Polarisation studies on the Raman spectra of cubic crystals - Part II: Calcium fluoride and potassium aluminium sulphate

Polarisation characters of the Raman lines of calcium fluoride (fluorspar) and potassium aluminium sulphate (alum) were investigated under the following conditions. Unpolarised light was incident normally on a face of the crystal making an angle 22.5° with a cubic face and the light scattered transversely along a cubic axis was analysed by a double image prism kept with its principal axes inclined at 45° to the vertical. Under these conditions the depolarisation factors of the Raman lines belonging to the totally symmetric (A), the doubly degenerate (E) and the triply degenerate (F) modes should be respectively =1, >1 and <1. The characteristic Raman line of CaF2 at 322 cm-1 exhibited a depolarisation value less than 1, showing thereby that the corresponding mode is a triply degenerate one (F). The Raman lines observed in the spectrum of K-alum were also classified and the results were compared with those given by previous investigators using standard crystal orientations.

Copper phthalocyanine organic thin-film transistors with calcium fluoride gate insulator

We report the fabrication of organic thin-film transistors (OTFTs) with copper phthalocyanine (CuPc) as the semiconductor and calcium fluoride (CaF2) as the gate dielectric on the glass substrate. The fabricated transistors show a gate voltage dependent carrier field effect mobility that ranges from 0.001 to 0.5 cm(2) V-1 s(-1). In the devices, the CaF2 dielectric is formed by thermal evaporation; thus OTFTs with a top-gate structure can be fabricated. This provides a convenient way to produce high-performance OTFTs on a large scale and should be useful for the integration of organic displays.

AN INTEGRATED CALCIUM-FLUORIDE CRYSTAL IR THIN-LAYER CELL AND ITS APPLICATION TO IDENTIFICATION OF ELECTROCHEMICAL REDUCTION PRODUCT OF BILIRUBIN

An integrated CaF2 crystal optically transparent infrared (ir) thin-layer cell was designed and constructed without using any soluble adhesive materials. It is suitable for both aqueous and nonaqueous systems, and can be used not only in ir but also in uv-vis studies. Excellent electrochemical and spectroelectrochemical responses were obtained in evaluating this cell by cyclic voltammetry and steady-state potential step measurements for both ir and uv-vis spectrolectrochemistry with ferri/ferrocyanide in aqueous solution, and with ferrocene/ferrocenium in organic solvent as the testing species, respectively. The newly designed ir cell was applied to investigate the electrochemical reduction process of bilirubin in situ, which provided direct information for identifying the structure of the reduction product and proposing the reaction mechanism.

Radiation-induced defects in calcium fluoride and their influence on material properties under 193 nm laser irradiation

Calcium fluoride (CaF2) is one of the key lens materials in deep-ultraviolet microlithography because of its transparency at 193 nm and its nearly perfect optical isotropy. Its physical and chemical properties make it applicable for lens fabrication. The key feature of CaF2 is its extreme laser stability. rnAfter exposing CaF2 to 193 nm laser irradiation at high fluences, a loss in optical performance is observed, which is related to radiation-induced defect structures in the material. The initial rapid damage process is well understood as the formation of radiation-induced point defects, however, after a long irradiation time of up to 2 months, permanent damage of the crystals is observed. Based on experimental results, these permanent radiation-induced defect structures are identified as metallic Ca colloids.rnThe properties of point defects in CaF2 and their stabilization in the crystal bulk are calculated with density functional theory (DFT). Because the stabilization of the point defects and the formation of metallic Ca colloids are diffusion-driven processes, the diffusion coefficients for the vacancy (F center) and the interstitial (H center) in CaF2 are determined with the nudged elastic band method. The optical properties of Ca colloids in CaF2 are obtained from Mie-theory, and their formation energy is determined.rnBased on experimental observations and the theoretical description of radiation-induced point defects and defect structures, a diffusion-based model for laser-induced material damage in CaF2 is proposed, which also includes a mechanism for annealing of laser damage. rn

The influence of saliva on the dissolution of calcium fluoride after application of different fluoride gels in vitro

OBJECTIVE: To determine the formation and dissolution of calcium fluoride on the enamel surface after application of two fluoride gel-saliva mixtures. METHOD AND MATERIALS: From each of 80 bovine incisors, two enamel specimens were prepared and subjected to two different treatment procedures. In group 1, 80 specimens were treated with a mixture of an amine fluoride gel (1.25% F-; pH 5.2; 5 minutes) and human saliva. In group 2, 80 enamel blocks were subjected to a mixture of sodium fluoride gel (1.25% F; pH 5.5; 5 minutes) and human saliva. Subsequent to fluoride treatment, 40 specimens from each group were stored in human saliva and sterile water, respectively. Ten specimens were removed after each of 1 hour, 24 hours, 2 days, and 5 days and analyzed according to potassium hydroxide-soluble fluoride. RESULTS: Application of amine fluoride gel resulted in a higher amount of potassium hydroxide-soluble fluoride than did sodium fluoride gel 1 hour after application. Saliva exerted an inhibitory effect according to the dissolution rate of calcium fluoride. However, after 5 days, more than 90% of the precipitated calcium fluoride was dissolved in the amine fluoride group, and almost all potassium hydroxide-soluble fluoride was lost in the sodium fluoride group. Calcium fluoride apparently dissolves rapidly, even at almost neutral pH. CONCLUSION: Considering the limitations of an in vitro study, it is concluded that highly concentrated fluoride gels should be applied at an adequate frequency to reestablish a calcium fluoride-like layer.

Preparation and optimization of calcium fluoride particles for dental applications.

