Desenvolvimento e caracterização de recobrimentos de Ni-Co e de seus óxidos mistos para a produção de oxigênio por eletrólise alcalina da água

This paper describes the development and characterisation of Ni-Co coatings to be used as anodes in water electrolysis. Chemical oxidation of the surface was performed through thermal treatment at 400ºC for 10 h. The resulting surfaces were analysed by X-ray diffraction, EDX, SEM, cyclic voltammetry and constant current electrolysis. The electrochemical oxidation occurring on bare surfaces during electrolysis promotes the formation of thick oxide layers resulting in loss of activity. In oxidised surfaces the chemical Ni-Co oxide grown during the thermal treatment prevents further oxidation thus retaining their activity towards oxygen evolution. An optimum condition for the growth of mixed oxide with high activity was found for the bath containing 50 g L-1 CoSO4.

Caracterização de filmes finos de Nb2O5 com propriedades eletrocrômicas

The sols for thin electrochromic coatings of Nb2O5 were obtained by synthesis of the niobium butoxide from BuONa and NbCl5. The ~300nm thick films were deposited by dip-coating technique from the alkoxide solution and calcined at 560ºC in O2 atmosphere during 3 hours. The particles size of niobium oxide (V) powder (~20mm) was obtained from x-ray diffraction using the Scherrer equation. The coatings were characterized by cyclic voltammetry and cronoamperommetry techniques. The spectral variation of the optical transmittance were determined in situ as a function of the cyclical potencial and memory effect. The insertion process of lithium is reversible and change the film color from transparent (T=80%) to dark blue (T=20%).

Efeito da adição de Na2O na viscosidade e devitrificação do vidro obtido a partir de cinzas volantes e Li2O

Glass-ceramic materials can be produced by the addition of LiO2 to fly ashes disposible in Southern Brazil. These glass-ceramics are based on the Al2O3-SiO2-Li 2O system. The high viscosity of the obtained glasses, however, makes forming useful articles with these materials difficult. In this study we investigate the effect of adding low cost Na2CO3 on the melt viscosity and on the nature of the developed crystalline phases. It was intended that the ultimate crystalline phase (LiAlSi3O8) should not be altered. With additions up to 3 wt. % Na2CO3, the viscosity was apparently lowered and no new crystalline phase were detected.

Determination of compression behaviour of coating layer

The strength properties of paper coating layer are very important in converting and printing operations. Too great or low strength of the coating can affect several problems in printing. One of the problems caused by the strength of coating is the cracking at the fold. After printing the paper is folded to final form and the pages are stapled together. In folding the paper coating can crack causing aesthetic damage over printed image or in the worst case the centre sheet can fall off in stapling. When folding the paper other side undergoes tensile stresses and the other side compressive stresses. If the difference between these stresses is too high, the coating can crack on the folding. To better predict and prevent cracking at the fold it is good to know the strength properties of coating layer. It has measured earlier the tensile strength of coating layer but not the compressive strength. In this study it was tried to find some way to measure the compressive strength of the coating layer and investigate how different coatings behave in compression. It was used the short span crush test, which is used to measure the in-plane compressive strength of paperboards, to measure the compressive strength of the coating layer. In this method the free span of the specimen is very small which prevent buckling. It was measured the compressive strength of free coating films as well as coated paper. It was also measured the tensile strength and the Bendtsen air permeance of the coating film. The results showed that the shape of pigment has a great effect to the strength of coating. Platy pigment gave much better strength than round or needle-like pigment. On the other hand calcined kaolin, which is also platy but the particles are aggregated, decreased the strength substantially. The difference in the strength can be explained with packing of the particles which is affecting to the porosity and thus to the strength. The platy kaolin packs up much better than others and creates less porous structure. The results also showed that the binder properties have a great effect to the compressive strength of coating layer. The amount of latex and the glass transition temperature, Tg, affect to the strength. As the amount of latex is increasing, the strength of coating is increasing also. Larger amount of latex is binding the pigment particles better together and decreasing the porosity. Compressive strength was increasing when the Tg was increasing because the hard latex gives a stiffer and less elastic film than soft latex.

Estudo espectroscópico de vidros a base de aluminato de cálcio contendo Nd3+

Multicomponent ( Al2O3, CaO, SiO2, MgO) calcium aluminate-based glasses containing Nd3+ were prepared in order to evaluate their possibilities as laser host materials. The refractive index, UV-visible-near IR absorption spectrum, IR and visible luminescence spectra, and fluorescence decay time were measured. Judd-Ofelt model was used to obtain experimental intensity parameters ( omega2, omega4 and omega6), emission cross-section, radiative lifetimes, emission branching ratios and quantum efficiency.

