Research progress on reuse of fluid catalytic cracking waste from oil refinery in cement-based materials

Present paper present the main results obtained in the scope of an ongoing project which aims to contribute to the valorization of a waste generated by the Portuguese oil company in construction materials. This waste is an aluminosilicate with high pozzolanic reactivity. Several different technological applications had already been tested with success both in terms of properties and compliance with the corresponding standards specifications. Namely, this project results already demonstrated that this waste can be used in traditional concrete, self-compacted concrete, mortars (renders, masonry mortar, concrete repair mortars), cement main constituent as well as alkali activated binders.

Pozzolanic behavior of bamboo leaf ash: Characterization and determination of the kinetic parameters

The paper presents a characterization and study of the pozzolanic behavior between calcium hydroxide (CH) and bamboo leaf ash (BLAsh), which was obtained by calcining bamboo leaves at 600 degrees C for 2 h in a laboratory electric furnace. To evaluate the pozzolanic behavior the conductometric method was used, which is based on the measurement of the electrical conductivity in a BLAsh/CH solution with the reaction time. Later, the kinetic parameters are quantified by applying a kinetic-diffusive model. The kinetic parameters that characterize the process (in particular, the reaction rate constant and free energy of activation) were determined with relative accuracy in the fitting process of the model. The pozzolanic activity is quantitatively evaluated according to the values obtained of the kinetic parameters. Other experimental techniques, such as X-ray diffraction (XRD) and scanning electron microscopy (SEM), were also employed. The results show that this kind of ash is formed by silica with a completely amorphous nature and a high pozzolanic activity. The correlation between the values of free energy of activation (Delta G(#)) and the reaction rate constants (K) are in correspondence with the theoretical studies about the rate processes reported in the literature. (C) 2010 Elsevier Ltd. All rights reserved.

A study of the chemical and physical properties of cashew nut shell ash for use in cement materials.

A study of the chemical and physical properties of cashew nut shell ash for use in cement materials. Ash occupies a prominent place among agro-industrial wastes, as it is derived from energy generation processes. Several types of ash have pozzolanic reactivity, and might be used as replacement material for cement, resulting in less energy waste and lower cost. This work aimed to investigate the physical and chemical properties of the cashew nut shell ash (CNSA), by performing the following measurement tests: chemical analysis, bulk density, specific mass, leaching and solubilization process, X-ray diffraction (XrD), specific surface area (BET) and pozzolanicity analysis with cement and lime. The results indicate a low reactivity of CNSA and the presence of heavy metals, alkalis and phenol.

Effects of calcining conditions on the microstructure of sugar cane waste ashes (SCWA): Influence in the pozzolanic activation

in this paper a study of calcining conditions on the microstructural features of sugar cane waste ash (SCWA) is carried out. For this purpose, some microparticles (< 90 mu m) of sugar cane straw ash and sugar cane bagasse ash of samples calcined at 800 degrees C and 1000 are studied by combining the bright field and the dark field images with the electron diffraction patterns in the transmission electron microscopy (TEM). It is appreciated that the morphology and texture of these microparticles change when silicon or calcium are present. Furthermore, it is observed that iron oxide (magnetite Fe(3)O(4)) is located in the calcium-rich particles. The microstructural information is correlated with the results of a kinetic-diffusive model that allows the computing of the kinetic parameters of the pozzolanic reaction (mainly the reaction rate constant). The results show that the sugar cane wastes ash calcined at 800 and 1000 degrees C have properties indicative of high pozzolanic activity. The X-ray diffraction patterns, the TEM images and the pozzolanic activity tests show the influence of different factors on the activation of these ashes. (c) 2008 Elsevier Ltd. All rights reserved.

Study of the pozzolanic reaction kinetics in sugar cane bagasse-clay ash/calcium hydroxide system: kinetic parameters and pozzolanic activity

This paper presents a study of the pozzolanic reaction kinetics between calcium hydroxide and a mixture of sugar cane bagasse with 20 and 30% of clay, burned at 800 and 1000 degrees C (SCBCA) by electrical conductivity measurements. A kinetic-diffusive model produced in previous studies by some of the authors was used. The model was fitted to the experimental data, which allowed the computation of the kinetic parameters of the pozzolanic reaction (reaction rate constant and free energy of activation) that rigorously characterised the pozzolanic activity of the materials. The results show that SCBCA demonstrated reactivity and good pozzolanic qualities in the range 800-1000 degrees C.

