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2017
Kullberg, A. T. G., A. A. S. Lopes, J. P. B. Veiga, and R. C. C. Monteiro. "Crystal growth in zinc borosilicate glasses." Journal of Crystal Growth. 457 (2017): 239-243. AbstractWebsite

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.

2016
Barbosa, A. R. J. a, A. A. S. a Lopes, S. I. H. a Sequeira, J. P. a Oliveira, A. b Davarpanah, F. b Mohseni, V. S. b Amaral, and R. C. C. a Monteiro. "Effect of processing conditions on the properties of recycled cathode ray tube glass foams." Journal of Porous Materials. 23 (2016): 1663-1669. AbstractWebsite

Cathode ray tube glass waste was used to produce glass foams by a powder sintering route. The glass waste powder was mixed with small amounts (5 and 8 wt%) of coal fly ash, which acted as foaming agent, and the compacts of the mixed powders were heated at different sintering temperatures in the range 600–800 °C for various dwell times (30–120 min). The effect of the different processing conditions on the microstructural characteristics (porosity, pore size and pore size distribution), mechanical resistance and thermal conductivity of the produced foams was investigated. The volume of pores tended to increase with sintering temperature and time, and glass foams (with a porosity higher than 50 %) were only achieved after sintering at 750 °C. The average pore size increased with sintering temperature and dwell time, and pore growth was particularly accentuated at 800 °C, where coalescence of the pores occurred, with a consequent decrease in compressive strength. Selected combinations of the sintering temperature, dwell time and foaming agent led to glass foams with a satisfactory microstructural homogeneity, which exhibited mechanical strength and thermal conductivity values similar to commercial foams used as thermal insulating materials. © 2016, Springer Science+Business Media New York.

Kullberg, A. T. G., A. A. S. Lopes, J. P. B. Veiga, M. M. R. A. Lima, and R. C. C. Monteiro. "Formation and crystallization of zinc borosilicate glasses: Influence of the ZnO/B2O3 ratio." Journal of Non-Crystalline Solids. 441 (2016): 79-85. AbstractWebsite

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.

2015
Nico, C. a, R. a Fernandes, M. P. F. a Graça, M. a Elisa, B. A. b Sava, R. C. C. c Monteiro, L. a Rino, and T. a Monteiro. "Erratum: Eu3+ luminescence in aluminophosphate glasses (Journal of Luminescence (2014) 145 (582-587))." Journal of Luminescence. 161 (2015): 465. AbstractWebsite
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Barbosa, A. R. a, A. a Lopes, R. a Monteiro, and F. b Castro. "Use of different inorganic solid wastes to produce glass foams." Wastes: Solutions, Treatments and Opportunities - Selected Papers from the 3rd Edition of the International Conference on Wastes: Solutions, Treatments and Opportunities, 2015. 2015. 25-30. Abstract

Cathode Ray Tube (CRT) waste glasses produced from dismantling TV sets were used to prepare glass foams by a simple and economic processing route, consisting of a direct sintering process of mixtures of CRT waste as glass powder with different foaming agents (coal fly ash and limestone quarrying residues). The influence of firing temperature, amount and type of foaming agent on the apparent density, pore size distribution and compressive strength have been studied. The aim of the work was to investigate the possibility to obtain glass foams using exclusively wastes as starting materials, and therefore replacing the conventional raw materials. © 2015 Taylor & Francis Group, London.

2014
Soares, R. S. a, R. C. C. a Monteiro, A. A. S. a Lopes, M. M. R. A. a Lima, B. A. b Sava, and M. b Elisa. "Crystallization and microstructure of Eu3 +-doped lithium aluminophosphate glass." Journal of Non-Crystalline Solids. 403 (2014): 9-17. AbstractWebsite

A transparent Eu3 +-doped lithium aluminophosphate glass was prepared by melt-quenching technique. The thermal behavior of the glass was investigated by differential thermal analysis (DTA), the structure was studied by X-ray diffraction (XRD) and the morphology was observed by optical polarization microscopy and scanning electron microscopy (SEM). The activation energy of glass transition and the activation energy of crystallization and Avrami exponent have been evaluated under non-isothermal conditions from the data obtained by DTA at different heating rates. DTA curves exhibited an endothermic peak associated with the glass transition and two exothermic peaks. The mean value calculated for the activation energy of glass transition was 545 kJ mol- 1. The activation energy of crystallization was   400 kJ mol- 1 for the first exothermic peak and   170 kJ mol- 1 for the second peak. The Avrami exponent was   1 for both peaks indicating surface crystallization. XRD results showed that the main crystalline phase, aluminum metaphosphate, Al(PO3)3, and aluminum phosphate, AlPO4, were formed together with lithium barium phosphate, Li 3Ba(PO3)7, during the first exothermic peak and together with barium pyrophosphate, Ba2P2O7, during the second peak. Morphological study of heat-treated glass samples revealed microstructural features that confirmed a surface crystallization process. © 2014 Elsevier B.V.

