Orientador: Elson Longo da Silva / Banca: Fenelon Martinho Lima Pontes / Banca: Ieda Lucia Viana Rosa / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Tungstatos em geral têm despertado um grande interesse tecnológico devido às suas propriedades eletro-ópticas, como material para as mais variadas aplicações dentro de faixa específica do espectro fotoluminescente. Neste trabalho, pós de tungstatos de bário (BaW 'O IND. 4') foram preparados pela síntese química de co-precipitação na presença de hidróxido de amônio e processados nos sistemas de hidrotermal convencional e em hidrotermal assistido por irradiação de microondas. Após síntese por co-precipitação, as amostras foram separadas em três grupos, onde no primeiro o material foi deixado em repouxo ao resguardo da luz na temperatura de 28ºC por 48 horas, para verificar se há formação da fase tetragonal. No segundo e terceiro grupo o material foi encaminhado para processamento em hidrotermal convencional e hidrotermal assistido por microondas na temperatura de 140°C em diferentes tempos. Cada material obtido nos três processos foi lavado com água destilada e seco com acetona. Posteriormente aos tratamentos técnicos os pós foram caracterizados utilizando as técnicas de difração de raios X (DRX), espectroscopia Raman com transformadas de Fourier, espectroscopia na região do ultravioleta visível (UV-Vis), Fotoluminescência (FL) e microscopia eletrônica de varredura por canhão de emissão de campo de alta resolução (MEV-FEG). / Abstract: Tungstates, in a general way, have attracted a great technological interest due to their electro-optical properties, as materials for the most diversified applications within the especific range of the photoluminecent spectra. In this work, powders of barium tungstates were prepared by coprecipitation in the presence of ammonium hydroxide. The materials were processed by conventional hydrothermal and also by microwave-assisted hydrothermal technique. After the synthesis by coprecipitation, the samples were aged in a light sensitive storage device at 28°C and 48°C, in order to investigate the formation of a tetragonal phase. In the second and third groups, the samples were heat-treated in the conventional and the microwave-assisted hydrothermal systems at 140°C for different times. Each sample of the three processes was washed with distilled water and drid with acetone. Subsequently to the heat treatments, the powders were characterized by X-Ray Diffraction (XRD), Fourier-transform Raman Spectrocopy, UV-Visible spectrocopy (UV-Vis), Photoluminescence (PL) and Field Emission Gun Scanning Electronic Microscopy (FEG). / Mestre

Co-precipitation and absorption methods were investigated for removal of boron from produced water, which is groundwater brought to the surface during oil and natural gas extraction. Boron can be toxic to many crops and often needs to be controlled to low levels in irrigation water. The present research focused on synthetic reverse osmosis (RO) concentrate modeled on concentrate expected from a future treatment facility at the Arroyo Grande Oil Field on the central coast of California. The produced water at this site is brackish with a boron concentration of 8 mg/L and an expected temperature of 80°C. The future overall produced water treatment process will include lime softening, micro-filtration, cooling, ion exchange, and finally RO. Projected boron concentrations in the RO concentrate are 20 to 25 mg/L. Concentrate temperature will be near ambient. This RO concentrate will be injected back into the formation. To prevent an accumulation of boron in the formation, it is desired to reduce boron concentrations in this concentrate and partition the boron into a solid sludge that could be transported out of the area. The primary method explored for boron removal during this study was adsorption and co-precipitation by magnesium chloride. Some magnesium oxide tests were also conducted. Jar testing was used to determine the degree of boron removal as a function of initial concentration, pH, temperature, and reaction time. Synthetic RO concentrate was used to control background water quality factors that could potentially influence boron removal. The standard synthetic RO concentrate contained 8 g NaCl/L, 150 