Niobium and rare earth minerals from the Virulundo carbonatite, Namibe, Angola

The Virulundo carbonatite in Angola, one of the biggest in the world, contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias, trachytoids). The composition of the primary pyrochlore crystals is very close to fluornatrocalciopyrochlore in all these units. High-temperature hydrothermal processes caused the pseudomorphic replacement of the above crystals by a second generation of pyrochlore, characterized by lower F and Na contents. Low-temperature hydrothermal replacement of the above pyrochlores, associated with production of quartz-carbonates-fluorite veins, controled the development of a third generation of pyrochlore, characterized by high Sr contents. Finally, supergene processes produced the development of a secondary paragenesis in the carbonatite, consisting in late carbonates, goethite, hollandite and REE minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Separation of Ce from the other REE was allowed by oxidizing conditions. Therefore, Ce4+ was also incorporated into a late generation of pyrochlore, which is also strongly enriched in Ba and strongly depleted in Ca and Na

Niobium and rare earth minerals from the Virulundo carbonatite, Namibe, Angola

The Virulundo carbonatite in Angola, one of the biggest in the world, contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias, trachytoids). The composition of the primary pyrochlore crystals is very close to fluornatrocalciopyrochlore in all these units. High-temperature hydrothermal processes caused the pseudomorphic replacement of the above crystals by a second generation of pyrochlore, characterized by lower F and Na contents. Low-temperature hydrothermal replacement of the above pyrochlores, associated with production of quartz-carbonates-fluorite veins, controled the development of a third generation of pyrochlore, characterized by high Sr contents. Finally, supergene processes produced the development of a secondary paragenesis in the carbonatite, consisting in late carbonates, goethite, hollandite and REE minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Separation of Ce from the other REE was allowed by oxidizing conditions. Therefore, Ce4+ was also incorporated into a late generation of pyrochlore, which is also strongly enriched in Ba and strongly depleted in Ca and Na

Del Noguerola al Segre: els problemes de la qualitat ambiental de l'aigua

Treball de recerca realitzat per un alumne d'ensenyament secundari i guardonat amb un Premi CIRIT per fomentar l'esperit científic del Jovent l'any 2009. Els principals objectius del treball són intentar demostrar, cinc anys més tard, si el riu Noguerola és encara fruit d'abocaments residuals en el seu pas subterrani per la ciutat de Lleida, i observar i analitzar com el riu Segre sofreix múltiples impactes ambientals provinents, especialment, de les activitats agrícoles i ramaderes. Es van fer dos campanyes de mostrejos en les confluències de 10 afluents dels marges dret i esquerre del riu Segre, i en 5 punts al llarg d'aquest. Per a cada mostra es van analitzar: conductivitat, temperatura, ph, nitrats, nitrits, amoni, fosfats, duresa i microorganismes. A més a més, es van delimitar i determinar les superfícies de les conques i es van fer balanços hidrometeorològics per determinar les aportacions naturals de l’aigua de pluja, i es van estimar els excedents de reg de totes les conques, per així calcular les masses totals de cada paràmetre, aportades per cada afluent. Les principals conclusions a què s’ha arribat són: que el riu Noguerola continua sent fruit d'abocaments residuals en el seu pas subterrani per la ciutat de Lleida. I que, tant les activitats agrícoles i ramaderes, com les captacions d'aigua dels canals de Balaguer i de Seròs per a l’obtenció d’energia hidroelèctrica, provoquen greus impactes ambientals al riu Segre.

Nanosized Nb-TiO2 gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO2 modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100 C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600 C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600 C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.

Nanosized Nb-TiO2 gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO2 modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100 C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600 C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600 C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.

Effects of Nb doping on the TiO2 anatase-to-rutile phase transition

We study the influence of Nb doping on the TiO2 anatase-to-rutile phase transition, using combined transmission electron microscopy, Raman spectroscopy, x-ray diffraction and selected area electron diffraction analysis. This approach enabled anatase-to-rutile phase transition hindering to be clearly observed for low Nb-doped TiO2 samples. Moreover, there was clear grain growth inhibition in the samples containing Nb. The use of high resolution transmission electron microscopy with our samples provides an innovative perspective compared with previous research on this issue. Our analysis shows that niobium is segregated from the anatase structure before and during the phase transformation, leading to the formation of NbO nanoclusters on the surface of the TiO2 rutile nanoparticles.

