Influence of pH and fluoride concentration on titanium passivating layer: stability of titanium dioxide.

Titanium and titanium alloy biomaterials are considered as being corrosion resistant, because of the formation of a titanium oxide passivating layer, which is not easily soluble even in acid media. In odontology, using dental preparations containing fluorides could alter the behaviour of titanium. After a review of the experimental works dealing with the effects of fluoride ions at different pH on titanium salts in solution, it was proceeded to a thermodynamic investigation at 25 degrees C in the range of concentrations and pH corresponding to the solutions commonly used. Such a study gives a possibility to specify which species could be involved in the corrosion reaction to calculate the corresponding potentials, and lastly to define the domain of insolubility of TiO(2). From these results, the reaction of titanium in laboratory spontaneous corrosion and voltammetric experiments was interpreted. From the recent experiments described and discussed in this article, it becomes evident that the close connection with the results obtained in this study contributes to support our thermodynamic model.

About a synthetic saliva for in vitro studies.

Numerous artificial salivas have been used during studies in odontology. These salivas have compositions, which are more or less the same as that of natural saliva. In this article, we are presenting a discussion about the various media described in the related literature. A review of nearly 60 artificial salivas was carried out to clarify the role of some of the compounds most frequently met in the proposed formulae. The study focused on the buffer effect, the role played by CO(2) gas and the presence of calcium ions, hydrogenocarbonates, hydrogenophosphates and thiocyanates. The SAGF medium, which we proposed some years ago, was used as a reference and some in vitro behavioral tests of dental biomaterials were studied in a comparative way. Using the SAGF medium allowed us to specify the mode of fluoride ions release from glass ionomer cements and the corrosion behavior of the dental amalgams.

Corrosion by galvanic coupling between carbon fiber posts and different alloys.

OBJECTIVES: The corrosion of metal type (NiCr, copper, etc.) posts in post and core restorations has been a well known fact over the last few years. A new generation of carbon fiber posts is now playing an extensive role in dental prosthetics, but these posts may, in some cases come in contact with alloys used for restoration purposes. The objective of this paper is to study the electrochemical behaviour of these posts in an artificial SAGF medium (Artificial Saliva Gal Fovet) for comparison with that observed for different alloys (gold, NiCr and amalgams) in the same medium, and to assess the coupling that might occur between these posts and alloys. METHODS: Posts of different diameters (1-2.1 mm) were molded in resin, thus forming 10 x 3 mm pads that were mounted on a rotating electrode. Pads of identical dimensions were also made for each alloy. Voltammograms (current-tension curves) were plotted for every material in the SAGF medium at 25 degrees C with normal aeration and low aeration (bubbling purified argon) using a potentiometer with three electrodes to determine the position of the zero current potentials. Evans graphs were then plotted once the anode part of the alloy curves and the cathode part of the post curves had been processed with computer software. The potentials and the maximum coupling current densities were estimated. RESULTS: Posts may be involved in galvanic coupling in the presence of oxygen. Galvanic activity in an aerated solution is highly probable upon contact with amalgams, but may also occur if the material in contact is NiCr alloy. Coupling between precious alloys and posts is improbable and can only induce very low currents in the presence of oxygen. SIGNIFICANCE: This study devoted to coupling of carbon fiber posts and metals in the mouth, attracts attention to the fact that a corrosion reaction can be set-up in the infiltration conditions relevant to the prosthetic restoration.

Formation constants beta(2) of calcium and magnesium fluorides at 25 degrees C.

Until now, scientific work on the reactions of the complexation in water of fluoride ions with calcium or magnesium ions considered only soluble order 1 complexes (CaF(+) and MgF(+)). The precipitation of the compounds CaF(2) and MgF(2) did not take into account the preliminary formation in solution of these order 2 complexes (CaF(2)(0) and MgF(2)(0)). We therefore studied their formation using a direct potentiometric method in the F(-) ion-selective electrode at 25 degrees C. This experiment, together with a computerized thermodynamic study, allowed us to determine the values of formation constants at ionic strength equal to zero: log beta (CaF (2)(0))=5.7 and log beta (CaF (2)(0))=3.2 , as well as limiting solubilities: S(CaF(2))=10(-4.8) and S(MgF(2))=10(-5) mol l(-1). Then, some examples were studied showing the necessity to take into account the formation constant of CaF(2): the supersaturation of solutions, the validity of results from the fluoride selective electrode, the difference between released fluoride in distilled water and in artificial saliva in restorative dentistry, the fluoride concentration in hard waters and its health consequences.

In vitro fluoride release from restorative materials in water versus artificial saliva medium (SAGF).

OBJECTIVES: An extensive number of investigations have focused in recent years on the process of fluoride release by glass-ionomer cements. In order to compare the fluoride release of two recent resin-modified glass-ionomer cements (RMGICs) and one compomer, we investigated the initial and subsequent fluoride release in distilled water and in a mineral medium with composition similar to saliva (SAGF), as well as the renewal effect of the media on the release. METHOD: A preliminary thermodynamic study defined conditions under which the measurements by fluoride-selective electrode potentiometry were not affected by the presence of Ca2+ ions in SAGF. Disk-shaped samples (5 mm x 3 mm) for each material were placed in 5 ml of distilled water (n = 12) or 5 ml of SAGF (n = 12) and fluoride released was measured after 1, 2 and 7 days. For the investigation of medium renewal effect, RMGIC sample were dipped into distilled water for 5 days. Subsequently 12 samples of each material were placed for 7 days into water or SAGF, with or without daily renewal of the medium before fluoride-release measurements. The elements present on the surface of the RMGICs were analyzed by scanning electron microscopy. RESULTS: RMGICs released significantly more fluoride in water than in artificial saliva. The presence of CaF2 at the interface accounts for this phenomenon. The thickness of the CaF2 layer depends on the speed of its initial formation and renewal of the testing medium. A pattern of CaF2 formation was proposed.

Calcium carbonate solubility: a reappraisal of scale formation and inhibition.

Considerable disparity exists in the published thermodynamic data for selected species in the Ca(2+) /CO(2)/H(2)O system near 25 degrees C and 1 atm pressure. Some authors doubt the significance of CaCO(3)(0)aq) complexes although there is experimental evidence of their occurrence. Evaluation of all the published experimental and estimated data for aqueous calcium carbonate species confirms that the consistent set of constants given by Plummer and Busenberg in 1982 is the best available, and suggests a formation constant log beta = 3.22 for CaCO(3)(0)(aq). This value was confirmed by additional experimental data and calculations using a specially developed computer program. The solubility s and solubility product K(s) are critically evaluated for each solid polymorph (amorphous CaCO(3), ikaite, vaterite, aragonite and calcite) using a hydrated ion pair model and we give coherent explanations for the calcium carbonate precipitation/dissolution process and the existence of supersaturated waters. The practical cases of scale formation and its inhibition by phosphonate-type compounds are discussed and explained with the same model, taking into account the CaCO(3)(0)(aq) species.

Thermodynamic study in aqueous solutions of weakly soluble ionic compounds.

Any investigation for a better knowledge of precipitation/dissolution problems necessitates the availability of all the beta formation constants of the uncharged soluble species (ion-pair). Several difficulties dealing with solubility measurements are briefly reviewed, especially related to phase structure variations, time-lag or supersaturation phenomena. Thanks to some thermodynamic considerations, the evolution of the uncharged soluble species with hydration and solid phase modifications can give a new explanation about the observed dispersion in literature values for some weakly soluble ionic compounds. When not given elsewhere, the evaluation of thermodynamic data of interest (formation constants, solubility product, etc.) is made possible according to given methods.