Characterization of crystal phases,morphology and crystallization processes in lithium aluminosilicate glass-ceramic

The nucleation and crystallization processes of Li₂O-Al₂O₃-SiO₂ glass-ceramics were investigated by differential thermal analysis. The crystalline phases produced during thermal treatment at different temperatures and the residual glassy phase were characterized by X-ray diffraction, SEM and image analysis techniques. The activation energy of the crystallization process was calculated as E=380±20 kJ mol^–1. The influence of nucleating agents (TiO₂, ZrO₂) was evaluated to obtain glass-ceramics transparent to visible light. The stability of the glassy phase in cooling was determined by means of temperature-time-transformation curves.     

Influence of Fe3+/Fe2+ Ratio on the Crystallization of Iron-Rich Glasses Made with Industrial Wastes

The influence of the Fe³⁺/Fe²⁺ ratio on the crystallization of iron-rich glasses was investigated in this study. The glass batches were made from two hazardous industrial wastes: mud (goethite and jarosite) originating from the zinc hydrometallurgical process and electric arc furnace dust (EAFD). Glass compositions were prepared by adding different percentages of carbon powder. The crystallization process was investigated by a combined thermogravimetry/differential thermal analysis technique, in air or nitrogen atmospheres, using powder and bulk glass samples. The crystalline phases formed, i.e., pyroxene and spinels, and their relative ratio were determined by X-ray diffractometry. The experimental results indicated that melting temperature and crystallization behavior were influenced by the initial Fe³⁺/Fe²⁺ ratio and by the amount of carbon added to the glass batch. For goethite and jarosite glass compositions, decreasing the Fe³⁺/Fe²⁺ ratio increased the crystallization rate by favoring magnetite formation. For EAFD glass compositions, the addition of carbon to the batch inhibited chromite–magnetite spinel formation and favored the attainment of an amorphous glassy phase.     

Crystallization of glasses obtained by recycling goethite industrial wastes to produce glass-ceramic materials

Goethite waste, originated in the hydrometallurgy of zinc, was characterized and recycled, in combination with raw materials, for producing glass-ceramic (GC) materials. Four base compositions were prepared with an Fe₂O₃ content ranging from 15 to 25 wt%. The mixtures were melted at 1400–1450 °C and quenched to obtain the glass. The nucleation and crystallization temperatures and the activation energy of the crystallization process were determined by differential thermal analysis. The glass samples were nucleated at 660 °C for times ranging from 1 to 4 h and crystallized at 800–900 °C for 1 to 4 h. X-ray diffraction and fluorescence analysis were performed on the glasses and GC samples and the crystalline phases characterized. The percentage of crystallinity was determined as a function of the temperature and duration of the thermal treatment. The fractional factorial experimental approach was carried out on the 20 wt% Fe₂O₃ composition with the aim of evaluating the influence of the nucleation temperature and time, the crystallization temperature and time and the presence of a reducing agent on the glass devitrification process.     

Preparation and characterization of bulk ZnGa2O4

High-quality bulk ZnGa₂O₄ has been synthesized from equimolar mixtures of ZnO and Ga₂O₃ by the conventional solid-state method. For the first time, the sample has been characterized in detail to confirm the formation of pure single phase of spinel ZnGa₂O₄. The formation of ZnGa₂O₄ has been confirmed by sintering the mixtures of ZnO and Ga₂O₃ at different temperatures, ranging from 900–1200 °C. It is observed that the single phase of ZnGa₂O₄ has been formed at and above 1000 °C sintering temperature for 24 h. The crystallinity and phase formation of this single phase has been confirmed by X-ray diffraction. X-ray photoelectron spectroscopic studies have been carried out for bulk ZnGa₂O₄ sintered at 1000 °C for 24 h which showed 14% Zn, 28% Ga and 58% O, indicating stoichiometric ZnGa₂O₄. A new parameter, the energetic separation between the Zn 2p_3/2 and Ga 2p_3/2 peaks, has been used as a sensitive tool to distinguish between a complete formation of ZnGa₂O₄ compound and a mixture of ZnO and Ga₂O₃ powders. Surface morphology studies by scanning electron microscopy reveal that the formation of ZnGa₂O₄ takes place in mosaic rod-like structure. The purity of the compound has also been checked by the energy dispersive X-ray method, indicating the absence of foreign ions and the ratio of zinc to gallium has been calculated and found to be 1 : 2, indicating stoichiometric ZnGa₂O₄.     

