The nucleation of C-S-H via prenucleation clusters.

The nucleation and growth of calcium-silicate-hydrate (C-S-H) is of fundamental importance for the strength development and durability of the concrete. However, the nucleation process of C-S-H is still not fully understood. The present work investigates how C-S-H nucleates by analyzing the aqueous phase of hydrating tricalcium silicate (C3S) by applying inductively coupled plasma-optical emission spectroscopy as well as analytical ultracentrifugation. The results show that the C-S-H formation follows non-classical nucleation pathways associated with the formation of prenucleation clusters (PNCs) of two types. Those PNCs are detected with high accuracy and reproducibility and are two species of the 10 in total, from which the ions (with associated water molecules) are the majority of the species. The evaluation of the density and molar mass of the species shows that the PNCs are much larger than ions, but the nucleation of C-S-H starts with the formation of liquid precursor C-S-H (droplets) with low density and high water content. The growth of these C-S-H droplets is associated with a release of water molecules and a reduction in size. The study gives experimental data on the size, density, molecular mass, and shape and outlines possible aggregation processes of the detected species.

Development of novel tricalcium silicate-based endodontic cements with sintered radiopacifier phase.

OBJECTIVES: All implants, bone and endodontic cements need to be sufficiently radiopaque to be able to be distinguished from neighbouring anatomical structures post-operatively. For this purpose, radiopacifying materials are added to the cements to render them sufficiently radiopaque. Bismuth oxide has been quite a popular choice of radiopacifier in endodontic materials. It has been shown to cause dental discoloration. The aim of this study was to develop, characterize and assess the properties of tricalcium silicate cement with alternative radiopacifiers, which are either inter-ground or sintered to the tricalcium silicate cement. METHODS: Custom-made endodontic cements based on tricalcium silicate and 20 % barium, calcium or strontium zirconate, which were either inter-ground or sintered at high temperatures, were produced. The set materials stored for 28 days in Hank's balanced salt solution were characterized by scanning electron microscopy and X-ray diffraction analysis. Assessment of pH, leaching, interaction with physiological solution, radiopacity, setting time, compressive strength and material porosity were investigated. Mineral trioxide aggregate (MTA) Angelus was used as control. RESULTS: Addition of radiopacifying materials improved the radiopacity of the material. The sintered cements exhibited the formation of calcium zirconate together with the respective radiopacifier phase. All materials produced calcium hydroxide on hydration, which interacted with tissue fluids forming hydroxyapatite on the material surface. The physical properties of the tricalcium silicate-based cements were comparable to MTA Angelus. CONCLUSIONS: A novel method of producing radiopaque tricalcium silicate-based cements was demonstrated. The novel materials exhibited properties, which were either comparable or else improved over the control. CLINICAL RELEVANCE: The novel materials can be used to replace MTA for root-end filling, perforation repair and other clinical applications where MTA is indicated.

Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

OBJECTIVES: BioAggregate™ is a novel material introduced for use as a root-end filling material. It is tricalcium silicate-based, free of aluminium and uses tantalum oxide as radiopacifier. BioAggregate contains additives to enhance the material performance. The purpose of this research was to characterize the un-hydrated and hydrated forms of BioAggregate using a combination of techniques, verify whether the additives if present affect the properties of the set material and compare these properties to those of MTA Angelus™. METHODS: Un-hydrated and hydrated BioAggregate and MTA Angelus were assessed. Un-hydrated cement was tested for chemical composition, specific surface area, mineralogy and kinetics of hydration. The set material was investigated for mineralogy, microstructure and bioactivity. Scanning electron microscopy, X-ray energy dispersive spectroscopic analysis, X-ray fluorescence spectroscopy, X-ray diffraction and isothermal calorimetry were employed. The specific surface area was investigated using a gas adsorption method with nitrogen as the probe. RESULTS: BioAggregate was composed of tricalcium silicate, tantalum oxide, calcium phosphate and silicon dioxide and was free of aluminium. On hydration, the tricalcium silicate produced calcium silicate hydrate and calcium hydroxide. The former was deposited around the cement grains, while the latter reacted with the silicon dioxide to form additional calcium silicate hydrate. This resulted in reduction of calcium hydroxide in the aged cement. MTA Angelus reacted in a similar fashion; however, since it contained no additives, the calcium hydroxide was still present in the aged cement. Bioactivity was demonstrated by deposition of hydroxyapatite. BioAggregate exhibited a high specific surface area. Nevertheless, the reactivity determined by isothermal calorimetry appeared to be slow compared to MTA Angelus. The tantalum oxide as opposed to bismuth oxide was inert, and tantalum was not leached in solution. BioAggregate exhibited high calcium ion release early, which was maintained over the 28-day period as opposed to MTA Angelus, which demonstrated low early calcium ion release which increased as the material aged. CONCLUSIONS: The mineralogical composition of BioAggregate was different to MTA Angelus. As opposed to MTA Angelus, BioAggregate did not contain aluminium and contained additives such as calcium phosphate and silicon dioxide. As a consequence, BioAggregate reacted more slowly and formation of calcium hydroxide and leaching of calcium ions in solution were not evident as the material aged. The additives in BioAggregate modify the kinetics and the end products of hydration. CLINICAL SIGNIFICANCE: Although newer generation tricalcium silicate-based materials contain similar constituents to MTA, they do not undergo the same setting reactions, and thus, their clinical performance will not be comparable to that of MTA.