mg Si/L and 30 mg B/L. After synthetic RO concentrate was prepared, amendments (e.g. sulfate, sodium chloride) were added and the pH adjusted to the desired value. Each solution was then carried through a mixing and settling protocol (5 min at 200 RPM, 10 min at 20 RPM, followed by 30 min settling and filtration). Boron concentrations from the jar tests were determined using the Carmine colorimetric method. Boron removal with magnesium chloride was greatest at a pH of 11.0. At this pH 87% of boron was removed using 5.0 g/L MgCl2◦6H2O at 20°C. Mixing time did not greatly affect boron removal for mixing periods of 5 to 1321 minutes. This result indicates equilibrium was achieved during the 45-min experimental protocol. Maximum boron removal was observed in the temperature range of 29°C to 41°C. At 68°C boron removal decreased five-fold compared to the reduction observed at 29°C to 41°C. For treatment of the cool concentrate, this relatively low optimal temperature range gives magnesium chloride an advantage over magnesium oxide, which is effective only at high temperatures. Neither sodium chloride nor sodium sulfate affected boron removal by magnesium chloride for the chloride and sulfate concentrations expected in the produced water at this site. In contrast, silica did inhibit boron removal, with removal decreasing from 30% to 5% when silica concentration was increased from 0 to 100 mmols/L. This result was unexpected because other researchers have reported silica is necessary for effective removal of boron by magnesium chloride. To investigate the reasons for the differing boron removal results for magnesium chloride and magnesium oxide, solids produced by the two reagents were compared using X-ray diffraction spectroscopy (XRD). Solids from magnesium chloride contained 30% amorphous material versus 10% for magnesium oxide. The crystalline components from the magnesium oxide treatment were for the most part magnesium oxide, whereas magnesium chloride crystalline solids were a combination of brucite (Mg(OH)2) and magnesium chloride hydroxide. The greater boron adsorption observed with magnesium chloride could thus either be attributed to the greater surface area of the amorphous precipitate and/or the higher boron affinity of brucite and magnesium chloride hydroxide. Adsorption isotherms were plotted for boron removal by magnesium compounds formed during precipitation. Boron adsorption followed a linear isotherm (r2= 0.92) for boron concentrations up to 37.8 mg B/L. While the data also fit Langmuir and Freundlich models the data fell in the linear range of those models. The linearity of the adsorption curves indicates that adsorption sites for boron were not saturated at these concentrations. The linearity means that higher boron concentrations in the RO concentrate will lead to greater mass removal, up to concentrations of at least 37.8 mg/L boron. Using magnesium chloride, boron removal by co-precipitation was more effective than by adsorption to pre-formed precipitate. Removal approximately doubled for a given dose of magnesium chloride. The effectiveness of co-precipitation presumably occurs due to entrapment of boron as the precipitate forms. This study has shown the potential of magnesium chloride as an agent for boron removal by determining those conditions most effective for boron co-precipitation and adsorption. Magnesium chloride has been shown to be more effective than magnesium oxide. Magnesium chloride also out-performed treatment with slaked quicklime, which was tested previously by others. Two important limitations of boron removal with magnesium chloride are the high chemical requirements (5 g/L MgCl2) and sludge production (1 g/g MgCl2 used). These are greatly mitigated by treatment of RO concentrate rather than the full produced water flow. In addition, reagent use and sludge production might be decreased by recycling sludge from the up-front lime softening process. Compared to magnesium oxide, magnesium chloride removes greater quantities of boron per mole of magnesium added (20 mg B/g MgCl2). The magnesium chloride isotherm demonstrated that treatment of RO concentrate required less reagent and produced less sludge per mass of boron removed than treatment of the more dilute feed water.