Lopes, A. A. S. a, R. C. C. a Monteiro, R. S. a Soares, M. M. R. A. a Lima, and M. H. V. b Fernandes. "Crystallization kinetics of a barium-zinc borosilicate glass by a non-isothermal method." Journal of Alloys and Compounds. 591 (2014): 268-274. AbstractWebsite

The crystallization kinetics of a glass with a molar composition 40BaO-20ZnO-30B2O3-10SiO2 was investigated. The kinetic parameters, activation energy for crystallization (Ec) and Avrami exponent (n), were evaluated under non-isothermal conditions using the results obtained by differential thermal analysis (DTA) performed at different heating rates. DTA curves exhibited two overlapping exothermic peaks associated with the crystallization of the glass. Barium borate (BaB4O 7) was the first crystalline phase to be formed and it was followed by the formation of barium zinc silicate (BaZnSiO4), as identified by XRD. For the first exothermic peak, when the fraction of crystallization (χ) increased from 0.1 to 0.9, the local activation energy (E c(χ)) decreased from 700 to 500 kJ/mol, while for the second exothermic peak, Ec(χ) slightly increased from 490 to 570 kJ/mol. For the range of 0.1 < χ < 0.9, the local Avrami exponent (n(χ)) increased from ∼1 to 1.4 for the first exothermic peak and it decreased from ∼1.7 to 1.4 for the second exothermic peak. Observation by SEM of the microstructure of sintered glass samples revealed that crystallization started at the surface of glass particles, with growth of lamellar crystallites, that together with some quasi-spherical nano-sized crystallites progressed towards the inside of the glass at the highest sintering temperatures. The change of the local activation energy with the fraction of crystallization suggested that a multi-step kinetic reaction took place during sintering and crystallization of the glass. © 2013 Elsevier B.V. All rights reserved.

Soares, R. S., R. C. C. Monteiro, M. M. R. A. Lima, and R. J. C. Silva. "Crystallization of lithium disilicate-based multicomponent glasses - Effect of silica/lithia ratio." Ceramics International. 41 (2014): 317-324. AbstractWebsite

Two glass compositions were prepared from the system SiO2-Li2O-K2O-ZrO2-P2O5 with different SiO2/Li2O ratio (2.39 and 3.39) and the crystallization behavior was investigated by differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The crystallization kinetic parameters (activation energy of crystallization and Avrami exponent) were evaluated by different methods from the data obtained by DTA performed at different heating rates. For both glasses, two exothermic peaks were observed in the DTA curves, and the crystallization peak temperatures increased with SiO2/Li2O ratio. XRD analysis revealed that the first peak corresponds to the crystallization of lithium metasilicate (Li2SiO3) and the second to the formation of lithium disilicate (Li2Si2O5). After heating the glasses at a temperature above the second crystallization peak (900 °C), both Li2Si2O5 and Li2SiO3 were found in samples having the lowest SiO2/Li2O ratio, whereas no Li2SiO3 was detected in samples with the highest SiO2/Li2O ratio. For both glasses, the value obtained by different methods for the activation energy of crystallization was in the range of 225-275 kJ mol-1 for the first exothermic peak and in the range of 425-500 kJ mol-1 for the second peak. The estimated Avrami exponent was close to 1 for the first exothermic peak, indicating surface crystallization, and close to 3 for the second exothermic peak, suggesting volume crystallization. This was confirmed by the morphological study made by SEM that showed needle-like crystals in the microstructure of samples with lithium metasilicate and granular crystals in the microstructure of samples having lithium disilicate. © 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Nico, C. a, R. a Fernandes, M. P. F. a Graça, M. b Elisa, B. A. b Sava, R. C. C. c Monteiro, L. a Rino, and T. a Monteiro. "Eu3+ luminescence in aluminophosphate glasses." Journal of Luminescence. 145 (2014): 582-587. AbstractWebsite

