pilarização aumentou o espaçamento basal da argila natural de 14,02 para 18,84 Å e a área superficial de 44,30 para 198,03 m²/g (Al/Argila=25meq/g de argila, pH=4). O material preparado com relação Al/Argila=25meq/g de argila mostrou a incorporação máxima de Al. A estabilidade térmica da argila natural foi melhorada pelo procedimento de pilarização.

Smectite-type clays from the state of Pará, Brazil, were characterized by XRD, 27Al MAS NMR, FTIR and textural analysis by nitrogen adsorpition-desorption isotherms. In the production of pillared clays, the Al13 ion (keggin's ion) was used. This ion was obtained by the reaction of AlC(l3)6H2O/NaOH solutions with OH/Al=2 molar ratio and with Al/clay ratios of 5, 10, 15, 20, 25 meq/g of clay, intercalated at 25 ºC during 3 h and calcined at 450 ºC (adequate temperature for calcination). The results showed that the pillarization process increased the basal spaces of the natural clay from 14.02 to 18.84 Å and the surface area from 44.30 to 198.03 m²/g (Al/g of clay = 25 meq/g of clay, pH=4). Materials prepared with different Al/g clay ratio showed the maximum Al incorporation for Al/g of clay = 25 meq/g of clay. The thermal stability of the natural clay was improved by the pillaring procedure.

O composto lamelar fenilarsonato de titânio foi sintetizado e intercalado com alquilmonoaminas (metil a heptil), diaminoetano e diaminobutano, lutidina e alfa-picolina. A matriz original foi caracterizada por análise elementar, difração de raios X, análise de superfície, porosidade, espectroscopia de absorção na região do infravermelho, termogravimetria e microscopia eletrônica de varredura. Os difratogramas de raios X não mostraram aumento significativo de distâncias interlamelares, e a intercalação foi comprovada por técnicas como a termogravimetria que indicou a perda de massa correspondendo às aminas. A condição ideal de intercalação foi efetuada com injeções de 30,0x10-6 dm³ da amina 0,50 mol dm-3 em suspensão de aproximadamente 10x10-3 g das matrizes. Os números de moles intercalados com as alquilmonoaminas seguiram uma ordem aleatória em relação ao aumento da cadeia alifática, com valores entálpicos de -9,18 ± 0,07; -12,10 ± 0,20; -7,61 ± 0,02; -6,88 ± 0,01; -9,47 ± 0,03; -12,84 ± 0,10 e -14,78 ± 0,10 kJ mol-1 para a seqüência das alquilmonoaminas e variaram de -3,66 ± 0,30 a -10,92 ± 1,50 kJ mol-1 para alquildiaminas. Com as aminas aromáticas não ocorreu um efeito térmico significativo nas intercalações, fato que foi atribuído ao grande volume do grupo fenila presente no interior das lamelas, que impede a inserção da base na cavidade lamelar.

The lamellar compound titanium phenylarsonate was synthesized and intercalated with alkylmonoamines (methyl to heptyl), diaminoethane, diaminobutane, lutidine and alpha-picoline. The host was characterized through elemental analysis, X-ray diffraction, surface analysis, porosity, infrared spectroscopy, thermogravimetry and electronic scanning microscopy. The intercalated compounds did not show significant increases in the interlamellar distances through X-ray diffractometry. The intercalation was confirmed by the thermogravimetric technique, indicating mass losses that correspond to the amines. The ideal intercalation was established by adding increments of 30.0x10-6 dm³ of 0.50 mol dm-3 of each amine into a suspension of about 10x10-3 g of matrix. The number of moles intercalated with alkylmonoamines followed an aleatory order in relation to the increase of the aliphatic chain and the enthalpic values gave -9.18 ± 0.07; -12.10 ± 0.20; -7.61 ± 0.02; -6.88 ± 0.01; -9.47 ± 0.03; -12.84 ± 0.10 and -14.78 ± 0.10 kJ mol-1 for the sequence of alkylmonoamines and varied from -3.66 ± 0.30 to -10.92 ± 1.50 kJ mol-1 for the alkyldiamines. The aromatic amines presented small thermal effects and the unfavorable intercalation is attributed to the large volume of the phenyl group inside the lamella, which hinders insertion of these bases inside the lamellar cavity.

The present work reviews recent advances in the preparation of new reversed phase packing materials such as sterically protected, bidentate, hybrid organic-inorganic and monolithic phases and phases containing embedded polar groups. The bonding chemistry involved in the preparation of these phases as well as their advantages over conventional C8 and C18 reversed phases are discussed. Understanding the reasons behind the development of these newer column packings helps analysts select the best stationary phase for a given application.

Heterogenization of molybdenum species, starting either with Mo(CO)6 or MoO2(acac)2, on the surface of functionalized silicas bearing one (Si-Et1) or two (Si-Et2) ethylenediamine ligands was studied. The resulting systems are active in the catalytic epoxidation of cyclohexene by tert-butyl hydroperoxide. Using fresh catalysts, Si-Et2 results in higher selectivity, regardless of the Mo precursor. However, MoO2(acac)2-based systems are far more active. Formation of diols was never detected. Although XPS analyses point mainly to Mo(VI) species on the surface of all systems, UV-vis spectra suggest different ligands in their coordination sphere