Phase relations in the system Ca-Ta-O and thermodynamics of calcium tantalates in relation to calciothermic reduction of Ta2O5

Phase equilibria of the system Ca-Ta-O is established by equilibrating eleven samples at 1200 K for prolonged periods and phase identification in quenched samples by optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Four ternary oxides are identified: CaTa4O11, CaTa2O6, Ca2Ta2O7 and Ca4Ta2O9. Isothermal section of the phase diagram is composed using the results. Thermodynamic properties of the ternary oxides are measured in the temperature range from 975 to 1275 K employing solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells essentially measure the chemical potentials of CaO in two-phase fields (Ta2O5 + CaTa4O11), (CaTa4O11 + CaTa2O6), (CaTa2O6 + Ca2Ta2O7), and (Ca2Ta2O7 + Ca4Ta2O9) of the pseudo-binary system CaO-Ta2O5. The standard Gibbs energies of formation of the four ternary oxides from their component binary oxides Ta2O5 and CaO are given by: Delta G(f)((ox))(o) (CaTa4O11) (+/- 482)/J mol(-1) = -58644+21.497 (T/K) Delta G(f)((ox))(o) (CaTa2O6) (+/- 618)/J mol(-1) = -55122+21.893 (T/K) Delta G(f)((ox))(o) (Ca2Ta2O7) (+/- 729)/J mol(-1) = -82562+31.843 (T/K) Delta G(f)((ox))(o) (Ca4Ta2O9) (+/- 955)/J mol(-1) = -126598+48.859 (T/K) The Gibbs energy of formation of the four ternary compounds obtained in this study differs significantly from that reported in the literature. The thermodynamic data and phase diagram are used for understanding the mechanism and kinetics of calciothermic and electrochemical reduction of Ta2O5 to metal. (C) 2014 Elsevier B.V. All rights reserved.

A study of slag corrosion of oxides and oxide-carbon refractories during steel refining

The use of ceramic material as refractories in the manufacturing industry is a common practice worldwide. During usage, for example in the production of steel, these materials do experience severe working conditions including high temperatures, low pressures and corrosive environments. This results in lowered service lives and high consumptions of these materials. This, in turn, affects the productivity of the whole steel plant and thereby the cost. In order to investigate how the service life can be improved, studies have been carried out for refractories used in the inner lining of the steel ladles. More specifically, from the slag zone, where the corrosion is most severe. By combining thermodynamic simulations, plant trails and post-mortem studies of the refractories after service, vital information about the behaviour of the slagline refractories during steel refining and the causes of the accelerated wear in this ladle area has been achieved. The results from these studies show that the wear of the slagline refractories of the ladle is initiated at the preheating station, through reduction-oxidation reactions. The degree of the decarburization process is mostly dependent on the preheating fuel or the environment. For refractories without antioxidants, refractory decarburization is slower when coal gas is used in ladle preheating than when a mixture of oil and air is used. In addition, ladle preheating of the refractories without antioxidants leads to direct wear of the slagline refractories. This is due to the total loss of the matrix strength, which results in a sand-like product. Thermal chemical changes that take place in the slagline refractories are due to the MgO-C reaction as well as the formation of liquid phases from impurity oxides. In addition, the decrease in the system pressure during steel refining makes the MgO-C reaction take place at the steel refining temperatures. This reduces the refractory’s resistance to corrosion. This is a serious problem for both the magnesia-carbon and dolomite-carbon refractories. The studies of the reactions between the slagline refractories and the different slag compositions showed that slags rich in iron oxide lead mostly to the oxidation of carbon/graphite in the carbon-containing refractories. This leads to an increased porosity and wettability and therefore an enhanced penetration of slag into the refractory structure. If the slag contains high contents of alumina and or silica (such as the steel refining slag), reactions between the slag components and the dolomite-carbon refractory are promoted. This leads to the formation of low-temperature melting phases such as calcium-aluminates and silicates. The state of these reaction products during steel refining leads to an accelerated wear of the dolomite-carbon refractory. The main products of the reactions between the magnesia-carbon refractory and the steel refining slag are MgAl2O4 spinels, and calcium-aluminates, and silicates. Due to the good refractory properties of MgAl2O4 spinels, the slag corrosion resistance of the magnesiacarbon refractory is promoted.

