Cement As a Waste Form for Nuclear Fission Products: The Case of 90Sr and Its Daughters

One of the main challenges faced by the nuclear industry is the long-term confinement of nuclear waste. Because it is inexpensive and easy to manufacture, cement is the material of choice to store large volumes of radioactive materials, in particular the low-level medium-lived fission products. It is therefore of utmost importance to assess the chemical and structural stability of cement containing radioactive species. Here, we use ab initio calculations based on density functional theory (DFT) to study the effects of ⁹⁰Sr insertion and decay in C-S-H (calcium-silicate-hydrate) in order to test the ability of cement to trap and hold this radioactive fission product and to investigate the consequences of its β-decay on the cement paste structure. We show that ⁹⁰Sr is stable when it substitutes the Ca²⁺ ions in C-S-H, and so is its daughter nucleus ⁹⁰Y after β-decay. Interestingly, ⁹⁰Zr, daughter of ⁹⁰Y and final product in the decay sequence, is found to be unstable compared to the bulk phase of the element at zero K but stable when compared to the solvated ion in water. Therefore, cement appears as a suitable waste form for ⁹⁰Sr storage.

Development of an experimental glass ionomer cement containing niobium and fluoride

Glass ionomer cements (GICs) are currently used for various dental applications such as luting cements or as restorative materials. The calcium fluoro-alumino-silicate system is the basis for degradable glasses used to obtain the GICs. The purpose of the present paper is to add niobium to conventional glass system because according to previous papers niobium addition improves the chemical resistance and the mechanical properties of glasses. Therefore, the GICs prepared from these glasses would result in cements with higher chemical and mechanical resistance. The niobium fluoride powders were prepared using the sol-gel process and were characterized by X-ray diffraction, differential thermal analysis (DTA) and Al-27 and Si-29 MAS NMR. The results obtained by XRD showed that the powders prepared by this method are glass-ceramic. In the DTA curve was detected the presence of T-g and T-c temperatures. The analysis of MAS NMR spectra indicated that the framework of the powders is formed by SiO4 and AlO4 linked tetrahedra which are essential structures to yield the cements. Thus, we concluded that niobium fluoride silicate powders can be used in the preparation of GICs. (c) 2005 Elsevier B.V. All rights reserved.

Evaluation of glass ionomer cements properties obtained from niobium silicate glasses prepared by chemical process

Glass ionomer cements (GICs) are glass and polymer composite materials. These materials currently find use in the dental field. The purpose of this work is to obtain systems based on composition 4.5SiO(2)-3Al(2)O(3)-XNb2O5-2CaO to be used in Dentistry. The systems were prepared by chemical route at 700 degrees C. The results obtained by XRD and DTA showed that all systems prepared are glasses. The structures of the obtained glasses were compared to commercial material using Al-27 and Si-29 MAS NMR. The analysis of MAS NMR spectra indicated that the systems developed and commercial material are formed by SiO4 and AlO4 linked tetrahedra. The properties of glass ionomer cements based on the glasses prepared with several niobium contents were studied. Setting and working times of the cement pastes, microhardness and diametral tensile strength were evaluated for the experimental GICs and commercial luting cements. It was concluded that setting time of the cement pastes increased with increasing niobium content of the glasses (X). The properties to the GICs such as setting time and microhardness were influenced by niobium content. (c) 2005 Elsevier B.V. All rights reserved.

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.

Effect of different radiopacifying agents on the physicochemical properties of white portland cement and white mineral trioxide aggregate

Introduction: The aim of this study was to evaluate the pH, calcium ion release, setting time, and solubility of white mineral trioxide aggregate (WMTA) and white Portland cement (WPC) combined with the following radiopacifying agents: bismuth oxide (BO), calcium tungstate (CT), and zirconium oxide (ZO). Methods: Fifty acrylic teeth with root-end filling material were immersed in ultrapure water for measurement of pH and calcium release (atomic absorption spectrophotometry) at 3, 24, 72, and 168 hours. For evaluation of setting time, each material was analyzed according to the American Society for Testing and Materials guidelines 266/08. The solubility test was performed according to American National Standards Institute/American Dental Association specification no. 57/2000. Solubility, setting time, and pH values were compared by using analysis of variance and Tukey test, and the values of calcium release were compared by the Kruskal-Wallis and Miller tests. The significance level was set at 5%. Results: The pH and calcium release were higher at 3 and 24 hours. WPC was the material with the higher values for both properties. WMTA had the greatest solubility among all materials (P <.05). All radiopacifiers increased the setting time of WPC, and WMTA had the shortest setting time among all materials (P < .05). Conclusions: All materials released calcium ions. Except for WPC/CT at 168 hours, all materials promoted an alkaline pH. On the basis of the obtained results, ZO and CT can be considered as potential radiopacifying agents to be used in combination with Portland cement. Copyright © 2012 American Association of Endodontists.

