Estudo de massa cerâmica triaxial visando à otimização do ciclo de queima da indústria de cerâmica estrutural

Over recent years the structural ceramics industry in Brazil has found a very favorable market for growth. However, difficulties related to productivity and product quality are partially inhibiting this possible growth. An alternative for trying to solve these problems and, thus, provide the pottery industry the feasibility of full development, is the substitution of firewood used in the burning process by natural gas. In order to contribute to this process of technological innovation, this paper studies the effect of co-use of ceramic phyllite and kaolin waste on the properties of a clay matrix, verifying the possible benefits that these raw materials can give to the final product, as well as the possibility of such materials to reduce the heat load necessary to obtain products with equal or superior quality. The study was divided into two steps: characterization of materials and study of formulations. Two clays, a phyllite and a residue of kaolin were characterized by the following techniques: laser granulometry, plasticity index by Atterberg limits, X-ray fluorescence, X-ray diffraction, mineralogical composition by Rietveld, thermogravimetric and differential thermal analysis. To study the formulations, specifically for evaluation of technological properties of the parts, was performed an experimental model that combined planning involving a mixture of three components (standard mass x phyllite x kaolin waste) and a 23 factorial design with central point associated with thermal processing parameters. The experiment was performed with restricted strip-plot randomization. In total, 13 compositional points were investigated within the following constraints: phyllite ≤ 20% by weight, kaolin waste ≤ 40% by weight, and standard mass ≥ 60% by weight. The thermal parameters were used at the following levels: 750 and 950 °C to the firing temperature, 5 and 15 °C/min at the heating rate, 15 and 45min to the baseline. The results showed that the introduction of phyllite and/or kaolin waste in ceramic body produced a number of benefits in properties of the final product, such as: decreased absorption of water, apparent porosity and linear retraction at burn; besides the increase in apparent specific mass and mechanical properties of parts. The best results were obtained in the compositional points where the sum of the levels of kaolin waste and phyllite was maximal (40% by weight), as well as conditions which were used in firing temperatures of 950 °C. Regarding the prospect of savings in heat energy required to form the desired microstructure, the phyllite and the residue of kaolin, for having small particle sizes and constitutions mineralogical phases with the presence of fluxes, contributed to the optimization of the firing cycle.

Estudo da adição de resíduo de scheelita em matriz cerâmica: formulação, propriedades físicas e microestrutura

Extractivism mineral is considered an activity highly degrading, due to the large volume of material that he moves in the form of ore and residues. The vast majority of mining companies do not show any technology or economically viable application that will allow the recycling of mineral residue, these being launched in areas receiving located the "open skies" degrade the environment. In Rio Grande do Norte to the production of ceramic red restricts their activities to the production of products such as: solid bricks, ceramic blocks, tiles, among others. Seeking to unite experiences and technical information that favor sustainable development, with important benefits to the construction sector and civil society in general, the present work studies the incorporation of the residue of scheelite in ceramic matrix kaolinitic, coming from the municipality of Boa Saúde - RN, in percentage of 5 %, 10 %, 20 %, 30% 40% and 50 %, by evaluating its microstructure, physical properties and formulation. The raw materials were characterized through the trials of X ray fluorescence, Diffraction of X rays, Differential Thermal Analysis and Termogravimetric Analysis. The samples were formed and fired at temperatures of 850o, 900o, 1000o, 1050o, 1100o, 1150o and 1200 oC, with isotherm of 1 hour and heating rate of 10 oC/min. Assays were performed technological of loss to fire, Water Absorption, Apparent Porosity, Apparent Density, Mass Loss in Fire and Bending Resistance; in addition to the Scanning Electron Microscopy, analyzing their physical and mechanical properties. The use of residue of scheelite in ceramic mass kaolinitic provided a final product with technological properties that meet the technical standards for the production of bricks and roofing tiles, with the percentage of 20% of waste that showed the best results

Efeito da velocidade de aquecimento nas propriedades de produtos da cerâmica estrutural