Il existe actuellement un important besoin en dispositifs électroniques dans le domaine des longueurs d’ondes millimétriques, tels que les circulateurs et les isolateurs fonctionnant dans la gamme de fréquence 30-100 GHz. Les aimants permanents qui garantissent la propagation de l’onde électromagnétique dans ces dispositifs comportent très généralement des éléments terres rares. En raison du coût à l’acquisition de ces éléments, d’une part, ainsi que de leur coût environnemental d’autre part, il existe une demande d’aimants permanents produits sans terres rares. Les ferrites durs peuvent présenter les propriétés demandées pour une intégration dans les dipositifs micoondes non réciproques. Ainsi, les particules de ferrite de baryum (BaM) possèdent un champ d’anisotropie magnétocristallin important, dirigé selon l’axe de facile aimantation. Un matériau autopolarisé, constitué d’un empilement de ces particules, peut donc présenter une aimantation permanente d’intensité suffisante pour les applications visées. De nombreuses méthodes d’élaboration de tels matériaux ont été mises au point. Cependant les mises en oeuvre de ces méthodes sont contraignantes. En revanche, nous avons mis au point dans le présent travail un processus de réalisation de ferrites de BaM massifs autopolarisés, dont l’aspect technologique est simple (basé sur des méthodes de chimie douce et des traitements thermiques adaptés), et très abordable financièrement. Les résultats obtenus sont très compétitifs (aimantation rémanente normalisée MR/MS comprise entre 0.87 et 0.90. Le champ coercitif HC atteint la valeur de 303 kA/m, rendant le matériau peu sensible aux effets démagnétisants), et permettent d’envisager la production de ces matériaux en vue d’applications à des fréquences allant jusqu’à 55 GHz. / Presently, there is a critical need for millimeter wave devices, among which are non-reciprocal devices such as isolators and circulators, which operate in the frequency range from about 30 GHz to 100 GHz.Permanent magnets that ensure the propagation of the wave in such devices are for long based on rare-earth elements. Nowadays, the escalation of rare earths cost encourages to look for alternative materials containing much less, or no, rare earth elements selected from the most common and most available. Alternatively, hard ferrites may show the required potential for integration into non-reciprocal microwave devices. Barium ferrite (BaM) is a wellknown, high-performance, permanent magnet material with a large magneto-crystalline anisotropy along the c-axis of its hexagonal structure. A suitable form of barium ferrite for mm-wave applications is a magnetically oriented bulk material.Several constraining processing techniques were therefore set up to perform the alignment and compaction of plate hexaferrite particles. In contrast to these methods, the present study demonstrates the feasibility of simple alternative ways to provide highly oriented bulk compacts made of BaM particles. In the present work efficient and inexpensive chemical processes (co-precipitation, dry mixing and wet mixing) are presented that produces highly oriented bulk compacts made of Barium hexaferrites (BaM) particles. Hysteresis loops that display very competitive squarenesses between 0.87 and 0.90 (normalized remanent magnetization) and coercivity as high as 303 kA/m are obtained. The sensitivity to demagnetizing effects is therfore reduced. These properties make these BaM bulk ferrite materials suitable for selfbiased applications at frequencies up to 55 GHz.

Device associated infections are a growing problem in the field of orthopaedics and dentistry. Bacteria adhering to implant surfaces and subsequent biofilm formation are challenging to treat with systemic administered antibiotics. Functionalization of implant surfaces with therapeutic coatings that are capable of inhibiting bacterial adhesion are therefore considered as a straight forward strategy to treat and prevent implant related infections. In this thesis, the use of crystalline, arc deposited TiO2 and biomimetic hydroxyapatite (HA) coatings were evaluated with respect to their potential as antibacterial surface modifications for bone-anchored implants. UV light induced photocatalysis of anatase dominated TiO2 coated surfaces was shown to provide a bactericidal effect against S. epidermidis under clinically relevant illumination times and doses. Major parts of the drug release work carried out was based on biomimetic HA (HA-B) coated fixation pins. The analysis of the coating characteristics revealed that the nanoporous structure of HA-B coatings in addition to the chemical composition and surface charge are essential parameters that influence the drug carrier performance. Loading by adsorption was demonstrated to be a feasible approach to quickly incorporate antibiotics. The controlled release of antibiotics was shown to facilitate bactericidal effects against S. aureus over application-relevant time periods, even when exposed to biomechanical forces during insertion into bone model materials. Antibiotic incorporation during coating growth was shown to promote somewhat longer drug release time periods than those obtained using adsorption loading. In summary, functionalization of implant surfaces with bioactive and biocompatible coatings is a promising concept to impact the clinical success for bone-anchored applications. The additional feature of optional, on-demand antibacterial properties of these coatings through either on-site drug release or photocatalytic antibacterial treatment is advantageous for the prevention and effective treatment of devices-associated infections. Both strategies provide an immediate response to the implant contamination by bacteria and are believed to contribute towards minimizing the origin of post-surgical infections, while at the same time improving the interfacial stability between implant and bone.