Effect of colloidal silica on the mechanical properties of fiber-cement reinforced with cellulosic fibers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Radiopacity, pH and antimicrobial activity of Portland cement associated with micro- and nanoparticles of zirconium oxide and niobium oxide

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of zirconium oxide and zinc oxide nanoparticles on physicochemical properties and antibiofilm activity of a calcium silicate-based material

The aim of the present study was to evaluate the antibiofilm activity against Enterococcus faecalis, compressive strength. and radiopacity of Portland cement (PC) added to zirconium oxide (ZrO2), as radiopacifier, with or without nanoparticulated zinc oxide (ZnO).The following experimental materials were evaluated: PC, PC + ZrO2, PC + ZrO2 + ZnO (5%), and PC + ZrO2 + ZnO (10%). Antibiofilm activity was analyzed by using direct contact test (DCT) on Enterococcus faecalis biofilm, for 5 h or 15 h. The analysis was conducted by using the number of colony-forming units (CFU/mL). The compressive strength was performed in a mechanical testing machine. For the radiopacity tests, the specimens were radiographed together with an aluminium stepwedge. The results were submitted to ANOVA and Tukey tests, with level of significance at 5%. The results showed that all materials presented similar antibiofilm activity (

A new calcium silicate-based material (Biodentine) for filling radicular perforation in an endodontic-periodontal lesion: a case report

This case report presents an apical radicular perforation management using new calcium silicate-based cement (Biodentine) in a combined endodontic-periodontal lesion. The presence of apical radicular perforation may interfere in the endodontic treatment prognosis. Radicular perforation filling with bioactive cement through endodontic surgery is a possible treatment. This study presents an apical radicular perforation with periodontal involvement, due to alveolar bone loss on the buccal radicular surface from an incorrect intracanal preparation for the fiber post placing. The chosen alternative was a periapical surgery, the perforation was filled with a silicate and calcium chloride bioactive cement (Biodentine; Septodont, Saint-Maur-des-Fosses Cedex, France), and the radicular surface was etched with citric acid, because the access from root canal was impossible. The follow-up was for 8 months, through clinical and radiographic analysis. At the end of the follow-up, radiographic analyses showed the bone healing, and no clinical changes in periodontal probing depth, gingival recession, and the height of the interproximal mesial and distal papillae were observed. The root perforation treatment has a difficult management, especially when the dental root has a simultaneous periodontal commitment. The Biodentine proves to be a promising material for use in these situations.

Niobium pentoxide as radiopacifying agent of calcium silicate-based material: evaluation of physicochemical and biological properties

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Supercritical carbonation treatment on extruded fibre-cement reinforced with vegetable fibres

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Retention of Root Canal Posts: Effect of Cement Film Thickness, Luting Cement, and Post Pretreatment.

The aim of this study was to investigate the effect of the cement film thickness of a zinc phosphate or a resin cement on retention of untreated and pretreated root canal posts. Prefabricated zirconia posts (CosmoPost: 1.4 mm) and two types of luting cements (a zinc phosphate cement [DeTrey Zinc] and a self-etch adhesive resin cement [Panavia F2.0]) were used. After removal of the crowns of 360 extracted premolars, canines, or incisors, the root canals were prepared with a parallel-sided drill system to three different final diameters. Half the posts did not receive any pretreatment. The other half received tribochemical silicate coating according to the manufacturer's instructions. Posts were then luted in the prepared root canals (n=30 per group). Following water storage at 37°C for seven days, retention of the posts was determined by the pull-out method. Irrespective of the luting cement, pretreatment with tribochemical silicate coating significantly increased retention of the posts. Increased cement film thickness resulted in decreased retention of untreated posts and of pretreated posts luted with zinc phosphate cement. Increased cement film thickness had no influence on retention of pretreated posts luted with resin cement. Thus, retention of the posts was influenced by the type of luting cement, by the cement film thickness, and by the post pretreatment.

Experimental Characterization and Quantification of Cement-Bentonite Interaction using Core Infiltration Techniques Coupled with X-ray Tomography

