(Table 1, page 220), Spot chemical analyses of a section of nodule 5133.7

Microscopic and electron probe examination of some manganese nodules show that they consist of segregations of manganese-iron oxides in an interstitial material almost free of manganese but rich in iron and silicates. The segregations are widely spaced in the volcanic cores of the nodules but become more abundant towards their outer crusts where they form the centres of linked polygons of interstitial materials. Most of the minor elements are concentrated in the segregations compared to the interstitial materials. It is suggested that the structures observed result partly from solution and reprecipitation of elements in the original volcanic cores of the nodules and partly from the replacement and coating of these cores by manganese-iron oxides precipitated from sea water.

Síntese e caracterização de nanomateriais superparamagnéticos do tipo core-shell para aplicação em catálise e biomedicina

As diversas aplicações tecnológicas de nanopartículas magnéticas (NPM) vêm intensificando o interesse por materiais com propriedades magnéticas diferenciadas, como magnetização de saturação (MS) intensificada e comportamento superparamagnético. Embora MNP metálicas de Fe, Co e bimetálicas de FeCo e FePt possuam altos valores de MS, sua baixa estabilidade química dificulta aplicações em escala nanométrica. Neste trabalho foram sintetizadas NPM de Fe, Co, FeCo e FePt com alta estabilidade química e rigoroso controle morfológico. NPM de óxido metálicos (Fe e Co) também foram obtidas. Dois métodos de síntese foram empregados. Usando método baseado em sistemas nanoheterogêneos (sistemas micelares ou de microemulsão inversa), foram sintetizadas NPM de Fe3O4 e Co metálico. Foram empregados surfactantes cátion-substituídos: dodecil sulfato de ferro(III) (FeDS) e dodecil sulfato de cobalto(II) (CoDS). Para a síntese das NPM, foram estudados e determinados a concentração micelar crítica do FeDS em 1-octanol (cmc = 0,90 mmol L-1) e o diagrama de fases pseudoternário para o sistema n-heptano/CoDS/n-butanol/H2O. NPM esferoidais de magnetita com3,4 nm de diâmetro e comportamento quase-paramagnético foram obtidas usando sistemas micelares de FeDS em 1-octanol. Já as NPM de Co obtidas via microemulsão inversa, apesar da larga distribuição de tamanho e baixa MS, são quimicamente estáveis e superparamagnéticas. O segundo método é baseado na decomposição térmica de complexos metálicos, pelo qual foram preparadas NPM esféricas de FePt e de óxidos metálicos (Fe3O4, FeXO1-X, (Co,Fe)XO1-X e CoFe2O4) com morfologia controlada e estabilidade química. O método não mostrou a mesma efetividade na síntese de NPM de FeAg e FeCo: a liga FeAg não foi obtida enquanto que NPM de FeCo com estabilidade química foram obtidas sem controle morfológico. NPM de Fe e FeCo foram preparadas a partir da redução térmica de NPM de Fe3O4 e CoFe2O4, as quais foram previamente recobertas com sílica. A sílica previne a sinterização inter-partículas, além de proporcionar caráter hidrofílico e biocompatibilidade ao material. As amostras reduzidas apresentaram aumento dos valores de MS (entre 21,3 e 163,9%), o qual é diretamente proporcional às dimensões das NPM. O recobrimento com sílica foi realizado via hidrólise de tetraetilortosilicato (TEOS) em sistema de microemulsão inversa. A espessura da camada de sílica foi controlada variando-se o tempo de reação e as concentrações de TEOS e de NPM, sendo então proposto um mecanismo do processo de recobrimento. Algumas amostras receberam um recobrimento adicional de TiO2 na fase anatase, para o qual foi empregado etilenoglicol como solvente e ligante para formação de glicolato de Ti como precursor. A espessura da camada de TiO2 (2-12 nm) é controlada variando as quantidades relativas entre NPM e o precursor de Ti. Ensaios de hipertermia magnética foram realizados para as amostras recobertas com sílica. Ensaios de hipertermia magnéticas mostram grande aumento da taxa de aquecimento das amostras após a redução térmica, mesmo para dispersões diluídas de NPM (0,6 a 4,5 mg mL-1). Taxas de aquecimento entre 0,3 e 3,0oC min-1 e SAR entre 37,2 e 96,3 W g-1. foram obtidos. A atividade fotocatalítica das amostras recobertas foram próximas à da fase anatase pura, com a vantagem de possuir um núcleo magnético que permite a recuperação do catalisador pela simples aplicação de campos magnéticos externos. Os resultados preliminares dos ensaios de hipertermia magnética e fotocatálise indicam um forte potencial dos materiais aqui relatados para aplicações em biomedicina e em fotocatálise.