This thesis investigated the impact of aluminum (Al) substitution in ferrihydrite (FH) on both its chemical and physical properties. Al was coprecipitated with FH under controlled hydrolysis conditions to yield various % mol substitutions. Sulfate adsorption was measured across pHs to examine any changes in surface reactivity. The samples’ morphology, specific surface areas (SSAs), crystallinity, and phase transformation upon heating were evaluated and parameterized to allow conclusions on the role of Al on the physical properties. Sulfate sorption diminished across pHs for all Al saturation levels. X-ray Diffraction revealed goethite (GT) presence was negatively influenced by Al. The SSAs of samples increased non-linearly with increasing % mol Al, indicating a decreasing particle size with more Al content. Transmission Electron Microscopy micrographs showed the FH nanoparticles transformed to acicular/blocky laths of GT crystals and lenticular/platy hematite (HM) crystals with occasional grainy appearance at both room temperature and upon active heating. The phase transformation alongside the derived aspect ratios (length/width) of the GT crystals were retarded by the Al substitution.

Understanding the link between the Sun and climate is vital in the current incidence of global climate change, and 10Be in natural archives constitutes an excellent tracer for this purpose. As cosmic rays enter the atmosphere, cosmogenic isotopes like 10Be and 14C are formed. Variations in solar activity modulate the amount of incoming cosmic rays, and thereby cosmogenic isotope production. Atmospherically produced 10Be enters natural archives such as sediments and glaciers by wet and dry deposition within about a year of production. 10Be from natural archives therefore provides information on past solar activity, and because these archives also contain climate information, solar activity and climate can be linked. One remaining question is to what degree 10Be in natural archives reflects production, and to what extent the local and regional environment overprints the production signal. To explore this, 10Be was measured at annual resolution over the last 600 years in a Greenland ice core. Measurement potentials for these samples benefited from the development of a new laboratory method of co-precipitating 10Be with niobium. To diversify geographic location and archive media type, a pioneer study of measuring 10Be with annual resolution in varved lake sediments from Finland was conducted, with samples from the entire 20th century. Pathways of 10Be into lake sediments are more complex than into glacial ice, inferring that contemporary atmospheric conditions may not be recorded. Here, it is shown for the first time that tracing the 11-year solar cycle through lake sediment 10Be variations is possible. Results also show that on an annual basis, 10Be deposition in ice and sediment archives is affected by local environmental conditions. On a slightly longer timescale, however, diverse 10Be records exhibit similar trends and a negative correlation with solar activity. Cyclic variability of 10Be deposition persisted throughout past grand solar minima, when little or no sunspot activity was recorded. 10Be levels indicate that although solar activity has been high during the 20th century, levels are not unprecedented in the investigated 600 years. Aerosol 10Be/7Be values indicate possible influence of stratosphere-troposphere exchange on isotope abundance and the production signal.

ABSRACT This study was to investigate the removal efficiency and kinetics in oxidation of ammonia solutions (NH3-N) in ranging from 400 mg/L to 1000 mg/L by adding Cu/La/Ce catalyst in process of Wet Air Oxidation (denoted by WAO). All experiments were conducted in semi-batch and continuous reactors in series. The major parameters included temperature, pressure, concentration and pH. In the semi-batch type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, temperatures ranging from 423 K to 503 K, a total pressure of 4.0 Mpa, and a pH of 12.0. A removal efficiency of 32.7%was obtained in WAO process at 503 K for180 min, but it could be significantly promote to 95.1% after adding a catalyst of molar ratio 7:2:1.The kinetics of WAO with this catalyst in oxidation of NH3-N solutions, using a test of half-life, was developed nearly to a zero order. The reaction constants were 10.12 KJ/mol, 9.12 KJ/mol, and 6.57 KJ/mol at 503 K, 473 K and 423 K. In the continuous type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, a temperature of 503 K, a total pressure of 2.0 Mpa, a pH of 12.0 and a liquid space velocity of 4.5 hr-1 (averagelyresidence time 14 min) . A removal efficiency of NH3-N of 6.5 % only was achieved in WAO process for a space velocity of 4.5 hr-1 (averagely residence time 14 min) , but after adding a catalyst of molar ratio 7:2:1 it increased to 72.3 % for a same residence time and a better efficiency of above 91 % was found for 1.5 hr-1 (averagely residence time 40 min) . For increasing the initial concentration of NH3-N into 600 mg/L, 800 mg/L, and 1000 mg/L the removal efficiency of NH3-N decreased with 85 %,75 % and 69 % for 1.5 hr-1 . Thus, the initial concentration of NH3-N in influent inhibits the removal efficiency in the oxidation process. The higher initial concentration the lower removal efficiency.