Bone repair using mineral trioxide aggregate combined to a material carrier, associated or not with calcium hydroxide in bone defects

Mineral trioxide aggregate (MTA) is a powder aggregate containing mineral oxides with a good biological action and may facilitate the regeneration of the periodontal ligament and formation of bone. Calcium hydroxide demonstrates antibacterial properties, enhances tissue dissolution, and induces bone formation. The objective of this study was to evaluate the MTA in the bone healing process and verify if the calcium hydroxide P.A. can improve and accelerate this process. It was used forty rnale Wistar rats, which were divided into two groups, considering or not the use of calcium hydroxide P.A. solution before treatment. Thus, each one of these groups was divided in four groups with five animals each, according to the treatment and the defect filled by: animal's coagulum, monoolein gel, MTA in aqueous solution, and MTA combined with monoolein gel. After 10 days, the animals were perfused and the right hemimandibles removed for histological analysis. Statistical analysis of the data showed significant difference between all analyzed groups when it was made comparisons using or not calcium hydroxide P.A. (p < 0.0001). There was found statistical difference between the groups that was inserted or not MTA, independently the calcium hydroxide application (p < 0.05). Results showed that the MTA used was able to induce bone regeneration and had its action optimized when combined to calcium hydroxide P.A. (C) 2007 Elsevier Ltd. All rights reserved.

Reaction of rat connective tissue to implanted dentin tubes filled with mineral trioxide aggregate or calcium hydroxide

This study was conducted to observe the rat subcutaneous connective tissue reaction to the implanted dentin tubes filled with calcium hydroxide or mineral trioxide aggregate. The animals were sacrificed after 7 and 30 days, and the specimens were prepared for morphological study. Some undecalcified specimens were prepared for histological analysis with polarized light and Von Kossa technique for calcium. The results were similar for both studied materials. At the tube openings, there were Von Kossa-positive granules that were birefringent to polarized light. Next to these granulations, there was an irregular tissue like a bridge that was Von Kossa-positive. The dentin walls of the tubes exhibited in the tubules a structure highly birefringent to polarized light, usually like a layer and at different depths. It is possible that the mechanism of action of both materials has some similarity. Copyright © 1999 by The American Association of Endodontists.

Reaction of rat connective tissue to implanted dentin tube filled with mineral trioxide aggregate, Portland cement or calcium hydroxide.

The subject of this study was to observe the rat subcutaneous connective tissue reaction to implanted dentin tubes filled with mineral trioxide aggregate, Portland cement or calcium hydroxide. The animals were sacrificed after 7 or 30 days and the undecalcified specimens were prepared for histological analysis with polarized light and Von Kossa technique for mineralized tissues. The results were similar for the studied materials. At the tube openings, there were Von Kossa-positive granules that were birefringent to polarized light. Next to these granulations, there was an irregular tissue like a bridge that was Von Kossa-positive. The dentin walls of the tubes exhibited in the tubules a structure highly birefringent to polarized light, usually like a layer and at different depths. The mechanism of action of the studied materials has some similarity.

Calcium salts deposition in rat connective tissue after the implantation of calcium hydroxide-containing sealers

This study was conducted to observe the rat subcutaneous connective tissue reaction to implanted dentin tubes that were filled with mineral trioxide aggregate, Sealapex, Calciobiotic Root Canal Sealer (CRCS), Sealer 26, and the experimental material, Sealer Plus. The animals were sacrificed after 7 and 30 days, and the specimens were prepared for histological analysis after serial sections with a hard-tissue microtome. The undecalcified sections were examined with polarized light after staining according to the Von Kossa technique for calcium. At the tube openings, there were Von Kossa-positive granules that were birefringent to polarized light. Next to these granulations, there was irregular tissue, like a bridge, that was Von Kossa-positive. The dentin walls of the tubes exhibited a structure highly birefringent to polarized light, usually like a layer, in the tubules. These results were observed with all the studied materials, except the CRCS, which didn't exhibit any kind of mineralized structure. The results suggest that among the materials studied, the CRCS could have the least possibility of encouraging hard tissue deposition.