Heating rate is one of the main variables that determine a fire cycle. In industrial processes that use high temperatures, greater fire great can reduce the cost of production and increase productivity. The use of faster and more efficient fire cycles has been little investigated by the structural ceramic industry in Brazil. However, one of the possibilities that aims at modernizing the sector is the use of roller kilns and the inclusion of natural gas as fuel. Thus, the purpose of this study is to investigate the effect of heating rate on the technological properties of structural ceramic products. Clay raw materials from the main ceramic industries in the state of Rio Grande do Norte were characterized. Some of the raw materials characterized were formulated to obtain the best physical and mechanical properties. Next, raw materials and formulations were selected to study the influence of heating rate on the final properties of the ceramic materials. The samples were shaped by pressing and extrusion and submitted to rates of 1 °C/min, 10 °C/min and 20 °C/min, with final temperatures of 850 °C, 950 °C and 1050 °C. Discontinuous cycles with rates of 10 °C/min or 15 °C/min up to 600 °C and a rate of 20 °C/min up to final temperature were also investigated. Technological properties were determined for all the samples and microstructural analysis was carried out under a number of fire conditions. Results indicate that faster and more efficient fire cycles than those currently in practice could be used, limiting only some clay doughs to certain fire conditions. The best results were obtained for the samples submitted to slow cycles up to 600 °C and fast fire sinterization up to 950 °C. This paper presents for the first time the use of a fast fire rate for raw materials and clay formulations and seeks to determine ideal dough and processing conditions for using shorter fire times, thus enabling the use of roller kilns and natural gas in structural ceramic industries

Aplicação da metodologia de planejamento de experimentos para formulação de massas cerâmicas para telhas

Rio Grande do Norte State stands out as one great producer of structural clay of the brazilian northeastern. The Valley Assu ceramic tiles production stands out obtained from ilitics ball clays that abound in the region under study. Ceramics formulation and the design of experiments with mixture approach, has been applied for researchers, come as an important aid to decrease the number of experiments necessary to the optimization. In this context, the objective of this work is to evaluate the effects of the formulation, temperature and heating rate in the physical-mechanical properties of the red ceramic body used for roofing tile fabrication of the Valley Assu, using design of mixture experiments. Four clays samples used in two ceramics industry of the region were use as raw material and characterized by X-ray diffraction, chemical composition, differential thermal analysis (DTA), thermogravimetric analysis (TGA), particle size distribution analysis and plasticity techniques. Afterwards, they were defined initial molded bodies and made specimens were then prepared by uniaxial pressing at 25 MPa before firing at 850, 950 and 1050 ºC in a laboratory furnace, with heating rate in the proportions of 5, 10 e 15 ºC/min. The following tecnologicals properties were evaluated: linear firing shrinkage, water absorption and flexural strength. Results show that the temperature 1050 ºC and heating rate of 5 ºC/min was the best condition, therefore presented significance in all physical-mechanical properties. The model was accepted as valid based of the production of three new formulations with fractions mass diferents of the initial molded bodies and heated with temperature at 1050 ºC and heating rate of 5 ºC/min. Considering the formulation, temperature and heating rate as variables of the equations, another model was suggested, where from the aplication of design of experiments with mixtures was possible to get a best formulation, whose experimental error is the minor in relation to the too much formulations

The influence of rock fabric in the durability of two sandstones used in the Andalusian Architectural Heritage (Montoro and Ronda, Spain)

Natural stone has been a popular and reliable building material throughout history appearing in many historic monuments and in more recent buildings. Research into the intrinsic properties of specific stones is important because it gives us a greater understanding of the factors that limit and act on them. This can help prevent serious problems from occurring in our buildings bringing both esthetic benefits and financial savings. To this end, the main objective of this research has been to study the influence of the fabric and the mineral composition of two types of sandstone on their durability. The first is a red continental sandstone from the Buntsandstein Age called “Molinaza Roja”, which is quarried in Montoro (Cordoba). The second is quarried in Ronda (Malaga) and is sold under the trade name of “Arenisca Ronda”. It is a light pink-whitish calcarenite deposited during the Late Tortonian to Late Messinian. We characterized their petrological and petrophysical properties by studying their rock fabrics, porous systems and mechanical properties. In order to obtain a complete vision of the behavior of their rock fabrics, we also carried out two decay tests, the salt crystallization and the freeze–thaw tests. We then measured the effects on the textures of the altered samples during and after the decay tests and we evaluated the changes in the porous system. By comparing the results between intact and altered samples, we found that Arenisca Ronda is less durable because it has a high quantity of expandable clays (smectites) and a high percentage of pores in the 0.1–1 μm range, in which the pressure produced by salt crystallization is strongest. In Molinaza Roja the decay agents caused significant sanding due to loss of cohesion between the clasts, especially during the salt crystallization test. In both stones, the anisotropies (oriented textures) have an important role in their hydric and dynamic behavior and also affect their mechanical properties (especially in the compression resistance). No changes in color were detected.

