Margarete Soares da Silva

Phase Formation in Copper and Calcium Titanate Dielectric Ceramic Obtained by Polymeric Precursor Method

The polycrystalline ceramic named calcium and copper titanate is a dielectric ceramic with very high dielectric constant applicable in several electronic devices. The powder form for that advanced ceramic can be synthesized through chemical route, like the Polymeric Precursor Method at relative lower temperatures the presence of alkaline earth cations harms the structural homogenization during the crystallization process. In this work, the calcium and copper titanate powder was obtained by Polymeric Precursors Method by imposing a slow thermal decomposition of polymeric precursor and several crushing steps before the calcination at 800 °C for 4 hours. The entire process was observed by thermogravimetric analysis and FTIR spectrometry, including the nitrogen adsorption-desorption isotherms and X-ray diffractometry techniques for calcined power samples. It was observed the crystallization of the cubic Im-3 Ca1/4Cu3/4TiO3 phase only starts after organics removal and full calcium carbonate elimination above 700 oC, which is followed by pore elimination and particle sintering. The chemical synthetic route used in this work shows the ability to prepare CCT powders sample with very structural homogeneity, which characteristics are required to manufacturing many electronic devices.

Morphological and Structural Analyses in Carbonated Magnesium-Aluminum Hydrotalcites Co-Substituted with Iron III

Magnesium-aluminum hydrotalcites can be co-substituted with others trivalent cations, such as iron III in aluminum site, which can be a promising way to modify the properties of that synthetic adsorptive material. In the present work, hydrotalcite containing 5 mol% iron III in co-substitution to the aluminum was prepared by precipitation process and compared with no co-substituted sample along the temperature of calcination at 100 and 500 oC for 4 hours. The calcined samples were characterized by simultaneous TG/DTA, X-ray Diffraction and nitrogen adsorption-desorption techniques. The iron (III) insertion showed positive results in order to provide more stable structure against high temperatures of calcination, which was observed by lesser structural decomposition of rhombohedral hydrotalcite and a more mesoporous structure.

The Effect of Iron (III) Co-Insertion in Magnesium-Aluminum Hydrotalcites Obtained by Precipitation Method at pH 11

Hydrotalcite are anionic clay material presenting LDH arrangement and high porosity and specific areas, which make it a good adsorbent for pollutant species in water. Besides that, that material type can be used as catalyst or catalyst support in several industrial processes. The most common compositions is based on metallic mix hydroxide with high content of magnesium, but their adsorptive properties arise from aluminum replacement in layer structure. The present work presents the synthesis of carbonated magnesium-aluminum hydrotalcite through the precipitation method in order to investigate the co-insertion of iron (III) in aluminum site. It was found the iron (III) co-inserted samples obtained at 100 and 200 oC for 4 hours present no substantial harming in relation to the common magnesium-aluminum composition. All of the samples presented high porosity and specific area, becoming an alternative anionic adsorptive.

Synthesis of Nickel-Silica Nanocomposite Embedded in Amorphous Carbon through the Polymeric Precursor Method

The direct synthesis methods such as Polymeric Precursor Method can be used as direct route for the synthesis of ceramic-metal composites with high dispersion of metallic nanoparticles. The control of the polymer decomposition in order to avoid the organic matter combustion permits the pyrolysis occurrence, which originates the metallic phase embedded in the ceramic matrix. In this work, a nickel-silica nanocomposite in additional amorphous carbon interphase was successfully obtained through the Polymeric Precursor Method. It was observed by Transmission Electronic Microscopy that metallic nickel nanoparticles nucleate with sizes from 10 to 50 nm inside the mesopore matrix composite. The analysis of Nitrogen Adsorption-Desorption Isotherms for samples pyrolysed at several times showed the existence of two sizes of mesopores, one with diameter of 3.8 nm, associated to the silica-carbon matrix and other above 10 nm, associated to the meso and macropores containing nickel nanoparticles.

The Use of Long Chain Diol for Obtaining Nickel Embedded in Silica-Carbon Matrix through the Polymeric Precursor Method

Silica-carbon composites have large surface area and porosity and combines low density with refractoriness and high corrosion resistance, which make it a good choice for application as mesoporous matrix for composite catalysts. The insertion of nanoparticulate active phase can originate new properties for that composite type, such as catalysts for industrial methane hydro-reforming or other applications. However, there is a strong dependence among the composite morphology, active phase dispersion and porosity, originating a wide variation in the final properties. In this work, the Precursor Polymeric Method was modified to insert a long chain diol as polymerizing agent in order to insert large amount of carbon phase in the composite. The samples were obtained through the pyrolysis of the polymeric precursor prepared with tetraethylene glycol. Composite samples with high dispersion of nickel nanoparticles were obtained even after 1 hour of pyrolysis, but the porosity showed to be dependent of time of pyrolysis, mainly for mesopores with 3.8 nm in diameter.