Influence of cristalline structure of two minerals clays of type 1/1 on their pozzolanic power

Two clayey materials, one provided by a patner in mineral sector and the other coming from Balengou (West Region Cameroon) were subject of a comparative study in order to evaluate the influence of their crystalline structure on their pozzolanic property. These two natural materials were preliminary enriched in clay minerals by wet sieving and the fractions obtained are denoted K and H respectively. K and H were calcinated at 700 °C, with a heating rate of 5 °C/min and 10 hours dwell at the peak temperature, the products obtained were named MK and MH. Samples K, H, MK and MH were physicochemically characterized by the chemical (ICP), thermal(TGA/DTA) and mineralogical (DRX and Spectrometry IR) analyses together with the measurement of specific surface (BET), crystallinity and the pouzzolanicity test. The results confirmed K as a kaolinitic and H halloysic clay. The kaolinite and the halloysite respectively presented in these clayey materials exhibited a poor crystallinity, but the degree of disorder is higher in K than in H. These results were largely affected by the significant fraction of gibbsite in kaolinitic clay K. At the crude state, the pozzolanic activity of the material H is weak compared with that of K, but the heat treatment makes largely improve this property for both samples.

Development of ultra-high-performance concrete (UHPC) using waste glass materials ─ towards innovative eco-friendly concrete