Evolução diagenética e caracterização dos reservatórios da seção devoniana na Bacia do Rio do Peixe-Nordeste do Brasil

The Rio do Peixe Basin represents a main basin of northeastern Brazil and pioneering work positioned the rocks of this basin in the Early Cretaceous. However, a recent study, based on integrated pollen analysis from three wells, found an unprecedented siliciclastic sedimentary section, in the region, of early Devonian age. Therefore, the present study aims a detailed petrographic and petrological analysis of this devonian section, in the Rio do Peixe Basin and proposes a diagenetic evolution, to understand the characteristics of the porous system, identify the main reservoir petrofacies with the main factors impacting on the quality of these rocks as reservoirs and a quick study on the provenance of this section. The petrographic study was based on samples obtained from subsurface and surface. The diagenetic evolution of petrofacies and its identification were based only on subsurface samples and the study of provenance was based on surface samples. The thin sections were prepared from sandstones, pelites and sandstones intercalated with pelites. The original detrital composition for this section is arcosean and the main diagenetic processes that affected these rocks occur in various depths and different conditions, which resulted in extensive diagenetic variety. The following processes were identified: early fracture and healing of grains; albitization of K-feldspar and plagioclase; siderite; precipitation of silica and feldspar; mechanical infiltration of clay and its transformation to illite/esmectite and illite; autigenesis of analcime; dissolution; autigenesis of chlorite; dolomite/ferrous dolomite/anquerite; apatite; calcite; pyrite; titanium minerals and iron oxide-hidroxide. The occurrence of a recently discovered volcanism, in the Rio do Peixe Basin, may have influenced the diagenetic evolution of this section. Three diagenetic stages affected the Devonian section: eo, meso and telodiagenesis. This section is compositionally quite feldspathic, indicating provenance from continental blocks, between transitional continental and uplift of the basement. From this study, we observed a wide heterogeneity in the role of the studied sandstones as reservoirs. Seven petrofacies were identified, taking into account the main diagenetic constituent responsible for the reduction of porosity. It is possible that the loss of original porosity was influenced by intense diagenesis in these rocks, where the main constituent for the loss of porosity are clays minerals, oxides and carbonate cement (calcite and dolomite)

La datation du site Mailhot-Curran : application de la luminescence optique sur des poteries iroquoiennes du Saint-Laurent

La luminescence optique (OSL) a été mesurée sur dix-sept fragments de poterie collectés à Mailhot-Curran (BgFn-2), un site archéologique du Sylvicole supérieur tardif localisé dans le sud-ouest du Québec. Le but principal de ce projet était de dater ce site qui est considéré jusqu’à maintenant comme le plus récent site préhistorique de la concentration de Saint-Anicet, afin de poser un jalon dans la chronologie des sites de cette région. L’OSL a été utilisée conjointement à la datation par radiocarbone (14C) et la sériation du matériel archéologique. L’hypothèse archéologique propose que le village aurait été occupé pendant les années 1518 à 1530 de notre ère (Chapdelaine 2015a). Les résultats que nous proposons dans ce présent mémoire appuient cette proposition. Nous avons obtenu un âge de 490 ± 49 ans (année de référence : 2013), correspondant à l’année 1523 de notre ère avec une probabilité d’occupation du site Mailhot-Curran entre les années 1474 et 1572. Le programme de datation par luminescence optique a été réalisé sur des fragments de poterie domestique composés d’argile de la Mer de Champlain datant de la période du Quaternaire récent. La datation par stimulation infrarouge (IRSL) a été préférentiellement utilisée sur des aliquotes de grains fins polyminéraliques. Pour la détermination des doses équivalentes, un protocole SAR (Murray et Wintle 2000) modifié pour la mesure des feldspaths et incluant un lessivage optique a été utilisé (Lamothe et al. 2004). Les valeurs g ont été mesurées en suivant le protocole proposé par Auclair et al. (2003). La correction de Huntley et Lamothe (2001) a été utilisée afin de corriger les doses équivalentes mesurées pour la décroissance anormale du signal feldspathique. Les doses annuelles ont pour leur part été déterminées par des mesures réalisées in situ et en laboratoire. Les résultats que nous présentons dans ce mémoire sont affectés par une dispersion assez large. Cette variabilité a été prise en compte par des méthodes statistiques pour la détermination de l’âge probable de l’occupation du site Mailhot-Curran.