Deep geological storage of radioactive waste foresees cementitious materials as reinforcement of tunnels and as backfill. Bentonite is proposed to enclose spent fuel canisters and as drift seals. Sand/bentonite (s/b) is foreseen as backfill material of access galleries or as drift seals. The emplacement of cementitious material next to clay material generates an enormous chemical gradient in pore-water composition that drives diffusive solute transport. Laboratory studies and reactive transport modeling predicted significant mineral alteration at and near interfaces, mainly resulting in a decrease of porosity in bentonite. The goal of this thesis was to characterize and quantify the cement/bentonite interactions both spatially and temporally in laboratory experiments. A newly developed mobile X-ray transparent core infiltration device was used to perform X-ray computed tomography (CT) scans without interruption of running experiments. CT scans allowed tracking the evolution of the reaction plume and changes in core volume/diameter/density during the experiments. In total 4 core infiltration experiments were carried out for this study with the compacted and saturated cores consisting of MX-80 bentonite and sand/MX-80 bentonite mixture (s/b; 65/35%). Two different high-pH cementitious pore-fluids were infiltrated: a young (early) ordinary Portland cement pore-fluid (APWOPC; K+–Na+–OH-; pH 13.4; ionic strength 0.28 mol/kg) and a young ‘low-pH’ ESDRED shotcrete pore-fluid (APWESDRED; Ca2+–Na+–K+–formate; pH 11.4; ionic strength 0.11 mol/kg). The experiments lasted between 1 and 2 years. In both bentonite experiments, the hydraulic conductivity was strongly reduced after switching to high-pH fluids, changing eventually from an advective to a diffusion-dominated transport regime. The reduction was mainly induced by mineral precipitation and possibly partly also by high ionic strength pore-fluids. Both bentonite cores showed a volume reduction and a resulting transient flow in which pore-water was squeezed out during high-pH infiltration. The outflow chemistry was characterized by a high ionic strength, while chloride in the initial pore water got replaced as main anionic charge carrier by sulfate, originating from gypsum dissolution. The chemistry of the high-pH fluids got strongly buffered by the bentonite, consuming hydroxide and in case of APWESDRED also formate. Hydroxide got consumed by mineral reactions (saponite and possibly talc and brucite precipitation), while formate being affected by bacterial degradation. Post-mortem analysis showed reaction zones near the inlet of the bentonite core, characterized by calcium and magnesium enrichment, consisting predominately of calcite and saponite, respectively. Silica got enriched in the outflow, indicating dissolution of silicate-minerals, identified as preferentially cristobalite. In s/b, infiltration of APWOPC reduced the hydraulic conductivity strongly, while APWESDRED infiltration had no effect. The reduction was mainly induced by mineral precipitation and probably partly also by high ionic strength pore-fluids. Not clear is why the observed mineral precipitates in the APWESDRED experiment had no effect on the fluid flow. Both s/b cores showed a volume expansion along with decreasing ionic strengths of the outflow, due to mineral reactions or in case of APWESDRED infiltration also mediated by microbiological activity, consuming hydroxide and formate, respectively. The chemistry of the high-pH fluids got strongly buffered by the s/b. In the case of APWESDRED infiltration, formate reached the outflow only for a short time, followed by enrichment in acetate, indicating most likely biological activity. This was in agreement to post-mortem analysis of the core, observing black spots on the inflow surface, while the sample had a rotten-egg smell indicative of some sulfate reduction. Post-mortem analysis showed further in both cores a Ca-enrichment in the first 10 mm of the core due to calcite precipitation. Mg-enrichment was only observed in the APWOPC experiment, originating from newly formed saponite. Silica got enriched in the outflow of both experiments, indicating dissolution of silicate-minerals, identified in the OPC experiment as cristobalite. The experiments attested an effective buffering capacity for bentonite and s/b, a progressing coupled hydraulic-chemical sealing process and also the preservation of the physical integrity of the interface region in this setup with a total pressure boundary condition on the core sample. No complete pore-clogging was observed but the hydraulic conductivity got rather strongly reduced in 3 experiments, explained by clogging of the intergranular porosity (macroporosity). Such a drop in hydraulic conductivity may impact the saturation time of the buffer in a nuclear waste repository, although the processes and geometry will be more complex in repository situation.

Mechanical behavior of alkali-cement as function of the temperature.

This investigation reports on a comparative study of the mechanical behavior at different temperatures of three different alkali-activated fly ash pastes chemically activated using sodium silicate. A control Portland cement (OPC) was used as a reference. In an attempt to simulate the conditions prevailing in the event of accidental fire, post-thermal mechanical tests were performed to determine the residual strength. It has therefore been established that FA based cements can be fabricated for construction purposes and these materials have great potential for fire resistance applications.

Nanoindentation Relaxation Study and Micromechanics of Cement-Based Materials

Ce travail évalue le comportement mécanique des matériaux cimentaires à différentes échelles de distance. Premièrement, les propriétés mécaniques du béton produit avec un bioplastifiant à base de microorganismes efficaces (EM) sont etudiées par nanoindentation statistique, et comparées aux propriétés mécaniques du béton produit avec un superplastifiant ordinaire (SP). Il est trouvé que l’ajout de bioplastifiant à base de produit EM améliore la résistance des C–S–H en augmentant la cohésion et la friction des nanograins solides. L’analyse statistique des résultats d’indentation suggère que le bioplastifiant à base de produit EM inhibe la précipitation des C–S–H avec une plus grande fraction volumique solide. Deuxièmement, un modèle multi-échelles à base micromécanique est dérivé pour le comportement poroélastique de la pâte de ciment au jeune age. L’approche proposée permet d’obtenir les propriétés poroélastiques requises pour la modélisation du comportoment mécanique partiellement saturé des pâtes de ciment viellissantes. Il est montré que ce modèle prédit le seuil de percolation et le module de Young non drainé de façon conforme aux données expérimentales. Un metamodèle stochastique est construit sur la base du chaos polynomial pour propager l’incertitude des paramètres du modèle à travers plusieurs échelles de distance. Une analyse de sensibilité est conduite par post-traitement du metamodèle pour des pâtes de ciment avec ratios d’eau sur ciment entre 0.35 et 0.70. Il est trouvé que l’incertitude sous-jacente des propriétés poroélastiques équivalentes est principalement due à l’énergie d’activation des aluminates de calcium au jeune age et, plus tard, au module élastique des silicates de calcium hydratés de basse densité.