Le béton conventionnel (BC) a de nombreux problèmes tels que la corrosion de l’acier d'armature et les faibles résistances des constructions en béton. Par conséquent, la plupart des structures fabriquées avec du BC exigent une maintenance fréquent. Le béton fibré à ultra-hautes performances (BFUP) peut être conçu pour éliminer certaines des faiblesses caractéristiques du BC. Le BFUP est défini à travers le monde comme un béton ayant des propriétés mécaniques, de ductilité et de durabilité supérieures. Le BFUP classique comprend entre 800 kg/m³ et 1000 kg/m³ de ciment, de 25 à 35% massique (%m) de fumée de silice (FS), de 0 à 40%m de poudre de quartz (PQ) et 110-140%m de sable de quartz (SQ) (les pourcentages massiques sont basés sur la masse totale en ciment des mélanges). Le BFUP contient des fibres d'acier pour améliorer sa ductilité et sa résistance aux efforts de traction. Les quantités importantes de ciment utilisées pour produire un BFUP affectent non seulement les coûts de production et la consommation de ressources naturelles comme le calcaire, l'argile, le charbon et l'énergie électrique, mais affectent également négativement les dommages sur l'environnement en raison de la production substantielle de gaz à effet de serre dont le gas carbonique (CO[indice inférieur 2]). Par ailleurs, la distribution granulométrique du ciment présente des vides microscopiques qui peuvent être remplis avec des matières plus fines telles que la FS. Par contre, une grande quantité de FS est nécessaire pour combler ces vides uniquement avec de la FS (25 à 30%m du ciment) ce qui engendre des coûts élevés puisqu’il s’agit d’une ressource limitée. Aussi, la FS diminue de manière significative l’ouvrabilité des BFUP en raison de sa surface spécifique Blaine élevée. L’utilisation du PQ et du SQ est également coûteuse et consomme des ressources naturelles importantes. D’ailleurs, les PQ et SQ sont considérés comme des obstacles pour l’utilisation des BFUP à grande échelle dans le marché du béton, car ils ne parviennent pas à satisfaire les exigences environnementales. D’ailleurs, un rapport d'Environnement Canada stipule que le quartz provoque des dommages environnementaux immédiats et à long terme en raison de son effet biologique. Le BFUP est généralement vendu sur le marché comme un produit préemballé, ce qui limite les modifications de conception par l'utilisateur. Il est normalement transporté sur de longues distances, contrairement aux composantes des BC. Ceci contribue également à la génération de gaz à effet de serre et conduit à un coût plus élevé du produit final. Par conséquent, il existe le besoin de développer d’autres matériaux disponibles localement ayant des fonctions similaires pour remplacer partiellement ou totalement la fumée de silice, le sable de quartz ou la poudre de quartz, et donc de réduire la teneur en ciment dans BFUP, tout en ayant des propriétés comparables ou meilleures. De grandes quantités de déchets verre ne peuvent pas être recyclées en raison de leur fragilité, de leur couleur, ou des coûts élevés de recyclage. La plupart des déchets de verre vont dans les sites d'enfouissement, ce qui est indésirable puisqu’il s’agit d’un matériau non biodégradable et donc moins respectueux de l'environnement. Au cours des dernières années, des études ont été réalisées afin d’utiliser des déchets de verre comme ajout cimentaire alternatif (ACA) ou comme granulats ultrafins dans le béton, en fonction de la distribution granulométrique et de la composition chimique de ceux-ci. Cette thèse présente un nouveau type de béton écologique à base de déchets de verre à ultra-hautes performances (BEVUP) développé à l'Université de Sherbrooke. Les bétons ont été conçus à l’aide de déchets verre de particules de tailles variées et de l’optimisation granulaire de la des matrices granulaires et cimentaires. Les BEVUP peuvent être conçus avec une quantité réduite de ciment (400 à 800 kg/m³), de FS (50 à 220 kg/m³), de PQ (0 à 400 kg/m³), et de SQ (0-1200 kg/m³), tout en intégrant divers produits de déchets de verre: du sable de verre (SV) (0-1200 kg/m³) ayant un diamètre moyen (d[indice inférieur 50]) de 275 µm, une grande quantité de poudre de verre (PV) (200-700 kg/m³) ayant un d50 de 11 µm, une teneur modérée de poudre de verre fine (PVF) (50-200 kg/m³) avec d[indice inférieur] 50 de 3,8 µm. Le BEVUP contient également des fibres d'acier (pour augmenter la résistance à la traction et améliorer la ductilité), du superplastifiants (10-60 kg/m³) ainsi qu’un rapport eau-liant (E/L) aussi bas que celui de BFUP. Le remplacement du ciment et des particules de FS avec des particules de verre non-absorbantes et lisse améliore la rhéologie des BEVUP. De plus, l’utilisation de la PVF en remplacement de la FS réduit la surface spécifique totale nette d’un mélange de FS et de PVF. Puisque la surface spécifique nette des particules diminue, la quantité d’eau nécessaire pour lubrifier les surfaces des particules est moindre, ce qui permet d’obtenir un affaissement supérieur pour un même E/L. Aussi, l'utilisation de déchets de verre dans le béton abaisse la chaleur cumulative d'hydratation, ce qui contribue à minimiser le retrait de fissuration potentiel. En fonction de la composition des BEVUP et de la température de cure, ce type de béton peut atteindre des résistances à la compression allant de 130 à 230 MPa, des résistances à la flexion supérieures à 20 MPa, des résistances à la traction supérieure à 10 MPa et un module d'élasticité supérieur à 40 GPa. Les performances mécaniques de BEVUP sont améliorées grâce à la réactivité du verre amorphe, à l'optimisation granulométrique et la densification des mélanges. Les produits de déchets de verre dans les BEVUP ont un comportement pouzzolanique et réagissent avec la portlandite générée par l'hydratation du ciment. Cependant, ceci n’est pas le cas avec le sable de quartz ni la poudre de quartz dans le BFUP classique, qui réagissent à la température élevée de 400 °C. L'addition des déchets de verre améliore la densification de l'interface entre les particules. Les particules de déchets de verre ont une grande rigidité, ce qui augmente le module d'élasticité du béton. Le BEVUP a également une très bonne durabilité. Sa porosité capillaire est très faible, et le matériau est extrêmement résistant à la pénétration d’ions chlorure (≈ 8 coulombs). Sa résistance à l'abrasion (indice de pertes volumiques) est inférieure à 1,3. Le BEVUP ne subit pratiquement aucune détérioration aux cycles de gel-dégel, même après 1000 cycles. Après une évaluation des BEVUP en laboratoire, une mise à l'échelle a été réalisée avec un malaxeur de béton industriel et une validation en chantier avec de la construction de deux passerelles. Les propriétés mécaniques supérieures des BEVUP a permis de concevoir les passerelles avec des sections réduites d’environ de 60% par rapport aux sections faites de BC. Le BEVUP offre plusieurs avantages économiques et environnementaux. Il réduit le coût de production et l’empreinte carbone des structures construites de béton fibré à ultra-hautes performances (BFUP) classique, en utilisant des matériaux disponibles localement. Il réduit les émissions de CO[indice inférieur 2] associées à la production de clinkers de ciment (50% de remplacement du ciment) et utilise efficacement les ressources naturelles. De plus, la production de BEVUP permet de réduire les quantités de déchets de verre stockés ou mis en décharge qui causent des problèmes environnementaux et pourrait permettre de sauver des millions de dollars qui pourraient être dépensés dans le traitement de ces déchets. Enfin, il offre une solution alternative aux entreprises de construction dans la production de BFUP à moindre coût.