With a 4f6 electronic configuration, europium ions in the trivalent charge state are known to be efficient activators in wide band gap matrices. Embedded in the aluminophosphate (Li2O-BaO-Al 2O3-La2O3-P2O 5) glasses the optically activated Eu3+ ions lead to intense room temperature orange/red luminescence with 16-23 Cd/m2 by using ultraviolet pumping. The as-prepared and heat treated europium doped glasses for temperatures below and above Tg were studied by room temperature Raman spectroscopy, absorption, photoluminescence excitation, temperature dependent and time dependent photoluminescence. When the samples are excited by 325 nm wavelength photons, an enhancement of the red luminescence intensity by ca. one order of magnitude was found to occur for temperatures between 14 K and 350 K, for all the doped glasses. On the other hand, by using resonant excitation on the 5L6 Eu3+ excited state (λexc 390 nm) the ion emission intensity was found to be nearly constant for temperatures up to 500 K. For higher temperatures a steeper decrease of the luminescence intensity occurs due to non-radiative competitive channels described by activation energies of ca. 235 meV and 450 meV by using 325 and 390 nm wavelength photons as excitation, respectively. The lifetime of the 5D0 level in these glasses is ca. 2.93 ms. A discussion of the thermal population and de-excitation mechanisms is performed. © 2013 Elsevier B.V.

Lopes, A. A. S., R. S. Soares, M. M. A. Lima, and R. C. C. Monteiro. "Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method." Journal of Applied Physics. 115 (2014). AbstractWebsite

The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B2O3-10SiO2were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (Tg) and of the maximum crystallization temperature (Tp) on the heating rate was used to determine the activation energy associated with the glass transition (Eg), the activation energy for crystallization (Ec), and the Avrami exponent (n). X-ray diffraction (XRD) revealed that barium borate (β-BaB2O4) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba5Si8O21). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (Ec(χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures. © 2014 AIP Publishing LLC.

Soares, R. S. a, R. C. C. a Monteiro, M. M. R. A. a Lima, B. A. b Sava, and M. b Elisa. "Phase transformation and microstructural evolution after heat treatment of a terbium-doped lithium-aluminum phosphate glass." Journal of Materials Science. 49 (2014): 4601-4611. AbstractWebsite

The crystallization kinetics and phase transformation of a transparent Tb3+-doped lithium-aluminum phosphate glass, prepared by melt quenching, were investigated. The energy associated to the glass transition and the crystallization parameters (activation energy for crystallization and Avrami exponent) were evaluated by different methods using the experimental data obtained by differential thermal analysis performed at different heating rates. Using an isoconversional method to determine the change of the activation energy for crystallization with the fraction of crystallization, it was verified that with the increase in the fraction of crystallization from 0.1 to 0.9, the value of the activation energy decreased slightly from  370 to  310 kJ mol -1 and that the Avrami exponent varied from 0.8 to 1, suggesting a surface crystal growth mechanism. Observation of the microstructural evolution of heat-treated glass samples confirmed a surface crystallization process revealing spherulitic crystals constituted mainly by aluminum metaphosphate. © 2014 Springer Science+Business Media New York.

2013
Lima, M. M. R. A., L. F. C. Braz, R. C. C. Monteiro, and JP Veiga. "Effect of phosphogypsum on the clinkerization temperature of portland cement clincker." Materials Science Forum. 730-732 (2013): 94-99. AbstractWebsite

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.

Nico, C. a, M. P. F. a Graça, M. b Elisa, B. A. b Sava, R. C. C. c Monteiro, L. a Rino, and T. a Monteiro. "Effects of ultraviolet excitation on the spectroscopic properties of Sm3+ and Tb3+ doped aluminophosphate glasses." Optical Materials. 35 (2013): 2382-2388. AbstractWebsite