Preparação e caracterização de pós cerâmicos de aluminatos de lítio

The preparation of gamma-LiAlO2 by coprecipitation and sol-gel synthesis was investigated. Ceramic powders obtained by coprecipitation synthesis were prepared from aqueous solutions of aluminum and lithium nitrates using sodium hydroxide as precipitant agent. By sol-gel synthesis, the ceramic powders were prepared from hydrolysis of aluminum isopropoxide. The materials obtained by two routes of synthesis were dried at 80ºC and calcined at 550, 750, 950 and 1150ºC. The characterization was done by X-ray diffraction, infrared spectroscopy, emission and absorption atomic spectrometry, helium picnometry, specific surface area (BET method) and scanning electronic microscopy. Mixtures of crystalline phases were obtained by coprecipitation synthesis: 80ºC- LiAl2(OH)7.2H2O + Al(OH)3; 550 and 750ºC- alpha-LiAlO2 + eta-Al2O3; 950 and 1150ºC- gamma-LiAlO2 + LiAl5O8. Chemical analysis showed molar ration Al/Li @ 3. Crystalline single-phases were obtained by sol-gel synthesis above 550ºC: 550ºC-alpha-LiAlO2; 750, 950 and 1150ºC-gamma-LiAlO2. These powders presented molar ration Al/Li @ 1. Thus, gamma-LiAlO2 crystalline phase was obtained at 750ºC by sol-gel synthesis while by coprecipitation synthesis, a mixture of crystalline phases was obtained. These results showed the superiority of the sol-gel synthesis for the preparation of pure gamma-LiAlO2.

Estudo do efeito do cloreto em catalisadores de paládio usando a análise no infravermelho e de fotoelétrons excitados por raios x

Chloride poisoning is known as having an inhibitor effect in the activity of metal catalysis. In this work in situ infrared spectroscopy (FTIR) of adsorbed carbon monoxide and x-ray photoelectron spectroscopy (XPS) were used to investigate the effect of chloride presence in the electronic metal density in the d subshell of palladium dispersed on alumina. The chloride poisoning effect was interpreted as an electronic effect since a weak back-bonded Pd-CO was formed due to the decrease in the electronic density of the d subshell of palladium, which could be also detected by the higher Pd 3d5/2 binding energy in the chloride presence. A similar poisoning effect was also observed for chloride free Pd/Al2O3 reduced at 500 ºC, and it was interpreted based on the interaction of metal with the alumina surface. The use of molybdena/alumina binary system as support, yield a contrary effect due to the metal-support interaction.

Estudo do efeito da quantidade de óxido de ferro em cinzas pesadas de carvão mineral na obtenção de vitrocerâmicos

Bottom ash has been used as raw material to glass and glass ceramic production because it is a source of SiO2 and Al2O3. However, the high concentration of iron (about 10% wt.) difficulty the control of the nucleation and the crystallization processes. The iron content was reduced by magnetic process, where the magnetite phase was mainly removed. In order to compare glass ceramics obtained from original and low iron bottom ashes, microstructural and dilatometric characterizations were performed.

Recuperação de metais de catalisadores mássicos e monometálicos

This work presents a study on the dissolution of some commercial monometallic and non-supported deactivated catalysts in HF + H2O2 mixtures (and, eventually, other media) under mild experimental conditions, after a previous oxidation step. The samples were neither crushed nor grinded. The best experimental conditions were dependent on the nature of the support and of the active phase. For example, the Pt/Al2O3 catalyst was dissolved in about 10 minutes, without agitation and heating; however, dissolution of the Pd/Al2O3, Ni/Al2O3, Ni/SiO2, Cu/Al2O3 and V2O5 samples required a temperature of 60 ºC and an agitation of 400 rpm. A careful addition of a NaOH solution allowed a quantitative precipitation of aluminium as criolite (Na3AlF6) or precipitation of Si as Na2SiF6; NaF was obtained as a by-product. As expected, processing of Pd/C, V2O5 and CuO.Cr2O3 samples was relatively simple. Metals recovery from catalysts reached a quantitative level in all samples studied; it is particularly interesting that platinum and palladium could be easily recovered in a single step process, thus separing them from aluminium.

Comparative effects of macro-sized aluminum oxide and aluminum oxide nanoparticles on erythrocyte hemolysis: influence of cell source, temperature and size

Al2O3 is the most abundantly produced nanomaterial and has been used in diverse fields, including the medical, military and industrial sectors. As there are concerns about the health effects of nanoparticles, it is important to understand how they interact with cells, and specifically with red blood cells. The hemolysis induced by three commercial nano-sized aluminum oxide particles (nanopowder 13 nm, nanopowder <50 nm and nanowire 2-6 nm × 200-400 nm) was compared to aluminum oxide and has been studied on erythrocytes from humans, rats and rabbits, in order to elucidate the mechanism of action and the influence of size and shape on hemolytic behavior. The concentrations inducing 50% hemolysis (HC50) were calculated for each compound studied. The most hemolytic aluminum oxide particles were of nanopowder 13, followed by nanowire and nanopowder 50. The addition of albumin to PBS induced a protective effect on hemolysis in all the nano-forms of Al2O3, but not on Al2O3. The drop in HC50 correlated to a decrease in nanomaterial size, which was induced by a reduction of aggregation Aluminum oxide nanoparticles are less hemolytic than other oxide nanoparticles, and behave differently depending on the size and shape of the nanoparticles. The hemolytic behavior of aluminum oxide nanoparticles differs from that of aluminum oxide.