Linear dimensional changes in plaster die models using different elastomeric materials

Dental impression is an important step in the preparation of prostheses since it provides the reproduction of anatomic and surface details of teeth and adjacent structures. The objective of this study was to evaluate the linear dimensional alterations in gypsum dies obtained with different elastomeric materials, using a resin coping impression technique with individual shells. A master cast made of stainless steel with fixed prosthesis characteristics with two prepared abutment teeth was used to obtain the impressions. References points (A, B, C, D, E and F) were recorded on the occlusal and buccal surfaces of abutments to register the distances. The impressions were obtained using the following materials: polyether, mercaptan-polysulfide, addition silicone, and condensation silicone. The transfer impressions were made with custom trays and an irreversible hydrocolloid material and were poured with type IV gypsum. The distances between identified points in gypsum dies were measured using an optical microscope and the results were statistically analyzed by ANOVA (p < 0.05) and Tukey's test. The mean of the distances were registered as follows: addition silicone (AB = 13.6 µm, CD=15.0 µm, EF = 14.6 µm, GH=15.2 µm), mercaptan-polysulfide (AB = 36.0 µm, CD = 36.0 µm, EF = 39.6 µm, GH = 40.6 µm), polyether (AB = 35.2 µm, CD = 35.6 µm, EF = 39.4 µm, GH = 41.4 µm) and condensation silicone (AB = 69.2 µm, CD = 71.0 µm, EF = 80.6 µm, GH = 81.2 µm). All of the measurements found in gypsum dies were compared to those of a master cast. The results demonstrated that the addition silicone provides the best stability of the compounds tested, followed by polyether, polysulfide and condensation silicone. No statistical differences were obtained between polyether and mercaptan-polysulfide materials.

Subcutaneous connective tissue response to primary root canal filling materials

This study evaluated the response of the subcutaneous connective tissue of BALB/c mice to root filling materials indicated for primary teeth: zinc oxide/eugenol cement (ZOE), Calen paste thickened with zinc oxide (Calen/ZO) and Sealapex sealer. The mice (n=102) received polyethylene tube implants with the materials, thereby forming 11 groups, as follows: I, II, III: Calen/ZO for 7, 21 and 63 days, respectively; IV, V, VI: Sealapex for 7, 21 and 63 days, respectively; VII, VIII, IX: ZOE for 7, 21 and 63 days, respectively; X and XI: empty tube for 7 and 21 days, respectively. The biopsied tissues were submitted to histological analysis (descriptive analysis and semi-quantitative analysis using a scoring system for collagen fiber formation, tissue thickness and inflammatory infiltrate). A quantitative analysis was performed by measuring the area and thickness of the granulomatous reactionary tissue (GRT). Data were analyzed by Kruskal-Wallis, ANOVA and Tukey's post-hoc tests (?=0.05). There was no significant difference (p>0.05) among the materials with respect to collagen fiber formation or GRT thickness. However, Calen/ZO produced the least severe inflammatory infiltrate (p<0.05). The area of the GRT was significantly smaller (p<0.05) for Calen/ZO and Sealapex. In conclusion, Calen/ZO presented the best tissue reaction, followed by Sealapex and ZOE.