Clinical and radiographic evaluation of pulpotomies employing calcium hydroxide and trioxide mineral aggregate

This study utilized clinical and radiographic examinations to compare the effectiveness of calcium hydroxide paste and mineral trioxide aggregate (MTA) for pulpotomies of primary molars in children. Ninety primary molars that showed clinical and radiographic indications for pulpotomy treatment were selected. The pulpotomies were performed in two sessions, using a corticosteroid/ antibiotic solution as therapeutic dressing. The sample was divided into two groups of 45 teeth, in which the pulpal remains were protected with either calcium hydroxide paste (Group 1) or MTA (Group 2). Radiographs were taken immediately and at 3-, 6-, and 12-month follow-up appointments. Three teeth in Group 1 failed after three months, while two cases failed after six months and one more failed at one year. Two failures were found in Group 2 at the 12-month follow-up. These results indicate that both materials may be utilized for pulpotomies in primary teeth.

Response of human dental pulp capped with MTA and calcium hydroxide powder

Objectives: To compare the response of human dental pulp capped with a mineral trioxide aggregate (MTA) and Ca(OH) 2 powder. Methods and Material: Pulp exposures were performed on the occlusal floor of 40 permanent premolars. The pulp was then capped with either Ca(OH) 2 powder (CH) or MTA and restored with resin composite. After 30 days (groups CH30 and MTA30) and 60 days (groups CH60 and MTA60), the teeth were extracted and processed for HE and categorized in a histological score system. The data were subjected to Kruskal-Wallis and Conover tests (α=0.05). Results: In regard to dentin bridge formation, CH30 showed a tendency towards superior performance compared to MTA30 (p>0.05), although the products showed comparable results at day 60. In the item Inflammation and General State of the Pulp (p>0.05), CH showed a tendency towards presenting a higher inflammatory response. In the item Other Pulpal Findings, MTA and Ca(OH) 2 showed equal and excellent performance after 30 and 60 days (p>0.05). Conclusion: After 30 days, Ca(OH) 2 powder covered with calcium hydroxide cement showed faster hard tissue bridge formation compared to MTA. After 60 days, Ca(OH) 2 powder or MTA materials showed a similar and excellent histological response with the formation of a hard tissue bridge in almost all cases with low inflammatory infiltrate. © Operative Dentistry, 2008.

Antimicrobial activity of endodontic sealers based on calcium hydroxide and MTA.

The aim of this study was to evaluate the antimicrobial activity of a new root canal sealer containing calcium hydroxide (Acroseal) and the root canal sealer based on MTA (Endo CPM Sealer), in comparison with traditional sealers (Sealapex, Sealer 26 and Intrafill) and white MTA-Angelus, against five different microorganism strains. The materials and their components were evaluated after manipulation, employing the agar diffusion method. A base layer was made using Müller-Hinton agar (MH) and wells were made by removing agar. The materials were placed into the wells immediately after manipulation. The microorganisms used were: Micrococcus luteus (ATCC9341), Staphylococcus aureus (ATCC6538), Pseudomonas aeruginosa (ATCC27853), Candida albicans (ATCC 10231), and Enterococcus faecalis (ATCC 10541). The plates were kept at room temperature for 2 h for prediffusion and then incubated at 37 degrees C for 24 h. The results showed that Sealapex and its base paste, Sealer 26 and its powder, Endo CPM Sealer and its powder, white MTA and its powder all presented antimicrobial activity against all strains. Intrafill and its liquid presented antimicrobial activity against all strains except P. aeruginosa and Acroseal was effective only against M. luteus and S. aureus.

