Regina Monteiro

Glass samples with a molar composition (64+x)ZnO–(16−x)B2O3–20SiO2, where x=0 or 1, were successfully synthesized using a melt-quenching technique. Based on differential thermal analysis data, the produced glass samples were submitted to controlled heat-treatments at selected temperatures (610, 615 and 620 °C) during various times ranging from 8 to 30 h. The crystallization of willemite (Zn2SiO4) within the glass matrix was confirmed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Under specific heat-treatment conditions, transparent nanocomposite glass-ceramics were obtained, as confirmed by UV–vis spectroscopy. The influence of temperature, holding time and glass composition on crystal growth was investigated. The mean crystallite size was determined by image analysis on SEM micrographs. The results indicated an increase on the crystallite size and density with time and temperature. The change of crystallite size with time for the heat-treatments at 615 and 620 °C depended on the glass composition. Under fixed heat-treatment conditions, the crystallite density was comparatively higher for the glass composition with higher ZnO content. © 2016 Elsevier B.V.

Different glasses based on the ZnO-B2O3-SiO2 system, with a ZnO content ≥ 60 mol% and a fixed SiO2 content (20 mol%), were synthesised using a melt-quenching method. Glass samples with zinc oxide concentrations as high as 65 mol% were prepared successfully without deteriorating the glass-forming ability. The glass samples were submitted to controlled heat-treatments, and the effect of the ZnO/B2O3 molar ratio on the formation of crystalline phases within the glass matrix was investigated by means of differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). DTA results indicated that the glass transition and the onset crystallization temperatures of the studied glasses tended to increase with the increment on the ZnO/B2O3 ratio. XRD data showed that the zinc binary crystalline phases, willemite (Zn2SiO4), a zinc orthosilicate, and zinc borate (Zn3B2O6) could be present in the crystallized glasses, depending on the heat-treatment conditions. The formation of willemite was promoted by an increasing ZnO/B2O3 ratio. Microstructural observations performed by SEM indicated that under controlled experimental parameters (glass composition, heat-treatment temperature and time) the precipitation of nanocrystals within the glass matrix can be achieved, resulting in transparent and translucent willemite glass-ceramics. © 2016 Elsevier B.V. All rights reserved.

Phosphogypsum (PG) is a pollutant residue resulting from the production of phosphoric acid in the phosphated fertilizers industry. About 180 millions of tons of PG are generated worldwide per year, which originates storage problems because of the environmental restrictions and the high costs of storage spaces. Taking into account the mineralizer properties of PG it has been studied a way to valorize this residue as an alternative material in the production of Portland cement clinker. The PG and the raw-materials (limestone, marl, sand and iron oxide) were chemical, mineralogical and thermally characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD) and differential thermal analysis and termogravimetric analysis (DTA/TGA). After milling, the phosphogypsum was mixed with the raw-materials in different amounts up to 10% weight. The raw mixtures were submitted to two types of firing schedules, heating up to 1500°C without any holding time or heating up to 1350°C and holding for 20 minutes. After firing, the clinkers were analyzed by optical microscopy, milled and characterized in terms of chemical and mineralogical compositions. The clinkers were used to produce cement mortar according to NP EN 196-1 standard. The resultant test specimens were mechanically tested at 2 and 28 days according to the same standard. The obtained results show a reduction of about 140°C in the clinkerization temperature, when a raw mixture with 5% phosphogypsum was used. Standard clinkers, without phosphogypsum addition, which were fired at 1500°C, originated test specimens with a compressive strength of 48.1MPa at 28 days. Test specimens produced with clinker containing 5% phosphogypsum present higher compressive strength values at 28 days, being 55.1MPa for clinkers produced at 1500°C, and 49.4 MPa for clinkers produced at 1350°C. © (2013) Trans Tech Publications, Switzerland.