Investigation on the cross sensitivity of NO2 sensors based on In2O3 thin films prepared by sol-gel and vacuum thermal evaporation

In₂O₃ thin films have been prepared from commercially available pure In₂O₃ powders by high vacuum thermal evaporation (HVTE) and from indium iso-propoxide solutions by sol-gel techniques (SG). The films have been deposited on sapphire substrates provided with platinum interdigital sputtered electrodes. The as-deposited HVTE and SG films have been annealed at 500°C for 24 and 1 h, respectively. The film morphology, crystalline phase and chemical composition have been characterised by SEM, glancing angle XRD and XPS techniques. After annealing at 500°C the films’ microstructure turns from amorphous to crystalline with the development of highly crystalline cubic In₂O_3−x (JCPDS card 6-0416). XPS characterisation has revealed the formation of stoichiometric In₂O₃ (HVTE) and nearly stoichiometric In₂O_3−x (SG) after annealing. SEM characterisation has highlighted substantial morphological differences between the SG (highly porous microstructure) and HVTE (denser) films. All the films show the highest sensitivity to NO₂ gas (0.7–7 ppm concentration range), at 250°C working temperature. At this temperature and 0.7 ppm NO₂ the calculated sensitivities (S=R_g/R_a) yield S=10 and S=7 for SG and HVTE, respectively. No cross sensitivity have been found by exposing the In₂O₃ films to CO and CH₄. Negligible H₂O cross has resulted in the 40–80% relative humidity range, as well as to 1 ppm Cl₂ and 10 ppm NO. Only 1000 ppm C₂H₅OH has resulted to have a significant cross to the NO₂ response.     

Microstructure and Humidity-Sensitive Characteristics of α-Fe2O3 Ceramic Sensor

The microstructure and humidity-sensitive characteristics of α -Fe₂O₃ porous ceramic were investigated. Microporous α -Fe₂O₃ powders were obtained by controlling the topotactic decomposition reaction of α -FeOOH. Water vapor adsorption thermogravimetrical experiments were carried out in the relative humidity (rh) range 0% to 95% on the α -Fe₂O₃ powder and the 900°C sintered compact. The microstructure was investigated by SEM, TEM, Hg intrusion, and N₂ adsorption porosimetry techniques. The humidity sensitivity was investigated by the impedance measurements technique in 0% to 95% rh on the compacts sintered at 50°C steps in the 850° to 1100°C range. Humidity response was found to be affected by the microstructure, i.e., the characteristics of the precursor powders and sintering temperatures.     

The comparative effect of two different annealing temperatures and times on the sensitivity and long-term stability of WO/sub 3/ thin films for detecting NO/sub 2/

We have deposited 150-nm-thick WO/sub 3/ films on Si/sub 3/N/sub 4//Si substrates provided with platinum interdigital electrodes and annealed in static air at 300/spl deg/C and 500/spl deg/C temperatures for 24 h and 200 h. The morphology, crystalline phase, and chemical composition of the films have been characterized using AFM, grazing incidence XRD and high resolution XPS techniques. The sensor resistance response curve has been obtained in the 0.2 -4 ppm NO/sub 2/ gas concentration range in humid air (50% relative humidity), varying the operating temperature between 25 and 250/spl deg/C. By plotting both sensor resistance and gas concentration logarithmically, the response is linear over the investigated dynamic range. Sensor sensitivities, here defined as the ratio of sensor resistance in gas to that in air (i.e., S=R/sub Gas//R/sub Air/), have been compared at a given NO/sub 2/ gas concentration (0.2 ppm). The long-term stability properties have been evaluated by recording film sensitivity for 1 yr under standardized test conditions. Increasing the annealing temperature from 300 to 500/spl deg/C causes the sensitivities to decrease. The 300/24h film is shown to be the most sensitive at S=233, but with poor long-term stability properties. The 300/200h film with S=32 is stable over the examined period. The 500/24 and the 500/200 films are shown to be less sensitive with S=16 and S=14, respectively. The longer the annealing time and the higher the temperature, the poorer the sensitivity, but with positive effects upon the long-term stability of the electrical response. The influence of the annealing conditions on sensitivity and long-term stability has been correlated with the concentration of surface defects, like reduced WO/sub 3/ phase (i.e., W/sup 4+/), which resulted in a strong effect on the sensors' response.     

Study of the kinetics of decomposition of goethitein vacuo and pore structure of product particles

The kinetics of decomposition of-goethite were investigated, under vacuum conditions, in the temperature range 170–250° C. The experimental thermogravimetric traces were interpreted according to the shrinking core model for cylindrical particles. The Arrhenius plot of InK (kinetic constant) against 1/T yielded an activation energy of 119±9 kJ mol^–1 at 210° C. The highest specific area,S _BET=118.4±5.5 m² g^–1, of the reaction product-hematite, was obtained by decompsition at 225° C. Information about the formation of micropores and their evolution with temperature was also obtained.