Histopathological evaluation of root canal filling materials for primary teeth

This study aimed to assess the response of apical and periapical tissues of dogs' teeth after root canal filling with different materials. Forty roots from dogs' premolars were prepared biomechanically and assigned to 4 groups filled with: Group I: commercial calcium hydroxide and polyethylene glycol-based paste (Calen®) thickened with zinc oxide; Group II: paste composed of iodoform, Rifocort® and camphorated paramonochlorophenol; Group III: zinc oxide-eugenol cement; Group IV: sterile saline. After 30 days, the samples were subjected to histological processing. The histopathological findings revealed that in Groups I and IV the apical and periapical regions exhibited normal appearance, with large number of fibers and cells and no resorption of mineralized tissues. In Group II, mild inflammatory infiltrate and mild edema were observed, with discrete fibrogenesis and bone resorption. Group III showed altered periapical region and thickened periodontal ligament with presence of inflammatory cells and edema. It may be concluded that the Calen paste thickened with zinc oxide yielded the best tissue response, being the most indicated material for root canal filling of primary teeth with pulp vitality.

Antibacterial activity of root canal filling materials for primary teeth: zinc oxide and eugenol cement, Calen paste thickened with zinc oxide, Sealapex and EndoREZ

This study evaluated in vitro the antibacterial activity of 4 root canal filling materials for primary teeth - zinc oxide and eugenol cement (ZOE), Calen paste thickened with zinc oxide (Calen/ZO), Sealapex sealer and EndoREZ sealer - against 5 bacterial strains commonly found in endodontic infections (Kocuria rhizophila, Enterococcus faecalis, Streptococcus mutans, Escherichia coli and Staphylococcus aureus) using the agar diffusion test (agar-well technique). Calen paste, 1% chlorhexidine digluconate (CHX) and distilled water served as controls. Seven wells per dish were made at equidistant points and immediately filled with the test and control materials. After incubation of the plates at 37oC for 24 h, the diameter of the zones of bacterial growth inhibition produced around the wells was measured (in mm) with a digital caliper under reflected light. Data were analyzed statistically by analysis of variance and Tukey's post-hoc test (?=0.05). There were statistically significant differences (p<0.0001) among the zones of bacterial growth inhibition produced by the different materials against all target microorganisms. K. rhizophila was inhibited more effectively (p<0.05) by ZOE, while Calen/ZO had its highest antibacterial activity against E. faecalis (p<0.05). S. mutans was inhibited by Calen/ZO, Sealapex and ZOE in the same intensity (p>0.05). E. coli was inhibited more effectively (p<0.05) by ZOE, followed by Calen/ZO and Sealapex. Calen/ZO and ZOE were equally effective (p>0.05) against S. aureus, while Sealapex had the lowest antibacterial efficacy (p<0.05) against this microorganism. EndoREZ presented antibacterial activity only against K. rhizophila and S. aureus. The Calen paste and Calen/ZO produced larger zones of inhibition than 1% CHX when the marker microorganism was E faecalis. In conclusion, the in vitro antibacterial activity of the 4 root canal filling materials for primary teeth against bacterial strains commonly found in endodontic infections can be presented in a decreasing order of efficacy as follows: ZOE>Calen/ZO>Sealapex>EndoREZ.