Radiopacity evaluation of root canal sealers containing calcium hydroxide and MTA

The purpose of this study was to evaluate the radiopacity of root canal sealers containing calcium hydroxide and MTA (Acroseal, Sealer 26, Sealapex, Endo CPM Sealer, Epiphany and Intrafill). Five disc-shaped specimens (10 x 1 mm) were fabricated from each material, according to the ISO 6876/2001 standard. After setting of the materials, radiographs were taken using occlusal film and a graduated aluminum stepwedge varying from 2 to 16 mm in thickness. The dental X-ray unit (GE1000) was set at 50 kVp, 10 mA, 18 pulses/s and distance of 33.5 cm. The radiographs were digitized and the radiopacity compared to that of the aluminum stepwedge using VIXWIN-2000 software (Gendex). The data (mmAl) were analyzed statistically by ANOVA and Tukey's test at the 5% significance level. Epiphany and Intrafill presented the highest radiopacity values (8.3 mmAl and 7.5 mmAl respectively, p < 0.05) followed by Sealer 26 (6.3 mmAl), Sealapex (6.1 mmAl) and Endo CPM Sealer (6 mmAl). Acroseal was the least radiopaque material (4 mmAl, p < 0.05). In conclusion, the calcium hydroxide- and MTA-containing root canal sealers had different radiopacities. However, all materials presented radiopacity values above the minimum recommended by the ISO standard. © 2009 Sociedade Brasileira de Pesquisa Odontológica.

Sealing ability of retrograde obturation materials containing calcium hydroxide or MTA

Newly available materials for retrograde obturation should have their sealing properties evaluated. The goal of this study was to evaluate the sealing ability of Endo CPM sealer, an MTA-based endodontic cement. Single-rooted extracted human teeth were endodontically treated. After apical sectioning, retrograde cavities were prepared. Teeth were divided into five experimental groups (n=12), in which the following materials were used: Sealer 26 (S26), white Mineral Trioxide Aggregate (MTA), Endo CPM Sealer (CPM1), Endo CPM Sealer in thicker consistency (CPM 2), and zinc oxide and eugenol cement (ZOE), and two control groups (n=3). After retrograde obturation, the teeth were immersed in 0.2% rhodamine B dye for 48 hours in a vacuum chamber Marginal leakage data were subjected to ANOVA and Tukey tests at 5% significance level. S26 presented greater sealing ability (p<0.05) than ZOE, MTA, CPM1, and CPM2, all of which had similar results (p>0.05). We concluded that Sealer 26 has the greatest sealing ability. Endo CPM Sealer, with sealing ability similar to MTA, could be used as a retrograde obturation material.

Growth of calcium phosphate coating on Ti-7.5Mo alloy after anodic oxidation

Titanium and its alloys are widely used as biomaterials due to their mechanical, chemical and biological properties. To enhance the biocompatibility of titanium alloys, various surface treatments have been proposed. In particular, the formation of titanium oxide nanotubes layers has been extensively examined. Among the various materials for implants, calcium phosphates and hydroxyapatite are widely used clinically. In this work, titanium nanotubes were fabricated on the surface of Ti-7.5Mo alloy by anodization. The samples were anodized for 20 V in an electrolyte containing glycerol in combination with ammonium fluoride (NH4F, 0.25%), and the anodization time was 24 h. After being anodized, specimens were heat treated at 450 °C and 600°C for 1 h to crystallize the amorphous TiO2 nanotubes and then treated with NaOH solution to make them bioactive, to induce growth of calcium phosphate in a simulated body fluid. Surface morphology and coating chemistry were obtained respectively using, field-emission scanning electron microscopy (FEG-SEM), AFM and X-ray diffraction (XRD). It was shown that the presence of titanium nanotubes induces the growth of a sodium titanate nanolayer. During the subsequent invitro immersion in a simulated body fluid, the sodium titanate nanolayer induced the nucleation and growth of nano-dimensioned calcium phosphate. It was possible to observe the formation of TiO2 nanotubes on the surface of Ti-7.5Mo. Calcium phosphate coating was greater in the samples with larger nanotube diameter. These findings represent a simple surface treatment for Ti-7.5Mo alloy that has high potential for biomedical applications. © (2013) Trans Tech Publications, Switzerland.