La datation du site Mailhot-Curran : application de la luminescence optique sur des poteries iroquoiennes du Saint-Laurent

La luminescence optique (OSL) a été mesurée sur dix-sept fragments de poterie collectés à Mailhot-Curran (BgFn-2), un site archéologique du Sylvicole supérieur tardif localisé dans le sud-ouest du Québec. Le but principal de ce projet était de dater ce site qui est considéré jusqu’à maintenant comme le plus récent site préhistorique de la concentration de Saint-Anicet, afin de poser un jalon dans la chronologie des sites de cette région. L’OSL a été utilisée conjointement à la datation par radiocarbone (14C) et la sériation du matériel archéologique. L’hypothèse archéologique propose que le village aurait été occupé pendant les années 1518 à 1530 de notre ère (Chapdelaine 2015a). Les résultats que nous proposons dans ce présent mémoire appuient cette proposition. Nous avons obtenu un âge de 490 ± 49 ans (année de référence : 2013), correspondant à l’année 1523 de notre ère avec une probabilité d’occupation du site Mailhot-Curran entre les années 1474 et 1572. Le programme de datation par luminescence optique a été réalisé sur des fragments de poterie domestique composés d’argile de la Mer de Champlain datant de la période du Quaternaire récent. La datation par stimulation infrarouge (IRSL) a été préférentiellement utilisée sur des aliquotes de grains fins polyminéraliques. Pour la détermination des doses équivalentes, un protocole SAR (Murray et Wintle 2000) modifié pour la mesure des feldspaths et incluant un lessivage optique a été utilisé (Lamothe et al. 2004). Les valeurs g ont été mesurées en suivant le protocole proposé par Auclair et al. (2003). La correction de Huntley et Lamothe (2001) a été utilisée afin de corriger les doses équivalentes mesurées pour la décroissance anormale du signal feldspathique. Les doses annuelles ont pour leur part été déterminées par des mesures réalisées in situ et en laboratoire. Les résultats que nous présentons dans ce mémoire sont affectés par une dispersion assez large. Cette variabilité a été prise en compte par des méthodes statistiques pour la détermination de l’âge probable de l’occupation du site Mailhot-Curran.

Stability of clay-based catalysts in contact with water vapour

The search for cleaner processes is one of the major challenges in modern chemical industries. In this context clay derived materials are environmentally friendly catalysts that can be easily tailored to optimize their catalytic activity for a precise reaction of interest. Furthermore, clay-based catalysts can be easily separated, recovered and reused and their versatility, low cost, high catalytic activity and/or selectivity render them very attractive materials. Considering that the stability towards water vapour is a crucial aspect for catalytic performance and reuse of the catalysts, we present a study of the pore structure stability, in the presence of water vapour, of clay catalysts prepared by acid activation with HCl solutions and ion-exchange with sodium, aluminium and iron, from a natural clay collected at Serra de Dentro (Porto Santo Island, Portugal) [1]. For elucidating the influence of water vapour on the pore structure stability, water vapour adsorption- -desorption isotherm, at 298 K, was determined on each sample by gravimetric method as well as n-pentane adsorption−desorption isotherms, at 298 K, which were determined before and after the corresponding water adsorption-desorption isotherms. Prior to the measurements, the samples were outgassed during 5 h at 473 K and the adsorptives were outgassed by repeated freeze–thaw cycles. The results to be reported in the communication allow us to state that, upon contact with water vapour, the less acid activated catalysts suffered some reduction in pore volume reflecting changes in the pore structure, while the more acid activated catalysts and those prepared by ion-exchange presented excellent stability upon one cycle of water vapour adsorption-desorption. The results are corroborated by nitrogen adsorption-desorption isotherms determined, at 77 K, before and after the water and n-pentane adsorption-desorption measurements.