Highly textured Sr, Nb, co-doped BiFeO3 thin films grown on SrRuO3/Si substrates by rf-sputtering

In this study, (011)-highly oriented Sr, Nb co-doped BiFeO3 (BFO) thin films were successfully grown on SrRuO3/Si substrates by rf-magnetron sputtering. The presence of parasite magnetic phases was ruled out based on the high resolution x-ray diffraction data. BFO films exhibited a columnar-like grain growth with rms surface roughness values of 5.3 nm and average grain sizes of 65-70 nm for samples with different thicknesses. Remanent polarization values (2Pr) of 54 lC cm 2 at room temperature were found for the BFO films with a ferroelectric behavior characteristic of an asymmetric device structure. Analysis of the leakage mechanisms for this structure in negative bias suggests Schottky injection and a dominant Poole-Frenkel trap-limited conduction at room temperature. Oxygen vacancies and Fe3þ/Fe2þ trap centers are consistent with the surface chemical bonding states analysis from x-ray photoelectron spectroscopy data. The (011)-BFO/ SrRuO3/Si film structure exhibits a strong magnetic interaction at the interface between the multiferroic film and the substrate layer where an enhanced ferromagnetic response at 5 K was observed. Zero-field cooled (ZFC) and field cooled (FC) magnetization curves of this film system revealed a possible spin glass behavior at spin freezing temperatures below 30 K depending on the BFO film thickness.

BS-SEM evaluation of the tisular interactions between cortical bone and calcium-phosphate covered titanium implants

The improvement of the reliability of the contact between the osseous tissues and the implant materials has been tested by recovering the metallic implants with ceramic materials, usually calcium phosphates. In our study, the calcium phosphate recovering layers were deposited by means of a pulsed-laser deposition technique. Our aim was to to evaluate the tissue interactions established between cortical bone and titanium implants covered by five different layers, ranging from amorphous calcium phosphate to crystalline hydroxyapatite, obtained by altering the parameters of the laser ablation process. The surgical protocol of the study consisted in the simultaneous implantation of the five types of implants in both the tibial dyaphisis of three Beagle dogs, sacrificed respectively one, two and three months after the last surgical procedures. After the sacrifice, the samples were submitted to a scheduled procedure of embedding in plastic polymers without prior decalcification, in order to perform the ultrastructural studies: scanning microscopy with secondary and backscattered electrons (BS-SEM). Our observations show that both in terms of the calcified tissues appearing as a response to the presence of the different coatings and of time of recovering, the implants coated with crystalline calcium phosphate layers by laser ablation present a better result than the amorphous-calcium-phosphate-coated implants. Moreover, the constant presence of chondroid tissue, related with the mechanical induction by forces applied on the recovering area, strongly suggests that the mechanisms implied in osteointegration are related to endomembranous, rather than endochondral ossification processes

BS-SEM evaluation of the tisular interactions between cortical bone and calcium-phosphate covered titanium implants

The improvement of the reliability of the contact between the osseous tissues and the implant materials has been tested by recovering the metallic implants with ceramic materials, usually calcium phosphates. In our study, the calcium phosphate recovering layers were deposited by means of a pulsed-laser deposition technique. Our aim was to to evaluate the tissue interactions established between cortical bone and titanium implants covered by five different layers, ranging from amorphous calcium phosphate to crystalline hydroxyapatite, obtained by altering the parameters of the laser ablation process. The surgical protocol of the study consisted in the simultaneous implantation of the five types of implants in both the tibial dyaphisis of three Beagle dogs, sacrificed respectively one, two and three months after the last surgical procedures. After the sacrifice, the samples were submitted to a scheduled procedure of embedding in plastic polymers without prior decalcification, in order to perform the ultrastructural studies: scanning microscopy with secondary and backscattered electrons (BS-SEM). Our observations show that both in terms of the calcified tissues appearing as a response to the presence of the different coatings and of time of recovering, the implants coated with crystalline calcium phosphate layers by laser ablation present a better result than the amorphous-calcium-phosphate-coated implants. Moreover, the constant presence of chondroid tissue, related with the mechanical induction by forces applied on the recovering area, strongly suggests that the mechanisms implied in osteointegration are related to endomembranous, rather than endochondral ossification processes

BS-SEM evaluation of the tisular interactions between cortical bone and calcium-phosphate covered titanium implants

The improvement of the reliability of the contact between the osseous tissues and the implant materials has been tested by recovering the metallic implants with ceramic materials, usually calcium phosphates. In our study, the calcium phosphate recovering layers were deposited by means of a pulsed-laser deposition technique. Our aim was to to evaluate the tissue interactions established between cortical bone and titanium implants covered by five different layers, ranging from amorphous calcium phosphate to crystalline hydroxyapatite, obtained by altering the parameters of the laser ablation process. The surgical protocol of the study consisted in the simultaneous implantation of the five types of implants in both the tibial dyaphisis of three Beagle dogs, sacrificed respectively one, two and three months after the last surgical procedures. After the sacrifice, the samples were submitted to a scheduled procedure of embedding in plastic polymers without prior decalcification, in order to perform the ultrastructural studies: scanning microscopy with secondary and backscattered electrons (BS-SEM). Our observations show that both in terms of the calcified tissues appearing as a response to the presence of the different coatings and of time of recovering, the implants coated with crystalline calcium phosphate layers by laser ablation present a better result than the amorphous-calcium-phosphate-coated implants. Moreover, the constant presence of chondroid tissue, related with the mechanical induction by forces applied on the recovering area, strongly suggests that the mechanisms implied in osteointegration are related to endomembranous, rather than endochondral ossification processes