The high-temperature superconductor Sr1-xCaxCuO2 was synthesized using sol-gel, solid-state reaction and co-precipitation methods. The analysis of its formation was made and the structure of the products was determined with the help of the X-ray diffraction. The termal processes, that take place during the synthesis, were analyzed with the help of differential-termal analysis. The experiment has showed that the SrCuO2 formes in the the process of heating the citrats precursors at the temperature of 800oC. And the S0,5Ca0,5CuO2 formes at 900oC by sol-gel, solid-state reaction methods. The best results are achieved using citric gel precursor at the temperature of 900oC. The increase of heating duration up to 36 hours, made no considerable diference in the qualitative composition, however this has changed the quantitative composition.

Original estimates of phosphorus (P) concentrations in the Precambrian oceans before 1.9 Ga gave a budget of ~10-25% of modern day levels. This budget was challenged by accounting for high silica (Si) concentrations that were believed to have outcompeted P for binding sites on precipitating iron oxide-hydroxide particles during the chemical oxidation and burial of iron (Fe). Such iron oxide-hydroxide particles are considered as proxies of ancient iron-rich sedimentary rocks, such as banded iron formations, which are often used to infer the dissolved chemistry of trace elements in the ancient oceans. This study raises the question of wether arsenic (As) had an effect of the binding of P to precipitating iron minerals, during the co-precipitation of Iron oxide- hydroxide in elevated Fe and Si concentrations characteristic of the early oceans. This hypothesis is based on the chemical similarities seen between P and As. Results show a more pH dependent competition between P and AsIII, whereby P outcompetes AsIII at a pH <7. The effect decreases as the pH rises until pH ~8 at which the effect cancels out and AsIII becomes somewhat predominant over P. AsV on the other hand, an analogue to P, is outcompeted by P throughout pH 5-10. Distribution coefficients (Kd) of P on iron oxide-hydroxide particles were not affected by the concentration of Si in solution. Average Kd and standard error between concentrations of Si, across the sample pH of 5-10 revealed an average Kd of 0.072 (±0.01) μM-1. This is strikingly similar to another experimental Kd at 0.075 (±0.003) μM-1, when the effects of Si are excluded. The average Kd in this study is also consistent with the average Kd of 0.06 μM-1 from a range of As-rich hydrothermal systems reported in a previous study, supporting the original idea of Precambrian P levels being low. The average Kd between concentrations of Fe revealed a Kd of 0.12 (±0.03) μM-1 although this was not statistically significant from the average Kd between groups of Si. In addition to low levels of P, the Precambrian oceans likely also contained high levels of As, due to the high hydrothermal activity. This scavenging of P from oceanic waters would have become increasingly important as surface oceans became more oxygenated and the presence of AsV would have been greater. Because the availability of Si does not show any great effect on the uptake of P by precipitating iron oxide-hydroxides, Si concentration is likely not a proxy for oceanic P concentrations. It is proposed that low dissolved P levels are consistent with early oceans that w!ere a lot more hydrothermally influenced than the oceans of today. / Prekambriska fosfor (P) nivåer var ursprungligen estimerade till ca 10-25% utav koncentrationen funnen i dagens havsvatten. Denna budget blev motsagd i och med att kisel (Si) sades kunna ersätta bundet fosfor på järn oxid-hydroxid partiklar som precipiterade genom kemisk oxidation och sedimentering av järn (Fe). Dessa järn oxid-hydroxid partiklar anses användbara som proxy för formationen av uråldriga järn-rika sedimentära bergarter såsom banded iron formation (BIF), vilka används idag för att bestämma mängden spårämnen i de uråldriga haven. Denna studie ställer frågan huruvida arsenik (As) påverkar mängden P som binder till precipiterande järn mineral under procession av co-precipitering av järn oxid-hydroxid i lösning med förhöjda koncentrationer av Fe och Si, karakteristiska för the uråldriga haven. Denna hypotes är baserad på de kemiska likheter som finns mellan P och As. Resultaten påvisar en pH beroende konkurrens mellan P och AsIII där P utkonkurrerar AsIII vid