“Losanga” decorated imitations of italic late republican black gloss tableware from South-Western Iberia: A multi-analytical/microchemical characterization

The micro-chemical/mineralogical composition of samples of grey-paste imitations of Italic Late Republican black gloss tableware displaying a particular kind of lozenge-shaped decoration (“Losanga pottery”) from Portuguese and Spanish archaeological sites in SW Iberia has been analysed by BSEM + EDS, μXRD, Powder XRD, Portable XRF and μRaman spectroscopy. “Losanga” decorated ceramics have been found throughout the Western Mediterranean. Most of the sherds display a green-brown to greyish-black engobe at the surface resembling the gloss found in Attic pottery from Classical Greece. The overall chemical, mineralogical and fossiliferous homogeneities of the ceramic paste show common features (low K-feldspar/plagioclase ratio, high Ca content, abundance of well-preserved fragments of foraminifera microfossils) that indicate low firing conditions in the kiln ranging from 650 to 900 °C. With respect to the ceramic body, analytical results confirm an enrichment in the surface gloss layer of iron, potassium and aluminium and a depletion in silicon and calcium; the very fine grain size of the surface coating suggests elutriation of iron oxide-rich clays as confirmed by the presence of magnetite, maghemite and goethite in μ-XRD scan. Chemical and mineralogical data also suggest that the firing process was performed in a 600–850 °C temperature range, adopting the well-known technique of alternating oxidizing and reducing firing conditions largely employed at the time. The analytical results, while compatible with the archaeological hypothesis of a common provenance of the raw materials for pottery production from the Guadalquivir valley workshops cannot be considered conclusive due to the similarity in the geological substrate in the two SW Iberian regions under study.

Tracing acidification induced by Deccan Phase 2 volcanism

The Deccan Volcanic Province (DVP) was built up by three major phases of eruptions; the most voluminous of which, the Deccan Phase 2, encompassed the Cretaceous–Palaeogene (KT) boundary. Deccan eruptions have been implicated as a contributor to the end-Cretaceous mass extinction, however, mechanism by which volcanic activity affected biota remains poorly understood. We applied a combination of rock magnetic techniques scanning electron microscopy to characterize mineral assemblages of three sections of intertrappean lacustrine sediments from the north-western Maharashtra Deccan Volcanic Provinces. Our results indicate that in sediments deposited during the early stages of the Deccan Phase 2, the Daïwal River and Dhapewada sequences, iron-bearing mineral association is dominated by detrital iron oxides (magnetite and hematite) sourced from the weathering of the surrounding basaltic bedrocks, with minor contribution form authigenic iron sulphides (framboidal pyrite, pyrrhotite and/or greigite). The sediments deposited during the final stages of Phase 2 (the Podgawan sequence) differ significantly in their characteristics. In particular, the Podgawan sediments have 1) very low magnetic susceptibility values, but higher terrigenous fraction (clays and shales) content; 2) more complex assemblage of magnetic minerals, 3) ubiquitous presence of Fe–Ca–Ce vanadates; and 4) unusual lithological variations in the middle part of the section (represented by a charcoal-rich level that is capped by a red clay layer containing fossilized bacterial colonies). We suggest that these unusual characteristics reflect increased acidity in the region during the deposition of the Podgawan sequence, likely due to cumulative effects of volcanic aerosols released during the Deccan Phase 2 eruptions. The combination of these features may be used to recognize episodes of increased acidity in the geological record. Our results also contribute to understanding of local vs. global effects of the Deccan volcanism.