Li2O-BaO-Al2O3-La2O 3-P2O5 glasses optically activated with rare earth ions with the 4f5, and 4f8 electronic configuration (Sm3+ and Tb3+, respectively) were analyzed by Raman spectroscopy, absorption, excitation photoluminescence, decay curves and temperature dependent photoluminescence. The spectroscopic characteristics of the as-prepared and heat treated samples at temperatures below and above T g were studied as well as their room temperature photometric properties under ultraviolet excitation. All the doped glasses exhibit typical signatures of the lanthanides in their trivalent charge state. For the samarium doped glass heat treated at 250 C (<Tg) the Sm2+ luminescence was also observed. The analysis of the luminescence efficiency was performed in the interval range of 14 K to room temperature, where the integrated intensity of the luminescence was found to decrease for the Sm 3+ and Tb3+ ions in the studied temperature range. Luminescence decay curves were found to be non-exponential for the 4G5/2 → 6H7/2 and 5D3 → 7F4 transitions of the Sm3+ and Tb3+ ions, respectively. The results strongly suggest the occurrence of energy transfer processes through cross relaxation phenomena, mediated by dipole-dipole interaction in all the studied samples. The decay of the 5D4 → 7F5 emission of the Tb3+ ions was found to be single exponential with a time constant of ∼3.1 ms. Based on the spectroscopic characteristics, models for recombination processes are proposed. The room temperature luminance photometric properties with ultraviolet excitation show that the samarium doped glasses have much lower luminance intensity (around 0.3 Cd/m2) when compared with the 6-7 Cd/m2 observed for the terbium doped ones. © 2013 Elsevier B.V. All rights reserved.

Elisa, M. a, B. A. a Sava, I. C. a Vasiliu, R. C. C. b Monteiro, C. R. a Iordanescu, I. D. a Feraru, L. a Ghervase, C. c Tanaselia, M. c Senila, and B. c Abraham. "Investigations on optical, structural and thermal properties of phosphate glasses containing terbium ions." IOP Conference Series: Materials Science and Engineering. Vol. 47. 2013. Abstract

{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

Elisa, M. a, B. A. a Sava, I. C. a Vasiliu, R. C. C. b Monteiro, J. P. B. Veiga, L. a Ghervase, I. a Feraru, and R. a Iordanescu. "Optical and structural characterization of samarium and europium-doped phosphate glasses." Journal of Non-Crystalline Solids. 369 (2013): 55-60. AbstractWebsite

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.

Sava, B. A. a, M. a Elisa, L. b Boroica, and R. C. C. c Monteiro. "Preparation method and thermal properties of samarium and europium-doped alumino-phosphate glasses." Materials Science and Engineering B: Solid-State Materials for Advanced Technology. 178 (2013): 1429-1435. AbstractWebsite

The present work investigates alumino-phosphate glasses from Li 2O-BaO-Al2O3-La2O3-P 2O5 system containing Sm3+ and Eu3+ ions, prepared by two different ways: a wet raw materials mixing route followed by evaporation and melt-quenching, and by remelting of shards. The linear thermal expansion coefficient measured by dilatometry is identical for both rare-earth-doped phosphate glasses. Comparatively to undoped phosphate glass the linear thermal expansion coefficient increases with 2 × 10-7 K-1 when dopants are added. The characteristic temperatures very slowly decrease but can be considered constant with atomic weight, atomic number and f electrons number of the doping ions in the case of Tg (vitreous transition temperature) and Tsr (high annealing temperature) but slowly increase in the case of Tir (low annealing temperature-strain point) and very slowly increase, being practically constant in the case of TD (dilatometric softening temperature). Comparatively to undoped phosphate glass the characteristic temperatures of Sm and Eu-doped glasses present lower values. The higher values of electrical conductance for both doped glasses, comparatively to usual soda-lime-silicate glass, indicate a slightly reduced stability against water. The viscosity measurements, showed a quasi-linear variation with temperature the mean square deviation (R 2) being ranged between 0.872% and 0.996%. The viscosity of doped glasses comparatively to the undoped one is lower at the same temperature. Thermogravimetric analysis did not show notable mass change for any of doped samples. DSC curves for both rare-earth-doped phosphate glasses, as bulk and powdered samples, showed Tg values in the range 435-450 C. Bulk samples exhibited a very weak exothermic peak at about 685 C, while powdered samples showed two weak exothermic peaks at about 555 C and 685 C due to devitrification of the glasses. Using designed melting and annealing programs, the doped glasses were improved regarding bubbles and cords content and strain elimination. © 2013 Elsevier B.V. All rights reserved.