Mercury intrusion porosimetry and assessment of cement-dentin interface of anti-washout-type mineral trioxide aggregate.

INTRODUCTION: One of the disadvantages of mineral trioxide aggregate (MTA) is washout (ie, the tendency of freshly prepared cement paste to disintegrate upon early contact with physiological fluids). A novel MTA (MTA Plus; Prevest Denpro, Jammu City, India) exhibits low washout and superior physical properties when mixed with a gel instead of water. When used as a root-end filler, MTA is in contact with both bone and root dentin. This study aimed to investigate the porosity and interfacial characteristics of the novel MTA mixed with water or antiwashout gel. METHODS: Porosity was evaluated after 1 or 28 days of immersion in Hank's balanced salt solution using mercury intrusion porosimetry. The root dentin to material interface was investigated using a scanning electron microscope and energy-dispersive X-ray spectroscopy complete with line scans and elemental maps. RESULTS: Anti-washout-type MTA Plus was found to have lower initial porosity than MTA Plus mixed with water although this trend was reversed after 28 days of immersion in physiological fluid. Both materials exhibited good marginal adaptation. The diffusion of silicon, calcium, and phosphorus across the cement/dentin interface was observed. CONCLUSIONS: MTA Plus mixed with antiwashout gel was found to have lower initial porosity than MTA Plus mixed with water. Both materials exhibited good marginal adaptation and the diffusion of silicon, calcium, and phosphorous across the cement/dentin interface. Thus, the anti-washout-type MTA can be considered to be a suitable substitute for ordinary MTA in all its indications.

Porosity and root dentine to material interface assessment of calcium silicate-based root-end filling materials.

OBJECTIVES: The aim of this study was to evaluate the porosity and assess the root dentine to material interface of four root-end filling materials based on tricalcium silicate cement using two microscopy techniques. METHODS: The porosity of Bioaggregate, Biodentine, a prototype radiopacified tricalcium silicate cement (TCS-20-Zr) and intermediate restorative material (IRM) was evaluated after immersion for 28 days in Hank's balanced salt solution (HBSS) using mercury intrusion porosimetry. The root dentine to material interface of the cements when used as root-end filling materials in extracted human teeth was assessed after 28 days of dry storage and immersion in HBSS using a confocal microscope together with fluorescent tracers and also a field emission gun scanning electron microscope. RESULTS: Biodentine and IRM exhibited the lowest level or degree of porosity. The confocal microscopy used in conjunction to fluorescent tracers demonstrated that dry storage resulted in gaps at the root dentine to material interface and also cracks in the material with Biodentine being the most affected. Zinc was shown to be present in root dentine adjacent to the IRM restorations. CONCLUSIONS: Dry storage of Biodentine resulted in changes in the material microstructure and cracks at the root dentine to Biodentine interface. Furthermore, the gaps resulting from material shrinkage allowed the passage of the fluorescent microspheres thus indicating that these gaps are significant and can potentially allow the passage of micro-organisms.

The setting characteristics of MTA Plus in different environmental conditions.

AIM: Characterization and assessment of the hydration reaction of mineral trioxide aggregate (MTA) Plus exposed to different environmental conditions. METHODOLOGY: The specific surface area, surface morphology and characterization of un-hydrated MTA Plus (Avalon Biomed Inc. Bradenton, FL, USA) were investigated. The specific surface area was compared with that of ProRoot MTA (Dentsply International, Tulsa Dental Specialties, Johnson City, TN, USA). The reaction rate was determined using calorimetry, and the hydrated cement was assessed for setting time (determined using an indentation technique), and the set material was characterized using X-ray diffraction analysis, scanning electron microscopy and X-ray energy-dispersive analysis. Atomic ratio plots were drawn to establish the relationship of the hydration products. Three different environmental conditions namely dry or immersed in either water or Hank's balanced salt solution (HBSS) were used. RESULTS: Mineral trioxide aggregate Plus had a higher specific surface area than ProRoot MTA. The hydration reaction was exothermic. The setting time of MTA Plus was retarded when in contact with fluids (P < 0.001). The setting time was longer when MTA Plus was in contact with HBSS than when in contact with water (P < 0.001). Hydration of MTA Plus resulted in the formation of calcium silicate hydrate, calcium hydroxide, ettringite and monosulfate phases. Bismuth was incorporated in the calcium silicate hydrate structure. The hydration of the core material was not affected by contact with the different solutions but the periphery exhibited microcracking, leaching of calcium hydroxide, partial decalcification of calcium silicate hydrate, inhibition of hydration in contact with the physiological solution. CONCLUSIONS: The novel MTA Plus was finer than ProRoot MTA but had a similar chemical composition. MTA Plus in direct contact with fluids exhibited partial decalcification of calcium silicate hydrate in contact with the solution, microcracking and leaching of calcium hydroxide. Interaction with a physiological solution resulted in inhibition of hydration.