Influence of Polyester Chain Type in the Morphology of Silica-Carbon Composites Obtained by the Polymeric Precursor Method

Particulate composite materials containing metallic phase in ceramic matrices may be obtained by direct routes with the advantage of avoiding the partial collapse of the composite structure when a subsequent step for metal insertion is carried out. The non-metallic silica-carbon matrix combines high values of pore volume and surface area with chemical refractivity and may be applied as molecular sieves, adsorbents, filters and catalyst support. The Polymeric Precursor Method is a versatile method to obtain this composite type as the metal precursor can be reduced to metallic phase by pyrolysis of organic matter. In this work, it was used three different diol chain sizes obtaining silica-carbon composites through the pyrolysis of polyester precursor at 600°C for 3 hours in closed tubular oven. It was observed a direct dependence between the amorphous carbon phase amount and the polyester chain size. All of the composite samples presented dual distribution for mesopore size, situated at 3.8 and 11 nm in diameter. However, the pore volume and surface area significantly lowers for larger polyester chain sizes.

Morphological Characterization of Nickel-Silica Nanocomposite in Residual Carbon Obtained by Direct Polymeric Route

Nickel-silica nanocomposites can be obtained by direct chemical route, such as the Polymeric Precursor Method. That methodology type permits to obtain material powders with significant specific area and porosity suitable for reactive gases or fluids permeation, which are required characteristics for application in heterogeneous catalysis process. The composite material obtained from pyrolysis of polymeric precursor has its porosity strongly dependent from precursor constitution, which affects the decomposition kinetic. In this study, it was obtained a polyester precursor based on triethylene glycol, which has been submitted at pyrolysis at 600 oC for several times in nitrogen atmosphere. The nickel-silica nanocomposite obtained through that methodology presents a residual amorphous carbon phase playing an important rule on the mechanism of pore formation. Nickel nanoparticles nucleate with sizes close to 10 nm in diameter and are highly dispersed in a hybrid amorphous carbon-silica matrix. The composite pore volume, calculated through the JBH method, presents a continuous increasing as a function of pyrolysis time, reaching more than 0.15 cc/g after 7 hours from initial decomposition process.

Morphological Analysis of the Amorphous Carbon Embedded Nickel-Silica Composite Submitted at Gradual Oxidation

Amorphous embedded nickel-silica composites can be directly obtained by Polymeric Precursor Method when the polymeric precursor is pyrolysed in controlled atmosphere. The metallic particles dispersion into the matrix composite is very important to material applications, but the resistance against the oxidation under extreme conditions is also required. In this work, nickel-silica nanocomposite sample was synthesized for containing amorphous carbon as matrix interphase through the direct route based on the Polymeric Precursor Method. The composite sample was obtained by pyrolysis of polymeric precursor at 600 oC for 1 hour under nitrogen flow and then submitted to oxidation in oxygen flow at 400 oC up to 7 hours. It was observed by Transmission Electron Microscopy the metallic nickel nanoparticles present high dispersion into matrix composite. However, in spite of the border of the composite particles are easily oxidized and originate nickel oxide phase, as proven by X-Ray Diffraction, the amorphous carbon phase acts as protective phase for the majority of the composite sample. By Nitrogen Adsorption-Desorption Isotherms at 77 K it was demonstrated the carbon phase also preserves significantly the mesoporous nature of the composite under oxidation process.

Effect of the Iron Doping on the Thermal Decomposition of the Polymeric Precursor for the Titanium Dioxide Powder Synthesis

The Polymeric Precursor Method has proved suitable for synthesizing reactive powders using low temperatures of calcination, especially when compared with conventional methods. However, during the thermal decomposition of the polymeric precursor the combustion event can be releases an additional heat that raises the temperature of the sample in several tens of degrees Celsius above the set temperature of the oven. This event may be detrimental to some material types, such as the titanium dioxide semiconductor. This ceramic material has a phase transition at around 600 ° C, which involves the irreversible structural rearrangement, characterized by the phase transition from anatase to rutile TiO2 phase. The control of the calcination step then becomes very important because the efficiency of the photocatalyst is dependent on the amount of anatase phase in the material. Furthermore, use of dopant in the material aims to improve various properties, such as increasing the absorption of radiation and in the time of the excited state, shifting of the absorption edge to the visible region, and increasing of the thermal stability of anatase. In this work, samples of titanium dioxide were synthesized by the Polymeric Precursor Method in order to investigate the effect of Fe (III) doping on the calcination stages. Thermal analysis has demonstrated that the Fe (III) insertion at 1 mol% anticipates the organic decomposition, reducing the combustion event in the final calcination. Furthermore, FTIR-PAS, XRD and SEM results showed that organic matter amount was reduced in the Fe (III)-doped TiO2 sample, which reduced the rutile phase amount and increased the reactivity and crystallinity of the powder samples.

Parameters optimization of heat treatment for obtaining luminescent PZT powders

Low crystalline PZT powder samples were successfully synthesized using polymeric precursor method and slow decomposition steps. The polymeric resin precursor was thermal treated in a muffle type oven varying the temperature from 250 °C to 700 °C and the time from 3 to 24 hours in order to investigate the order/disorder mechanism toward the amorphous powders. Powder samples with low crystalline phases were obtained at lower temperatures and long time of thermal treatment, demonstrating a kinetic dependence for organic removal and a thermodynamic barrier for crystallization processes. Through XRD and FTIR spectroscopy characterizations the long time thermal treated samples showed to be composed of the solid solution of metal oxides in absent of organic matter, originating broad XRD peaks profiles and no carbonaceous bands in FTIR spectra. A Photoluminescence characterization showed that the peak emission is higher for disordered and homogeneous phases, which only can be reached through the long time of thermal treatment.