Estudo eletroquímico de um novo banho galvânico de zinco alcalino livre de cianetos

A systematic electrochemical study of a novel cyanide free galvanic plating solution of alkaline zinc is presented. Cell Hull tests and potentiodynamic linear polarization measurements were carried out to evaluate the influence of operational parameters, such as concentration, current efficiency and degradation of additives. The stability of the bath was assessed by a long term test during 40 h at 200 A m-2. The morphology of the coatings was characterized by scanning electron microscopy. The results showed good performance of the plating solution. The cost is similar to that of the commercial cyanide bath and lower than that of the commercial cyanide free bath.

Comparative effects of macro-sized aluminum oxide and aluminum oxide nanoparticles on erythrocyte hemolysis: influence of cell source, temperature and size

Al2O3 is the most abundantly produced nanomaterial and has been used in diverse fields, including the medical, military and industrial sectors. As there are concerns about the health effects of nanoparticles, it is important to understand how they interact with cells, and specifically with red blood cells. The hemolysis induced by three commercial nano-sized aluminum oxide particles (nanopowder 13 nm, nanopowder <50 nm and nanowire 2-6 nm × 200-400 nm) was compared to aluminum oxide and has been studied on erythrocytes from humans, rats and rabbits, in order to elucidate the mechanism of action and the influence of size and shape on hemolytic behavior. The concentrations inducing 50% hemolysis (HC50) were calculated for each compound studied. The most hemolytic aluminum oxide particles were of nanopowder 13, followed by nanowire and nanopowder 50. The addition of albumin to PBS induced a protective effect on hemolysis in all the nano-forms of Al2O3, but not on Al2O3. The drop in HC50 correlated to a decrease in nanomaterial size, which was induced by a reduction of aggregation Aluminum oxide nanoparticles are less hemolytic than other oxide nanoparticles, and behave differently depending on the size and shape of the nanoparticles. The hemolytic behavior of aluminum oxide nanoparticles differs from that of aluminum oxide.

Análise estatística e optimização de perfis de redução termoprogramada (TPR)

The effect of operational variables and their interaction in TPR profiles was studied using a fractional factorial experimental design. The heating rate and the reducing agent concentration were found to be the most important variables determining the resolution and sensitivity of the technique. They showed opposite effects. Therefore, they should be manipulated preferentially in order to obtain optimized TPR profiles. The effect of sample particle size was also investigated. The tests were carried out within a Cu/Zn/Al2O3 catalyst used for the water-gas shift reaction that presented two distinct species of Cu2+ in TPR profiles.

Recuperação de metais de catalisadores de hidrorrefino usados via fusão com KHSO4

This work describes a process for metal recovery from spent NiMo and CoMo/Al2O3 commercial hydrorefining catalysts. The samples were treated by fusion with potassium hydrogen sulfate (5 h, 600 ºC) with a KHSO4/catalyst mass ratio of 10:1. After fusion the solid was solubilized in water (100 ºC), leaving silicon compounds as residue. Losses of nickel and cobalt may reach 16 wt% of the amount present in the sample, depending on the silicon content. Soluble metals were isolated by selective precipitation techniques (nickel, cobalt, aluminum) or by solvent extraction with methyl-isobutyl ketone (molybdenum) in a hydrochloric acid medium. All metals were recovered in very good yields except for nickel and cobalt in the presence of considerable amounts of silicon. Soluble wastes consist of potassium/sodium sulfates/chlorides. Solid wastes correspond to about 4 wt% of the catalyst and can be discarded in industrial dumps.

Estudo da influência dos íons K+, Mg2+, SO4(2-) e CO3(2-) na cristalização biomimética de fosfato de cálcio amorfo (ACP) e conversão a fosfato octacálcico (OCP)

The crystallization of hydroxyapatite (HA) in aqueous solution can be described by the mechanism ACP -> OCP -> HA. In this work, it was studied the influence of K+, Mg2+, SO4(2-) and CO3(2-) ions in the formation of ACP and in its conversion to OCP, using biomimetic coatings on metallic substrates of commercially pure titanium (Ti c.p.). The results showed that Mg2+ and CO3(2-) ions favored both the formation of ACP and its conversion to OCP. Differently, K+ and SO4(2-) ions did not influence the formation of ACP and, consequently, interfered in the conversion to OCP.