2012
PerdigãO, J. a, A. M. b Pinto, R. C. C. c Monteiro, F. M. c Braz Fernandes, P. b Laranjeira, and J. P. c Veiga. "Degradation of dental ZrO 2-based materials after hydrothermal fatigue. part I: XRD, XRF, and FESEM analyses." Dental Materials Journal. 31 (2012): 256-265. AbstractWebsite

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.

Monteiro, R. C. C. a, A. A. S. a Lopes, M. M. A. a Lima, J. P. a Veiga, R. J. C. a Silva, C. J. a Dias, E. J. R. b Davim, and M. H. V. b Fernandes. "Sintering, crystallization, and dielectric behavior of barium zinc borosilicate glasses-Effect of barium oxide substitution for zinc oxide." Journal of the American Ceramic Society. 95 (2012): 3144-3150. AbstractWebsite

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.

Lima, M. M. R. A. a, R. C. C. a Monteiro, M. P. F. b Graça, and M. G. c Ferreira Da Silva. "Structural, electrical and thermal properties of borosilicate glass-alumina composites." Journal of Alloys and Compounds. 538 (2012): 66-72. AbstractWebsite

Borosilicate glass-alumina composites with (1 - x) Glass + x Al 2O 3 (x = 0, 5, 10, 25 vol.%) were prepared and the effect of Al 2O 3 addition on the structural, electrical and thermal characteristics was investigated. XRD patterns revealed the presence of cristobalite (SiO 2) in sintered borosilicate glass and that the addition of Al 2O 3 hinders cristobalite formation. This behavior is due to the diffusion of some Al 3+ ions from alumina to glass, which leads to changes in glass structure and composition as identified by SEM/EDS. Cristobalite was undetected in composites containing 10% Al 2O 3 that attained the lowest thermal expansion coefficient value (∼4.6 × 10 -6 °C -1). Conductivity (dc and ac) increased with the amount of Al 3+ ions present in the glass structure as modifiers and formers. Dielectric constant values, in the range 5.0-7.2, increased with Al 2O 3 addition and the values of loss tan δ (1.5-2.1 × 10 -2) indicate that these materials are good insulators. © 2012 Elsevier B.V. All rights reserved.

2010
Ribeiro, A. S. M. a, R. C. C. b Monteiro, E. J. R. a Davim, and M. H. V. a Fernandes. "Ash from a pulp mill boiler-Characterisation and vitrification." Journal of Hazardous Materials. 179 (2010): 303-308. AbstractWebsite

The physical, chemical and mineralogical characterisation of the ash resulting from a pulp mill boiler was performed in order to investigate the valorisation of this waste material through the production of added-value glassy materials. The ash had a particle size distribution in the range 0.06-53μm, and a high amount of SiO2 (∼82wt%), which was present as quartz. To favour the vitrification of the ash and to obtain a melt with an adequate viscosity to cast into a mould, different amounts of Na2O were added to act as fluxing agent. A batch with 80wt% waste load melted at 1350°C resulting in a homogeneous transparent green-coloured glass with good workability. The characterisation of the produced glass by differential thermal analysis and dilatometry showed that this glass presents a stable thermal behaviour. Standard leaching tests revealed that the concentration of heavy metals in the leaching solution was lower than those allowed by the Normative. As a conclusion, by vitrification of batch compositions with adequate waste load and additive content it is possible to produce an ash-based glass that may be used in similar applications as a conventional silicate glass inclusively as a building ecomaterial. © 2010 Elsevier B.V.

Elisa, M. a, B. A. b Sava, A. c Volceanov, R. C. C. d Monteiro, E. e Alves, N. e Franco, F. A. f Costa Oliveira, H. g Fernandes, and M. C. g Ferro. "Structural and thermal characterization of SiO2-P2O5 sol-gel powders upon annealing at high temperatures." Journal of Non-Crystalline Solids. 356 (2010): 495-501. AbstractWebsite

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.

Drasovean, R. a, R. b Monteiro, and M. c Cherif. "Structure and morphology study of cobalt oxide doped silica nanocomposite films." AIP Conference Proceedings. Vol. 1203. 2010. 483-488. Abstract

Cobalt oxide doped silica films were synthesized by a dip-coating technique. Initial compounds were cobalt acetate Co(CH3COO)2-4H 2O and tetraethoxysilane Si(OC2H5)4. The chemical composition was studied by X-ray diffraction and UV-Vis spectroscopy. The morphology analyses were carried out by means of atomic force microscopy. The average diameter of cobalt oxide dispersed particles increases with the molar ratio Co:Si and with the aging time of the initial colloidal solution. © 2009 American Institute of Physics.