Estudo da obtenção de cerâmica composta de alumina e beta alumina sódica utilizando-se resíduo cerâmico de velas de ignição e pó químico de extintores de incêndio

Ceramic materials the alumina base are large industrial applications. They are required for these products, specific characteristics obtained by following strict criteria during the manufacturing process. However, after life, not always these products are reused by a suitable waste management process. In ceramist context, advance research aimed at the reuse of waste aimed at obtaining ceramics and composite materials, with marked reduction of conventional raw materials. Aiming to generate scientific, technological and environmental contribution, this work studied to obtain a composite of alumina ceramic (Al2O3) and sodium beta alumina (NaAl11O17 ), and as starting materials the residue of the ceramic insulator of spark plugs, as a source alumina (Al2O3) powder and unusable sodium bicarbonate (NaHCO3) of fire extinguishers, as a source of sodium oxide (Na2O). The final ceramic product was obtained from a conventional mixture of sodium aluminum oxide in appropriate molar proportions. Sample spark plugs were obtained, discarded by lifetime, specific to a manufacturer, which, after passing through mechanical stress (grinding, magnetic purification, washing, drying and grinding the high energy), which resulted in residue powder with ceramic content of 84.34 % alumina (Al2O3), found by FRX chemical analysis, the phases present and identified by DRX. The dry chemical fire extinguisher, baking soda-based (NaHCO3) with expired, was obtained through direct collection of the waste generated during maintenance. Subjected to heat treatment at 120 °C , the NaHCO3 powder was decomposed in sodium oxide ( Na2O), which, subjected to chemical analysis (FRX) and mineralogical (DRX) revealed a content of 86.62 % sodium oxide (Na2O) . In the following steps the experimental procedure, chemical formulations were made on a molar basis of the starting material (1:9, 1:10 and 1:11 de Na2O/ Al2O3) inclusion of additives, milling parameters, sieve analysis, dilatometry, conformation of specimens, sintering in firing steps at 800 °C , 1000 °C and 1.200 °C with varying stays 30 , 60 and 120 minutes in each of the levels. The characterization of the final product was made by the following physical tests: water absorption, porosity, linear shrinkage, mineralogical analysis by DRX and microstructural analysis by MEV. A higher formation of sodium beta alumina (NaAl11O17), in sintered specimens in levels of 1.200 °C and 120 minutes, despite the prevailing coexistence of alpha phase alumina (Al2O3). From the results obtained opens up prospects for the reuse of waste studied in this work, the potter context and in other technological areas.

Estudo da obtenção de cerâmica composta de alumina e beta alumina sódica utilizando-se resíduo cerâmico de velas de ignição e pó químico de extintores de incêndio