{Aluminophosphate glasses belonging to the Li2O-BaO-Al 2O3- La2O3-P2O 5 system doped with Tb3+ were prepared and investigated. Methods as Induced Coupled Plasma-Mass Spectrometry (ICP-MS), Induced Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) and X-ray diffraction (XRD) have been used to establish the elemental composition of these vitreous materials. The influence of the Tb3+ ions on the optical properties of the phosphate glasses has been investigated in relation with the structural characteristics of the vitreous matrix. The optical behavior has been studied by ultra-violet-visible (UV-Vis) spectroscopy, revealing electronic transitions specific for terbium ions. Fluorescence spectroscopy measurements have been performed by excitation in the UV and visible domains (377 nm and 488 nm) which resulted in the most significant fluorescence peaks in the Vis domain (540 and 547 nm). Structural information via vibration modes were provided by Fourier Transform Infrared (FTIR) absorption spectra in the 400-4000 cm-1 range. Absorption peaks specific for the vitreous phosphate matrix were put in evidence as P-O-P symmetrical and asymmetrical stretching vibration modes, P-O-P bend, PO2- symmetrical and asymmetrical stretching vibration modes

The work deals with optical and structural properties of aluminophosphate glasses from Li2O-BaO-Al2O3-La 2O3-P2O5 system containing Sm 3 + and Eu3 + ions. X-ray fluorescence (XRF) has been used to establish the elemental composition of these materials. The influence of Sm3 + and Eu3 + ions on the optical properties of these glasses has been investigated in relation with their structural characteristics. The optical behavior of these materials has been studied by ultra-violet-visible (UV-Vis) spectroscopy, revealing absorption maxima specific to the doping ions. Structural information via vibration modes was provided by Fourier Transform Infrared (FTIR) absorption spectra evidenced as POP symmetrical and asymmetrical stretching vibration modes, POP bend, PO 2- symmetrical and asymmetrical stretching vibration modes, PO stretching vibration mode and POH water absorbance. Raman spectra acquired by 514.5 nm laser excitation disclosed peaks specific to metaphosphate network. Information about the elemental compositional homogeneity of Sm 3 + and Eu3 +-containing glasses as well as about the defects of the doped-glasses is revealed by scanning electron microscopy/energy dispersive spectrometry (SEM/EDS). Fluorescence spectroscopy measurements put in evidence important fluorescence peaks found at 596 nm and 643 nm for Sm 3 + ions in phosphate matrix and 611 nm and 700 nm in the case of Eu3 +-doped glass. © 2013 Elsevier B.V.

The aim was to investigate the effect of simulated low-temperature degradation (s-LTD) and hydrothermal fatigue on the degradation of three ZrO2-based dental materials. Lava, IPS, and NanoZr discs were randomly assigned to (1) Control-Storage in distilled water at 37°C; (2) Aging at 134°C for 5 h (s-LTD); (3) Thermocycling in saliva for 30,000 cycles (TF). XRD revealed that ZrO 2 m phase was identified in all groups but TF increased the m phase only for Lava. Under the FESEM, Lava showed no alterations under s-LTD, but displayed corrosion areas up to 60 μm wide after TF. We conclude that TF accelerated the degradation of Lava through an increase in the m phase and grain pull-out from the material surface.

Barium zinc borosilicate glasses with a molar composition xBaO-(60-x)ZnO-30B 2O 3-10SiO 2, where x ranged from 0 to 60 mol%, were prepared using melt-quenching method. The effect of BaO substitution for ZnO on the sintering, crystallization, and dielectric characteristics has been investigated. The behavior of the studied barium zinc borosilicate glasses was mainly determined by the relative amount of the structural modifier oxides (BaO and ZnO) and the ionic size, and field strength of the modifying cations (Ba 2+, Zn 2+). Increased amounts of BaO decreased both glass transition temperature and crystallization temperature, while increasing the relative dielectric constant. Sintering occurred before crystallization for glasses where substitution of BaO for ZnO was up to 30 mol%, but for higher substitution levels, crystallization occurred during the sintering process hindering densification. © 2012 The American Ceramic Society.