Hydrogen ion and calcium releasing of MTA Fillapex® and MTA-based formulations

MTA is composed of various metal oxides, calcium oxide and bismuth. It has good biological properties and is indicated in cases of endodontic complications. Several commercial formulations are available and further studies are necessary to evaluate these materials. Objective: To evaluate pH and calcium releasing of MTA Fillapex® compared with gray and white MTA. Material and methods: Gray and white MTA (Angelus) and MTA Fillapex® (Angelus) were manipulated and placed into polyethylene tubes and immersed in distilled water. The pH of these solutions was measured at 24 hours, 7 days and 14 days. Simultaneously, at these same aforementioned periods, these materials' calcium releasing was quantified, through atomic absorption spectrophotometry. The results were submitted to ANOVA, with level of significance at 5%. Results: Concerning to pH, the materials present similar behaviors among each other at 24 hours (p > 0.05). At 7 and 14 days, MTA Fillapex® provided significantly lower pH values than the other materials (p < 0.05). Regarding to calcium releasing, at 24 hours and 7 days, MTA Fillapex® provided lower releasing than the other materials (p < 0.05). After 14 days, differences were found between MTA Fillapex® and gray MTA (p < 0.05). Conclusion: All materials showed alkaline pH and calcium releasing, with significantly lower values for MTA Fillapex® sealer.

Biogenic calcium phosphate transformation in soils over millennial time scales

Changes in bioavailability of phosphorus (P) during pedogenesis and ecosystem development have been shown for geogenic calcium phosphate (Ca-P). However, very little is known about long-term changes of biogenic Ca-P in soil. Long-term transformation characteristics of biogenic Ca-P were examined using anthropogenic soils along a chronosequence from centennial to millennial time scales. Phosphorus fractionation of Anthrosols resulted in overall consistency with the Walker and Syers model of geogenic Ca-P transformation during pedogenesis. The biogenic Ca-P (e.g., animal and fish bones) disappeared to 3% of total P within the first ca. 2,000 years of soil development. This change concurred with increases in P adsorbed on metal-oxides surfaces, organic P, and occluded P at different pedogenic time. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the crystalline and therefore thermodynamically most stable biogenic Ca-P was transformed into more soluble forms of Ca-P over time. While crystalline hydroxyapatite (34% of total P) dominated Ca-P species after about 600-1,000 years, beta-tricalcium phosphate increased to 16% of total P after 900-1,100 years, after which both Ca-P species disappeared. Iron-associated P was observable concurrently with Ca-P disappearance. Soluble P and organic P determined by XANES maintained relatively constant (58-65%) across the time scale studied. Disappearance of crystalline biogenic Ca-P on a time scale of a few thousand years appears to be ten times faster than that of geogenic Ca-P.

High exchangeable calcium concentrations in soils on Barro Colorado Island, Panama

The soils on four lithologies (basaltic conglomerates, Bohio; Andesite; volcanoclastic sediments with basaltic agglomerates, Caimito volcanic; foraminiferal limestone, Caimito marine) on Barro Colorado Island (BCI) have high exchangeable Ca concentrations and cation-exchange capacities (CEC) compared to other tropical soils on similar parent material. In the 0–10 cm layer of 24 mineral soils, pH values ranged from 5.7 (Caimito volcanic and Andesite) to 6.5 (Caimito marine), concentrations of exchangeable Ca from 134 mmolc kg− 1 (Caimito volcanic) to 585 mmolc kg− 1 (Caimito marine), and cation exchange capacities from 317 mmolc kg− 1 (Caimito volcanic) to 933 mmolc kg− 1 (Caimito marine). X-ray diffractometry of the fraction < 2 μm revealed that smectites dominated the clay mineral assemblage in soil except on Caimito volcanic, where kaolinite was the dominant clay mineral. Exchangeable Ca concentrations decreased with increasing soil depth except on Caimito marine. The weathering indices Chemical Index of Alteration (CIA), Plagioclase Index of Alteration (PIA) and Weathering Index of Parker (WIP) determined for five soils on all geological formations, suggested that in contrast to expectation the topsoil (0–10 cm) appeared to be the least and the subsoil (50–70 cm) and saprolite (isomorphically weathered rock in the soil matrix) the most weathered. Additionally, the weathering indices indicated depletion of base cations and enrichment of Al-(hydr)oxides throughout the soil profile. Tree species did not have an effect on soil properties. Impeded leaching and the related occurrence of overland flow seem to be important in determining clay mineralogy. Our results suggest that (i) edaphic conditions favor the formation of smectites on most lithologies resulting in high CEC and thus high retention capacity for Ca and (ii) that there is an external source such as dust or sea spray deposition supplying Ca to the soils.