Ceramic materials the alumina base are large industrial applications. They are required for these products, specific characteristics obtained by following strict criteria during the manufacturing process. However, after life, not always these products are reused by a suitable waste management process. In ceramist context, advance research aimed at the reuse of waste aimed at obtaining ceramics and composite materials, with marked reduction of conventional raw materials. Aiming to generate scientific, technological and environmental contribution, this work studied to obtain a composite of alumina ceramic (Al2O3) and sodium beta alumina (NaAl11O17 ), and as starting materials the residue of the ceramic insulator of spark plugs, as a source alumina (Al2O3) powder and unusable sodium bicarbonate (NaHCO3) of fire extinguishers, as a source of sodium oxide (Na2O). The final ceramic product was obtained from a conventional mixture of sodium aluminum oxide in appropriate molar proportions. Sample spark plugs were obtained, discarded by lifetime, specific to a manufacturer, which, after passing through mechanical stress (grinding, magnetic purification, washing, drying and grinding the high energy), which resulted in residue powder with ceramic content of 84.34 % alumina (Al2O3), found by FRX chemical analysis, the phases present and identified by DRX. The dry chemical fire extinguisher, baking soda-based (NaHCO3) with expired, was obtained through direct collection of the waste generated during maintenance. Subjected to heat treatment at 120 °C , the NaHCO3 powder was decomposed in sodium oxide ( Na2O), which, subjected to chemical analysis (FRX) and mineralogical (DRX) revealed a content of 86.62 % sodium oxide (Na2O) . In the following steps the experimental procedure, chemical formulations were made on a molar basis of the starting material (1:9, 1:10 and 1:11 de Na2O/ Al2O3) inclusion of additives, milling parameters, sieve analysis, dilatometry, conformation of specimens, sintering in firing steps at 800 °C , 1000 °C and 1.200 °C with varying stays 30 , 60 and 120 minutes in each of the levels. The characterization of the final product was made by the following physical tests: water absorption, porosity, linear shrinkage, mineralogical analysis by DRX and microstructural analysis by MEV. A higher formation of sodium beta alumina (NaAl11O17), in sintered specimens in levels of 1.200 °C and 120 minutes, despite the prevailing coexistence of alpha phase alumina (Al2O3). From the results obtained opens up prospects for the reuse of waste studied in this work, the potter context and in other technological areas.

Investigação da rota biohidrometalúrgica com Acidithiobacillus ferrooxidans/thiooxidans para recuperação do cobalto de baterias de íons lítio descartadas

The recycling of metals from secondary sources can be advantageous. Among the metals of interest, we have cobalt, a metal used for various purposes. As regards the secondary sources of cobalt, the lithium-ion batteries can be considered, since they contain cobalt oxide in their composition (LiCoO2). This way, the objective of this work was to use the microorganism strains (Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans) to bioleach the LiCoO2 extracted from discarded lithium ion batteries with emphasis on the recovery of cobalt for synthesis of new materials of interest. The lineage growth occurred in T&K medium and the growth investigation was made by observing the media, by platelet growth and microscope analysis. Then, the inoculum was standardized on 5 x 106 cells mL-1 and used in bioleaching tests. The bioleaching was investigated: the microorganism nature: separate strains and A. ferrooxidans and A. thiooxidans consortium, bioleaching time (0 to 40 days), inoculum proportion (5 to 50% v/v), energy source (iron and sulfur) and residue concentration (1063 to 8500 mg L-1 of cobalt). The cobalt concentration in the media was found by atomic absorption spectrometry and the medium pH was monitored during the bioleaching. The results show that the amount of bioleached cobalt increases with time and the iron concentration. The bioleaching with A. thiooxidans was not influenced by the addition of sulfur. The use of the two lineages together did not improve the bioleaching rates. Among the lineages, the A. thiooxidans presented better results and was able to bioleach cobalt amounts above 50% in most of the experiments. A. thiooxidans presented lower bioleaching rates, with a maximum of 50% after 24 days of experiment. After reprocessing by bioleaching, the cobalt in solution was used for synthesis of new materials: such as LiCoO2 cathode and as adsorbent pesticide double lamellar hydroxide (HDL Co-Al-Cl) by the Pechini and co-precipitation methods. The reprocessed LiCoO2 presented a unique stoichiometric phase relative to the HT-LiCoO2 structure similar to the JCPDS 44-0145, presenting electrochemical activity when tested as a cathode material. The double lamellar hydroxide Co-Al-Cl was tested as pesticide adsorbent, being possible to adsorb around 100% of the pesticide. The bioleaching was efficient in the recovery of cobalt present in lithium-ion batteries and microorganisms presented high tolerance to the residue, being able to bioleach even at higher LiCoO2 concentrations. The cobalt bioleaching medium did not impair the synthesis phases and the obtained materials presented structure and activity similar to the sintered materials from the reagents containing cobalt.