2008
Monteiro, R. C. C. a, C. F. a Figueiredo, M. S. a Alendouro, M. C. b Ferro, E. J. R. b Davim, and M. H. V. b Fernandes. "Characterization of MSWI bottom ashes towards utilization as glass raw material." Waste Management. 28 (2008): 1119-1125. AbstractWebsite

The characterization of the bottom ashes produced by two Portuguese municipal solid waste incinerators (MSWI) was performed with the aim of assessing the feasibility of using this waste as raw material in the production of glass that can be further processed as glass-ceramics for application in construction. Density and particle size distribution measurements were carried out for physical characterization. Chemical characterization revealed that SiO2, a network glass former oxide, was present in a relatively high content (52-58 wt%), indicating the suitability for this waste to be employed in the development of vitreous materials. CaO, Na2O and K2O, which act as fluxing agents, were present in various amounts (2-17 wt%) together with several other oxides normally present in ceramic and glass raw materials. Mineralogical characterization revealed that the main crystalline phases were quartz (SiO2) and calcite (CaCO3) and that minor amounts of different alkaline and alkaline-earth aluminosilicate phases were also present. Thermal characterization showed that the decomposition of the different compounds occurred up to 1100 °C and that total weight loss was <10 wt%. Heating both bottom ashes at 1400 °C for 2 h resulted in a melt with suitable viscosity to be poured into a mould, and homogeneous black-coloured glasses with a smooth shiny surface were obtained after cooling. The vitrified bottom ashes were totally amorphous as confirmed by X-ray diffraction. The results from the present experimental work indicate that the examined bottom ashes can be a potential material to melt and to obtain a glass that can be further processed as glass-ceramics to be applied in construction. © 2007 Elsevier Ltd. All rights reserved.

Monteiro, R. C. C., M. M. R. A. Lima, and C. S. Clemente. "Development of structural ceramics from fly ash and shale." Materials Science Forum. 587-588 (2008): 787-791. AbstractWebsite

The possibility of using fly ash and shale as alternative raw materials for the production of structural ceramics was investigated. Fly ash is a by-product from coal-burning power plants, and shale is a sedimentary rock that if ground finely enough can exhibit a clay-like plasticity. Ceramic samples containing 10-50 wt% fly ash were formed from mechanical mixing of both kinds of powders that were packed and sintered in the temperature range 950-1200°C It was verified that powders with larger fly ash content exhibited lower packing density resulting in compacts with a lower sintered density. Although an increase in fly ash content was associated to a larger presence of porosity in the sintered samples, as confirmed by microstructural analysis, all studied compositions when sintered at the highest temperatures exhibited satisfactory values for water absorption (< 10%), for flexural strength (20-64 MPa) and for hardness (20-30 GPa) indicating that they have potential to be applied in the production of structural ceramics.

Monteiro, R. C. C., M. M. R. A. Lima, and S. Alves. "Mechanical characteristics of clay structural ceramics containing coal fly ash." International Journal of Mechanics and Materials in Design. 4 (2008): 213-220. AbstractWebsite

In this work, the mechanical characterization of ceramic products processed from red clay with different amounts of added coal fly ash was investigated. Coal fly ash produced by power plants is a waste material that constitutes an alternative source of minerals for the production of traditional building ceramics, as it is a complex mixture of several oxides such as SiO2, Al2O3, CaO, Fe2O3, Na2O, TiO2, which are usually present in the composition of such ceramics. A powder technology and firing route was followed for the processing of the clay and coal fly ash based ceramics. Different proportions of waste (10, 25 and 50%, by weight) were added to red clay, and then the mixed powders were pressed to form compacts that were fired at a selected temperature in the range 850-1,150°C. The effects of waste content and of heating conditions on the microstructure and mechanical characteristics of the obtained materials were investigated. The density, porosity, water absorption, flexural strength, hardness and fracture toughness of the produced materials were evaluated. A comparison was made between the properties of the produced ceramics with those of traditional ceramic materials used in construction, e.g. floor or wall tiles, and it was observed that the clay based products with coal fly ash additions may be used in similar applications. © 2007 Springer Science+Business Media B.V.