Interactions between municipal solid waste incinerator bottom ash and bacteria (Pseudomonas aeruginosa).

Municipal solid waste incinerator bottom ash (MSWI BA) can be used in road construction where it can become exposed to microbial attack, as it can be used as a source of oligoelements by bacteria. The extent of microbial colonization of the bottom ash and the intensity of microbial processes can impact the rate of leaching of potentially toxic elements. As a consequence, our objective was to highlight the mutual interactions between MSWI bottom ash and Pseudomonas aeruginosa, a common bacteria found in the environment. Experiments were carried out for 133 days at 25 degrees C using a modified soxhlet's device and a culture medium, in a closed, unstirred system with weekly renewal of the aqueous phase. The solid products of the experiments were studied using a laser confocal microscopy, which showed that biofilms formed on mineral surfaces, possibly protecting them from leaching. Our results show that the total mass loss after 133 days is systematically higher in abiotic medium than in the biotic one in proportions going from 31 to 53% depending on element. Ca and Sr show that rates in biotic medium was approximately 19% slower than in abiotic medium during the first few weeks. However, in the longer term, both rates decreased to reach similar end values after 15 weeks. By taking into account the quantities of each tracer trapped in the layers we calculate an absolute alteration rate of MSWI BA in the biotic medium (531 microg m(-2) d(-1)) and in the abiotic one (756 microg m(-2) d(-1)).

Effect of Pb-rich and Fe-rich entities during alteration of a partially vitrified metallurgical waste.

Lead blast furnace (LBF) slags are mainly composed of an iron-silica-lime glass matrix and minor phases such as solid solutions of Mg-Cr-rich and Fe-Zn-rich spinel crystals, crystallized iron oxides such as wüstite and metallic lead droplets. In this study, results from Raman spectroscopy, transmission and scanning electron microscopy allow to argue that widely submicron iron-rich phases are very common in the glass matrix and could have an effect on the general alteration pattern of the glass matrix during leaching experiments. Open flow tests also point out close relationships between glass alteration ability and the presence of large lead droplets. According to numerous papers on nuclear glass leaching, acidic pH encountered in such open flow tests lead to preferential releases of the main alkali-earth metal composing the glass. Altered glass is mainly characterized by relative enrichments in iron. It is induced by high calcium or calcium-silicon depletions. Surprisingly, such type of alteration layer is not uniformly spread on the slag surface. In this work, it is also assumed that previous chemical analyses of the LBF glass matrix having micrometric resolution cannot give a realistic glass composition. A short discussion is also proposed about which characterization techniques can be used to correctly identify submicron iron-rich entities and evaluate their proportions and composition.

Methodology of management of dredging operations I. Conceptual developments.

This article presents a new methodology for the management of dredging operations. Partly derived from existing methodologies (OECD, UNEP, AIPCN), its aim is to be more complete, by integrating the qualities and complementarities of former methodologies. Moreover, it was carried out in a context of sustainable development. Indeed, it supports, according to a framework of industrial ecology, the development and the implementation of solutions of waste improvement of dredged materials, in order to minimize the environmental impact of dredging. It also uses a tool of MultiCriteria Decision-Making Aid (M.C.D.M.A.), in order to integrate local characteristics. In addition, this tool, called DRAGSED, allows to a dialogue to be established between all the parties concerned with a dredging project (harbour's authorities, industrialists, municipalities, administrations, populations, associations,...). Thus, the implementation of this methodology enables consensus to be reached for the dredging solution retained. It also proposes an environmental follow-up, which will allow an evaluation during its application.

Methodology of management of dredging operations II. Applications.

This paper presents the new methodology of management of dredging operations. Derived partly from existing methodologies (OECD, PNUE, AIPCN), it aims to be more comprehensive, mixing the qualities and the complementarities of previous methodologies. The application of the methodology has been carried out on the site of the Port of Dunkirk (FRANCE). Thus, a characterization of the sediments of this site has allowed a zoning of the Port to be established in to zones of probable homogeneity of sediments. Moreover, sources of pollution have been identified, with an aim of prevention. Ways of waste improvement have also been developed, to answer regional needs, from a point of view of competitive and territorial intelligence. Their development has required a mutualisation of resources between professionals, research centres and local communities, according to principles of industrial ecology. Lastly, a tool of MultiCriteria Decision-Making Aid (M.C.D.M.A.) has been used to determine the most relevant scenario (or alternative, or action) for a dredging operation intended by the Port of Dunkirk. These applications have confirmed the relevance of this methodology for the management of dredging operations.