This study deals with SiO2-P2O5 powders obtained by sol-gel process, starting from tetraethoxysilane (TEOS) as precursor for SiO2 and either triethylphosphate (TEP) or phosphoric acid (H3PO4) as precursors for P2O5. In the case of samples prepared with H3PO4, TG-DTA data showed an accentuated weight loss associated to an endothermic effect up to about 140 °C, specific for the evaporation of water and ethylic alcohol from structural pores, and also due to alkyl-amines evaporation. Sol-gel samples prepared with TEP exhibited different thermal effects, depending on the type of atmosphere used in the experiments, i.e. argon or air. XRD analysis revealed that annealed sol-gel samples prepared with H3PO4 showed specific peaks for silicophosphate compounds such as Si3(PO4)4, Si2P2O9, and SiP2O7. XRD results for annealed sol-gel samples prepared with TEP indicated mainly the presence of a vitreous (amorphous) phase, which could be correlated with SEM images. The presence of SiO2 in the sample might be expected. Thus, we have searched for any SiO2 polymorph possible to crystallize. Only potential peaks of cristobalite were identified but some of them are overlapping with peaks of other crystalline phosphates. SEM analysis indicated a decrease of the amount of crystalline phases with the increase in the annealing temperature. © 2009 Elsevier B.V. All rights reserved.

The thermoreactivity of a zinc acetate non-alkoxide solution used for the preparation of ZnO-based thin films was investigated in the temperature range 20-600°C by TG-DTA, XRD and SEM data. We found that the formation in air of ZnO crystallites from the sol-gel precursor occurs above 150°C simultaneously with the decomposition of an intermediary compound, most probably carbonate hydroxide (sciante and/or hydrozincite). At 200°C, the crystalline structure is well defined in terms of ZnO hexagonal lattice parameters, although residual organic compounds and water were not yet fully removed and an amorphous phase coexists. A kinetic investigation on the thermal decomposition of sol-gel precursor from DTA data using Kissinger differential equation is also presented. Apparent activation energy values of about. 100 kJ mol-1 corresponding to the non-isothermal decomposition of solid precursors in the temperature range 170-250°C have been found.

Transparent and conductive high preferential c-axis oriented ZnO thin films doped with Al have been prepared by sol-gel method using zinc acetate and aluminium chloride as cations source, 2-methoxiethanol as solvent and monoethanolamine as sol stabilizer. Film deposition was performed by dip-coating technique at a withdrawal rate of 1.5 cm min-1 on Corning 1737 glass substrate. The effect of dopant concentration, heating treatment and annealing in reducing atmosphere on the microstructure as well as on the electrical and optical properties of the thin films is discussed. The optical transmittance spectra of the films showed a very good transmittance, between 85 and 95%, within the visible wavelength region. The minimum resistivity of 1.3 × 10-3 Ω cm was obtained for the film doped with 2 wt.% Al, preheated at 400 °C and post-heated at 600 °C, after annealing under a reduced atmosphere of forming gas. © 2003 Elsevier B.V. All rights reserved.

This paper presents preliminary results on Al doped ZnO thin films prepared by the solgel method. The thin films were produced by a dip-coater technique on glass substrate, using zinc acetate dihydrate, aluminium chloride hexahydrate, 2-methoxyethanol and monoethanolamine as raw materials. The ZnO thin films were analysed by XRD, Hall effect and SEM measurements. In order to determine the influence of the thermal treatments on the film properties, a set of four different heat treatments (atmosphere and temperature) were studied. All the films are polycrystalline presenting a crystallographic c-axis orientation (002) perpendicular to the substrate. The best results were obtained for films pre-heated at 400°C and post-heated for 1 hour in air at 600°C, after annealing under a reduced atmosphere of forming gas, where a resistivity of 3.9×10-3 Ωcm, a Hall mobility of 34.1 cm2/Vs, a carrier concentration of 4.7×1019 cm-3 and an optical transmittance of 90% were achieved.

Hall effect measurements are one of the most powerful techniques for obtaining information about the conduction mechanism in polycrystalline semiconductor materials, which is the basis for understanding semiconductor gas sensors. In order to investigate the correlation between the microscopic characteristics and the macroscopic performances exhibited by undoped tin oxide gas sensors deposited by spray pyrolysis, Hall effect measurements were performed at different temperatures, from room temperature up to 500 K, and in the presence of two different atmospheres, air and methane. From these measurements, it was possible to infer the potential barrier and its dependence with the used atmosphere. The obtained results were analysed in terms of the oxygen mechanism at grain boundaries on the basis of the grain boundary-trapping model. In the presence of methane gas, the electrical resistivity decreases due to the lowering of the inter-grain boundary barrier height.