Oxygen-Nonstoichiometric YBaCo4O7+δ as a Catalyst in H2O2 Oxidation of Cyclohexene

Here we present oxygen-nonstoichiometric transition metal oxides as highly prominent candidates to catalyze the industrially important oxidation reactions of hydrocarbons when hydrogen peroxide is employed as an environmentally benign oxidant. The proof-of-concept data are revealed for the complex cobalt oxide, YBaCo4O7+δ (0 < δ < 1.5), in the oxidation process of cyclohexene. In the 2-h reaction experiments YBaCo4O7+δ was found to be significantly more active (>60 % conversion) than the commercial TiO2 catalyst (<20 %) even though its surface area was less than one tenth of that of TiO2. In the 7-h experiments with YBaCo4O7+δ, 100 % conversion of cyclohexene was achieved. Immersion calorimetry measurements showed that the high catalytic activity may be ascribed to the exceptional ability of YBaCo4O7+δ to dissociate H2O2 and release active oxygen to the oxidation reaction.

Characterization of the glaze and in-glaze pigments of the nineteenth-century relief tiles from the Pena National Palace, Sintra, Portugal

The glaze and in-glaze pigments of the historical nineteenth-century glazed tiles from the Pena National Palace (Sintra, Portugal) were characterized using a multi-analytical approach. Chemical composition and microstructural characterization were ascertained by µ-PIXE, µ-Raman, optical microscopy and VP-SEM–EDS. The manufacturing technique and colour palette in these tiles were found to be close to the ceramic pigments used in traditional majolica. The blue and purple colours derive from cobalt oxide and manganese oxide, respectively. A mixture of Pb–Sn–Sb yellow with cobalt oxide and iron oxide was used for green and dark yellow, respectively, while grey tonalities consist of a complex mixture of cobalt oxide, manganese oxide and Pb–Sn–Sb yellow in different proportions. Results obtained allowed the determination of the oxides and elements used in pigments as well as production techniques, resorting to traditional majolica manufacture, although the tiles were produced by the end of the nineteenth century.

Thermodynamics of cobalt-manganese alloys using fluoride and oxide electrolytes

Abstract is not available.

Thermodynamics of Cobalt (II, III) Oxide (Co3O4): Evidence of Phase Transition

The Gibbs' energy change for the reaction, 3CoO (r.s.)+1/2O2(g)→Co3O4(sp), has been measured between 730 and 1250 K using a solid state galvanic cell: Pt, CuO+Cu2O|(CaO)ZrO2|CoO+Co3O4,Pt. The emf of this cell varies nonlinearly with temperature between 1075 and 1150 K, indicating a second or higher order phase transition in Co3O4around 1120 (±20) K, associated with an entropy change of ∼43 Jmol-1K-1. The phase transition is accompanied by an anomalous increase in lattice parameter and electrical conductivity. The cubic spinel structure is retained during the transition, which is caused by the change in CO+3 ions from low spin to high spin state. The octahedral site preference energy of CO+3 ion in the high spin state has been evaluated as -24.8 kJ mol-1. This is more positive than the value for CO+2 ion (-32.9 kJ mol-1). The cation distribution therefore changes from normal to inverse side during the phase transition. The transformation is unique, coupling spin unpairing in CO+3 ion with cation rearrangement on the spinel lattice, DTA in pure oxygen revealed a small peak corresponding to the transition, which could be differentiated from the large peak due to decomposition. TGA showed that the stoichiometry of oxide is not significantly altered during the transition. The Gibbs' energy of formation of Co3O4 from CoO and O2 below and above phase transition can be represented by the equations:ΔG0=-205,685+170.79T(±200) J mol-1(730-1080 K) and ΔG0=-157,235+127.53T(±200) J mol-1(1150-1250 K).