Histidine buffering of acidic fluoridated solutions increases CaF<sub>2</sub>-like formation on carious enamel

To compare the dissolution time of two solutions, a fluoride solution and a sodium hypochlorite solution, both saturated with sodium chloride, during the electrochemical dissolution of instruments consisting of conventional nickel-titanium alloy and Gold thermomechanically treated nickel-titanium alloy. Two solutions, an NaF solution consisting of 12gL-1 NaF with 180gL-1 NaCl and an NaOCl solution consisting of 2.5% NaOCl with 180gL-1 NaCl, were evaluated in a polarization test of a sample of 48 ProTaper Universal F1 (PTU F1) and WaveOne Gold Small (WOGS) instruments. The electric potentials were 0.5V and 5V for the NaF and NaOCl solutions, respectively. The electrochemical cell consisted of three electrodes for the polarization test of the PTU F1 and WOGS instruments, which had 6mm of the tip immersed in the test solutions. The electric current was recorded for 540s. If complete dissolution of the immersed tip occurred in less than the expected time, the experiment was considered complete. The time variations (in seconds) of the instruments in the solutions were measured. Data were subjected to statistical analysis using the Mann-Whitney, Kruskal-Wallis and Dunn tests. The corrosion patterns of the instruments were evaluated by scanning electron microscopy (SEM). The NaF and NaOCl solutions were associated with significantly different (P=0.000) dissolution times of the instrument, with mean values of 12.96s and 83.63s, respectively. There was no significant difference (P=0.649) in dissolution time between the PTU F1 and WOGS instruments. NaF and NaOCl solutions were able to electrochemically dissolve PTU F1 and WOGS instruments. However, the NaF solution achieved dissolution in significantly less time.

It is well established that the fractionation of Li–F granitic magmas at depth leads to the accumulation of flux elements such as F and Li, and metal cations such as Ta and Nb in residual melts. However, it remains to be determined whether magmatic fractionation is sufficient to concentrate Nb and Ta into economically significant quantities, and what role hydrothermal–metasomatic processes play in the formation of such ore deposits. In the literature, reliable data about the solubility of Ta and Nb in hydrothermal solutions is missing or incomplete. This study provides a quantitative experimental estimation of the possible contribution from hydrothermal processes in Ta enrichment in cupolas of albitized and greisenized Li–F granite. Experimental studies of Ta2O5 and columbite–tantalite (Mn,Fe)(Nb,Ta)2O6 solubility were carried out in fluoride solutions consisting of HF, NaF, KF, and LiF. At low fluoride concentrations (0.01 and 0.1 m), Ta2O5 solubility at 550°C and 100 MPa under Co–CoO oxidizing conditions is low (near 10−5–10−4 m) in all fluoride solutions (HF, NaF, KF, LiF). At high fluoride concentrations (1 and 2 m) the highest Ta2O5 concentrations (10−1 m) were detected in HF solutions. In KF, NaF, and LiF solutions, the Ta2O5 solubility is also high (10−3–10−2 m). The dependence of columbite–tantalite (Nb2O5-59 wt. %, Ta2O5-18 wt. %) solubility as a function of solution composition, T, and P has also been investigated. Tantalum and Nb concentrations have the highest values in HF solutions at reduced conditions (up to 10−3 to 10−2 m Ta in 1 m HF). In 1 m NaF solutions, the concentrations of Nb and Ta are, respectively, 2.5 and 3 orders of magnitude less than those in the 1 m HF solutions. Solubility of Ta and Nb in KF solutions has intermediate values. It is established that in NaF and KF solutions the dependence of solubility on pressure is distinctly negative. The Nb and Ta contents increase with increasing concentrations of HF and KF in solution, however, they do not change with increasing NaF concentration. In NaHCO3, Na2CO3, and HCl solutions columbite–tantalite solubility is low. Even in 1 m chloride solutions the content is within the limits of 10−5 m for Nb and 10−6 to 10−8 m for Ta. We conclude that hydrothermal transport of Ta and Nb is possible only in concentrated fluoride solutions.

Susceptibility to delayed fracture of alpha–beta titanium alloy in fluoride solutions

A mathematical model for the mechanism of calcium fluoride formation on hydroxyapatite in buffered fluoride solutions is proposed. It takes into account the physical and chemical processes that occur during the reaction. With the model it is possible to evaluate a priori the fluoride uptake potential of fluoride solutions.