Accuracy of stone casts obtained by different impression materials

Several impression materials are available in the Brazilian marketplace to be used in oral rehabilitation. The aim of this study was to compare the accuracy of different impression materials used for fixed partial dentures following the manufacturers' instructions. A master model representing a partially edentulous mandibular right hemi-arch segment whose teeth were prepared to receive full crowns was used. Custom trays were prepared with auto-polymerizing acrylic resin and impressions were performed with a dental surveyor, standardizing the path of insertion and removal of the tray. Alginate and elastomeric materials were used and stone casts were obtained after the impressions. For the silicones, impression techniques were also compared. To determine the impression materials' accuracy, digital photographs of the master model and of the stone casts were taken and the discrepancies between them were measured. The data were subjected to analysis of variance and Duncan's complementary test. Polyether and addition silicone following the single-phase technique were statistically different from alginate, condensation silicone and addition silicone following the double-mix technique (p < .05), presenting smaller discrepancies. However, condensation silicone was similar (p > .05) to alginate and addition silicone following the double-mix technique, but different from polysulfide. The results led to the conclusion that different impression materials and techniques influenced the stone casts' accuracy in a way that polyether, polysulfide and addition silicone following the single-phase technique were more accurate than the other materials.

Effect of ageing and immersion in different beverages on properties of denture lining materials

OBJECTIVES: To evaluate the color stability and hardness of two denture liners obtained by direct and indirect techniques, after thermal cycling and immersion in beverages that can cause staining of teeth. MATERIAL AND METHODS: Seventy disc-shaped specimens (18 x 3 mm) processed by direct (DT) and indirect techniques (IT) were made from Elite soft (n=35) and Kooliner (n=35) denture liners. For each material and technique, 10 specimens were subjected to thermal cycling (3,000 cycles) and 25 specimens were stored in water, coffee, tea, soda and red wine for 36 days. The values of color change, Shore A hardness (Elite soft) and Knoop hardness (Kooliner) were obtained. The data were subjected to ANOVA, Tukey's multiple-comparison test, and Kruskal-Wallis test (P<0.05). RESULTS: The thermal cycling promoted a decrease on hardness of Kooliner regardless of the technique used (Initial: 9.09± 1.61; Thermal cycling: 7.77± 1.47) and promoted an increase in the hardness in the DT for Elite Soft (Initial: 40.63± 1.07; Thermal cycling: 43.53± 1.03); hardness of Kooliner (DT: 8.76± 0.95; IT: 7.70± 1.62) and Elite Soft (DT: 42.75± 1.54; IT=39.30± 2.31) from the DT suffered an increase after the immersion in the beverages. The thermal cycling promoted color change only for Kooliner in the IT. Immersion in the beverages did not promote color change for Elite in both techniques. The control group of the DT of Kooliner showed a significant color change. Wine and coffee produced the greatest color change in the DT only for Elite Soft when compared to the other beverages. CONCLUSION: The three variation factors promoted alteration on hardness and color of the tested denture lining materials.

Pulp capping materials exert an effect on the secretion of IL-1β and IL-8 by migrating human neutrophils

Pulp repair is a complex process whose mechanisms are not yet fully understood. The first immune cells to reach the damaged pulp are neutrophils that play an important role in releasing cytokines and in phagocytosis. The objective of this study was to analyze the effect of different pulp-capping materials on the secretion of interleukin-1 beta (IL-1β) and interleukin-8 (IL-8) by migrating human neutrophils. Neutrophils were obtained from the blood of three healthy donors. The experimental groups were calcium hydroxide [Ca(OH)2], an adhesive system (Single Bond), and mineral trioxide aggregate (MTA). Untreated cells were used as control. Transwell chambers were used in performing the assays to mimic an in vivo situation of neutrophil chemotaxis. The pulp-capping materials were placed in the lower chamber and the human neutrophils, in the upper chamber. The cells were counted and the culture medium was assayed using ELISA kits for detecting and quantifying IL-1β and IL8. The data were compared by ANOVA followed by Tukey's test (p < 0.05). The secretion of IL-8 was significantly higher in all groups in comparison to the control group (p < 0.05). The adhesive system group showed higher IL-8 than the MTA group (p < 0.05). The secretion of IL-1β was significantly greater only in the MTA group (p < 0.001). It was concluded that only MTA is able to improve the secretion of IL-1β, and all materials tested increased IL-8 secretion. These results combined with all the other biological advantages of MTA indicate that it could be considered the material of choice for dental pulp capping.