låg pH. Effekten av denna konkurrans minskar med ökande pH tills effekten blir omvänd omkring pH 8 och P blir istället till viss del utkonkurrerad av AsIII. AsV å andra sedan, en verklig kemisk analog till P, är kontinuerligt utkonkurrerad av P genom alla utförda pH, pH 5-10. Distribueringskoefficienter (Kd) för P på järn oxid-hydroxid partiklar visade ingen påverkan av mängden Si tillgängligt. Medelvärdet av Kd och standard error mellan data av alls pH, grupperat av Si, gav ett värde av 0.072 (±0.01) μM-1. Detta är påfallande nära ett experimentellt framtaget Kd värde av 0.075 (±0.03) μM-1 då effekten av Si är borttagen. Medelvärdet i denna studie är också sammanfallande med det Kd medelvärde man finner idag från olika hydrotemala system av 0.063 (±0.01) μM-1. Detta ger support till den originala idén att de prekambriska haven troligen hade låga halter P tillgängligt. Medelvärdet av Kd mellan koncentrationer av Fe gav ett värde av 0.12 (±0.03) μM-1, dock var detta värde ej statistiskt significant från det Kd utifrån koncentrationer av Si. Förutom de låga nivåer av P i de Prekambriska haven så var det troligen även höga halter av As på grund av utbredd hydrotermal aktivitet. Detta uppfångande av P i de tidiga haven var troligen en alltmer viktigare process då ytvatten blev syrerikare och den oxiderade formen av As, det vill säga AsV hade varit mer vanligt förekommande. Framför allt då den konkurrerande effekten av Si kan bortses när P såväl som As inte påverkas av dess närvaro till den grad man hade trott. Detta gör även att mängden Si troligen inte är en tillförlitlig proxy för att estimera P nivåer i de uråldriga haven. Därmed föreslås det att de prekambriska haven var k!arakteriserade av låga P nivåer, jämfört med idag.

Made available in DSpace on 2014-06-11T19:23:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-01-23Bitstream added on 2014-06-13T19:29:35Z : No. of bitstreams: 1 limajr_lf_me_bauru.pdf: 7258197 bytes, checksum: 7ee09909389a4e99da47b8de66b8a905 (MD5) / Tungstatos em geral têm despertado um grande interesse tecnológico devido às suas propriedades eletro-ópticas, como material para as mais variadas aplicações dentro de faixa específica do espectro fotoluminescente. Neste trabalho, pós de tungstatos de bário (BaW 'O IND. 4') foram preparados pela síntese química de co-precipitação na presença de hidróxido de amônio e processados nos sistemas de hidrotermal convencional e em hidrotermal assistido por irradiação de microondas. Após síntese por co-precipitação, as amostras foram separadas em três grupos, onde no primeiro o material foi deixado em repouxo ao resguardo da luz na temperatura de 28ºC por 48 horas, para verificar se há formação da fase tetragonal. No segundo e terceiro grupo o material foi encaminhado para processamento em hidrotermal convencional e hidrotermal assistido por microondas na temperatura de 140°C em diferentes tempos. Cada material obtido nos três processos foi lavado com água destilada e seco com acetona. Posteriormente aos tratamentos técnicos os pós foram caracterizados utilizando as técnicas de difração de raios X (DRX), espectroscopia Raman com transformadas de Fourier, espectroscopia na região do ultravioleta visível (UV-Vis), Fotoluminescência (FL) e microscopia eletrônica de varredura por canhão de emissão de campo de alta resolução (MEV-FEG). / Tungstates, in a general way, have attracted a great technological interest due to their electro-optical properties, as materials for the most diversified applications within the especific range of the photoluminecent spectra. In this work, powders of barium tungstates were prepared by coprecipitation in the presence of ammonium hydroxide. The materials were processed by conventional hydrothermal and also by microwave-assisted hydrothermal technique. After the synthesis by coprecipitation, the samples were aged in a light sensitive storage device at 28°C and 48°C, in order to investigate the formation of a tetragonal phase. In the second and third groups, the samples were heat-treated in the conventional and the microwave-assisted hydrothermal systems at 140°C for different times. Each sample of the three processes was washed with distilled water and drid with acetone. Subsequently to the heat treatments, the powders were characterized by X-Ray Diffraction (XRD), Fourier-transform Raman Spectrocopy, UV-Visible spectrocopy (UV-Vis), Photoluminescence (PL) and Field Emission Gun Scanning Electronic Microscopy (FEG).