The fracture of commercial pure titanium in acid and neutral fluoride solutions has been examined by a sustained tensile-loading test and hydrogen thermal desorption analysis. It was found that the fracture of titanium occurred in neutral 2.0% NaF solution as well as in 2.0% acidulated phosphate fluoride (APF) solution. The time to fracture decreased with increasing applied stress in both 2.0% APF and 2.0% NaF solutions. In the case of the same applied stress, the time to fracture in the 2.0% APF solution was shorter than that in the 2.0% NaF solution. General corrosion was exhibited on the side surface of the tested specimens. The formation of sodium titanium fluoride was observed on the surface of the immersed specimens in the 2.0% APF solution. Hydrogen desorption of the tested specimen in the 2.0% APF solution was observed with a peak at approximately 600 degrees C. The amount of absorbed hydrogen was >300 mass ppm in the 2.0% APF solution under an applied stress for 24 h. The results of the present study imply that applying stress to titanium by immersing in fluoride solutions leads to the degradation of its mechanical properties.

Effects of potential on hydrogen absorption and desorption behaviors of titanium in neutral fluoride solutions

Titanium fluoride (TiF4) reduces mineral loss and lesion depth more effectively than sodium fluoride (NaF). However, the pH values of TiF4 and NaF solutions are different. This study aimed to evaluate the effects of TiF4 solution on the inhibition of demineralization and elemental distribution in root dentin in comparison with NaF solution at the same pH and fluoride concentrations. This study was conducted using 0.5% TiF4 or 0.675% NaF solution adjusted to pH 5 or pH 7. Bovine dentin specimens of 200 [Formula: see text]m thickness were subjected to pH cycling (pH 4.5 and 7.0; 6 cycles/day; simulated oral conditions) for eight weeks to prepare artificial carious dentin. During this cycle, the specimens were soaked in each solution once a week for 5 min. The control group involved no fluoride application during the test period. After cycling, the demineralization depth was measured and the calcium, fluorine, and titanium distributions were analyzed and calculated using an in-air micro-proton-induced X-ray emission (PIXE)/proton-induced gamma emission (PIGE) system at TIARA. At pH 7, TiF4 solution yielded a lower lesion depth than the NaF solution. The NaF solution at pH 7 showed lower fluorine concentration than that with the other fluoride solutions. Thus, TiF4 is more effective in inhibiting demineralization than NaF in a solution adjusted to pH 7. Moreover, the presence of titanium may strengthen the tooth structure.

The susceptibility to hydrogen absorption and hydrogen thermal desorption of titanium alloys has been investigated in a neutral 2.0% NaF solution at 37°C under various applied cathodic potentials. Ti-0.2Pd, Ti-6Al-4V and Ti-11.3Mo-6.6Zr-4.3Sn alloys absorb hydrogen under less noble potentials than −1.5 V, −1.9 V and −1.4 V versus a saturated calomel electrode, respectively. The amounts of absorbed hydrogen of Ti-0.2Pd, Ti-6Al-4V and Ti-11.3Mo-6.6Zr-4.3Sn alloys under an applied potential of −2.0 V for 24 h are approximately 1200, 100 and 1100 mass ppm, respectively. Upon immersion in the 2.0% NaF solution under an applied potential, the hydrogen thermal desorption behavior of Ti-0.2Pd alloy differs from those immersed in acid fluoride solutions, whereas the hydrogen thermal desorption behaviors of Ti-6Al-4V and Ti-11.3Mo-6.6Zr-4.3Sn alloys are similar to those immersed in acid fluoride solutions. The present results indicate that in a neutral fluoride solution, the effects of an applied potential on the hydrogen absorption and desorption behaviors of Ti-6Al-4V alloy are considerably smaller than those of commercial pure titanium reported previously, Ti-0.2Pd and Ti-11.3Mo-6.6Zr-4.3Sn alloys.

Evaluation of hydrogen absorption properties of Ti–0.2 mass% Pd alloy in fluoride solutions

Effect of TiF4/NaF and chitosan solutions on the development of enamel caries under a microcosm biofilm model

Historically, there has been considerable debate concerning the roles of loosely bound (calcium fluoride) and firmly bound (fluorapatite) fluoride for caries prevention. Research now shows that fluorapatite (FAP) is a finite reaction product of enamel/apatite fluoridation with or without CaF2 formation, suggesting that CaF2 always be considered as a supplement to, rather than a substitute for, FAP formation. In the presence of low levels of fluoride in the solution phase, the crystallization of hydroxyapatite is enhanced, while the corresponding dissolution is retarded. Fluoride in the bulk FAP or CaF2 solid phase, in contrast, has limited impact on crystal growth or dissolution kinetics. Both FAP and CaF2 can provide F to the solution phase to enhance remineralization and retard demineralization of enamel HAP crystallites. The FAP provides most of this F under low pH conditions, while CaF2 provides F at neutral or lower pH. The reactivity of fluoride on sound and carious enamel differs significantly. Carious enamel acquires more fluoride, acquires it more quickly, and itself acts as a source of retained fluoride in comparison with the more limited reactivity of sound enamel. Overall, the most important question concerning fluoride reactivity relates to its efficiency in enhancing remineralization or retarding demineralization processes. This is influenced not only by the reaction products, e.g., loosely or firmly bound fluoride, but also by the nature of the enamel substrate and frequency of application of the topical fluoridating agent. Inasmuch as the reactivity of bulk HAP is dominated by surface layers of FAP material, the debate over usefulness of various fluoride reaction products solely on a chemical level is no longer critical. Instead, all factors influencing the efficiency of a fluoridating regimen must be considered in the development of improved systems for caries prevention.

Hydrogen-related degradation of the mechanical properties of a Ni-Ti superelastic alloy has been examined by means of delayed fracture tests in acidic and neutral fluoride solutions and hydrogen thermal desorption analysis. Delayed fracture took place in both solutions; the time to fracture was shorter in the acidic solutions than in the neutral solutions with the same fluoride concentration. The time to fracture was reduced in both solutions when applied stress exceeded the critical stress for martensite transformation. In the acidic solutions, Ni-Ti superelastic alloy underwent general corrosion and absorbed substantial amounts of hydrogen. Fractographic features suggested that the delayed fracture in the acidic solutions was attributable to hydrogen embrittlement, whereas in the neutral solutions, a different fracture mode appeared associated with localized corrosion only in the vicinity of the fracture initiation area. In the neutral solutions, the amount of absorbed hydrogen was much less than that in the acidic solutions, and the delayed fracture was likely to be induced by active path corrosion accompanying hydrogen absorption. The results of the present study imply that the hydrogen-related degradation of performance of Ni-Ti superelastic alloys occurs in the presence of fluoride.

Proteins can interact with corrosion reactions in several ways. In this study, we investigated the effect of albumin on the corrosion resistance of titanium in the presence of fluoride. The effects of the NaF concentration, albumin concentration, and pH on the corrosion characteristics of commercially pure titanium (CP-Ti) were examined by means of electrochemical techniques. The corrosion resistance of titanium decreased as the NaF concentration increased and as pH decreased. The corrosion resistance of titanium in NaF solutions was improved in the presence of albumin. The natural electrode potential was elevated, and the passive current density was reduced by albumin at a concentration of 0.01%. The polarization resistance rose with increased concentrations of albumin in fluoride solution. These results showed that the albumin in saliva and dental plaque affected the corrosion resistance of CP-Ti in fluoride solution.

Alloy 22 (N06022) is the current candidate alloy to fabricate the external wall of the high level nuclear waste containers for the designated Yucca Mountain repository. It was of interest to study and compare the localized corrosion susceptibility of several commercial nickel-chromium-molybdenum alloys in 1 M NaCl, 1 M NaF and 0.5 M NaCl + 0.5 M NaF solutions at different temperatures. Standard electrochemical tests such as polarization resistance and cyclic potentiodynamic polarization were used. Studied variables included the type of halide solution, temperature and alloying elements. In general, results show that Ni-Cr-Mo alloys are highly resistant to general and localized corrosion in both chloride and fluoride solutions; however, chloride solutions seemed more aggressive than fluoride solutions.

Multi-directional forging (MDFing) can improve the various properties of metals and alloys due to the evolution of an ultrafine-grained structure. In the present study, electrochemical properties and corrosion behaviors in a fluoride solution of MDFed pure titanium (MDF-Ti) were evaluated by comparing with conventional coarse-grained pure titanium (Ti). The Eopen value of MDF-Ti was significantly higher than that of Ti. However, similar potentiodynamic polarization profiles were obtained for Ti and MDF-Ti. Immersion in NaF solution caused no severe corrosion to Ti or MDF-Ti. However, immersion in acidulate phosphate fluoride solution (APF) revealed that MDF-Ti had better corrosion resistance than Ti at shorter time immersion periods and was more susceptible to corrosion for longer immersion. Significantly less release of titanium was observed for MDF-Ti in shorter immersion periods in APF. In conclusion, MDF-Ti showed similar electrochemical behaviors to Ti and less susceptible to corrosion in shorter time APF immersion.