Fluorides are used in dental care due to their beneficial effect in tooth enamel de-/remineralization cycles. To achieve a desired constant supply of soluble fluorides in the oral cavity, different approaches have been followed. Here we present results on the preparation of CaF2 particles and their characterization with respect to a potential application as enamel associated fluoride releasing reservoirs. CaF2 particles were synthesized by precipitation from soluble NaF and CaCl2 salt solutions of defined concentrations and their morphology analyzed by scanning electron microscopy. CaF2 particles with defined sizes and shapes could be synthesized by adjusting the concentrations of the precursor salt solutions. Such particles interacted with enamel surfaces when applied at fluoride concentrations correlating to typical dental care products. Fluoride release from the synthesized CaF2 particles was observed to be largely influenced by the concentration of phosphate in the solution. Physiological solutions with phosphate concentration similar to saliva (3.5 mM) reduced the fluoride release from pure CaF2 particles by a factor of 10-20 × as compared to phosphate free buffer solutions. Fluoride release was even lower in human saliva. The fluoride release could be increased by the addition of phosphate in substoichiometric amounts during CaF2 particle synthesis. The presented results demonstrate that the morphology and fluoride release characteristics of CaF2 particles can be tuned and provide evidence of the suitability of synthetic CaF2 particles as enamel associated fluoride reservoirs.

Effect of calcium pre-rinse and fluoride dentifrice on remineralisation of artificially demineralised enamel and on the composition of the dental biofilm formed in situ

Objective: This in situ blind crossover study investigated the effect of calcium (Ca) rinse prior to the use fluoride (F) dentifrice on remineralisation of artificially demineralised enamel and on the composition of biofilm. Design: During four phases of 14 days, 10 volunteers wore appliances containing two artificially demineralised bovine enamel blocks. Three times a day, they rinsed with 10 mL, of Ca (150 mM) or placebo rinse (1 min). A slurry (1:3, w/v) of F (1030 ppm) or placebo dentifrice was dripped onto the blocks. During I min, the volunteers brushed their teeth with the respective dentifrice. The appliance was replaced into the mouth and the volunteers rinsed with water. The biofilm formed on the blocks was analysed for F and Ca. Enamel alterations were evaluated by the percentage of surface microhardness change (%SMHC), cross-sectional microhardness (% mineral volume) and alkali-soluble F analysis. Data were analysed by ANOVA (p < 0.05). Results: the use of the Ca pre-rinse before the F dentifrice produced a six- and four-fold increase in biofilm F and Ca concentrations, respectively. For enamel, the remineralisation was significantly improved by the Ca pre-rinse when compared to the other treatments. There was a significantly higher concentration of alkali-soluble F in enamel when the F dentifrice was used, but the Ca pre-rinse did not have any significant additive effect. Conclusions: According to our protocol, the Ca pre-rinse significantly increased biofilm F concentration and, regardless the use of F dentifrice, significantly enhanced the remineralisation of artificially demineralised enamel. (c) 2007 Elsevier Ltd. All rights reserved.

In vitro assessment of an experimental coat applied over fluoride varnishes

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

Urinary fluoride output in children following the use of a dual-fluoride varnish formulation

Objective: This study evaluated the bioavailability of fluoride after topical application of a dual-fluoride varnish commercially available in Brazil, when compared to Duraphat T. Material and methods: The urinary fluoride output was evaluated in seven 5-year-old children after application of the fluoride varnishes, in two different phases. In the first phase (I), children received topical application of the fluoride varnish Duofluorid XII (2.92% fluorine, calcium fluoride + 2.71% fluorine, sodium fluoride, FGM (TM)). After 1-month interval (phase II), the same amount (0.2 mL) of the fluoride varnish Duraphat (2.26% fluorine, sodium fluoride, Colgate T) was applied. Before each application all the volunteers brushed their teeth with placebo dentifrice for 7 days. Urinary collections were carried out 24 h prior up to 48 h after the applications. Fluoride intake from the diet was also estimated. Fluoride concentration in diet samples and urine was analyzed with the fluoride ion-specific electrode and a miniature calomel reference electrode coupled to a potentiometer. Data were tested by ANOVA and Tukey's post hoc test (p < 0.05). Results: There were significant differences in the urinary fluoride output between phases I and II. The use of Duofluorid XII did not significantly increase the urinary fluoride output, when compared to baseline levels. The application of Duraphat caused a transitory increase in the urinary fluoride output, returning to baseline levels 48 h after its use. Conclusions: The tested varnish formulation, which has been shown to be effective in in vitro studies, also can be considered safe.

In situ evaluation of a low fluoride concentration gel with sodium trimetaphosphate in enamel remineralization

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

Differences in loosely bound fluoride formation and anticaries effect of resin-based fluoride varnishes

International Journal of Paediatric Dentistry 2013; 23: 166-172 Objective. Our in vitro study evaluated calcium fluoride formation in enamel and the anticaries effect of seven resin-based varnishes under cariogenic challenge. Methods. Enamel blocks were subjected to pH cycling. The experimental groups received fluoride varnish application, the positive control received topical fluoride gel treatment, and the negative control did not receive any treatment. The pH cycling surface hardness (SH1) and integrated loss of subsurface hardness (ΔKHN) were then determined. We measured the amount of fluoride released into the demineralizing and remineralizing (DE-RE) solutions used in pH cycling. The fluoride concentration in the enamel was determined 24h after application of the products as loosely bound fluoride and firmly bound fluoride. Results. Higher deposits of loosely bound fluoride were observed for Duofluorid, followed by Biophat. For Duraphat, Bifluorid, Duraflur, and Duofluorid, no difference was observed in the SH1 and ΔKHN values, with the lowest mineral loss compared to the other groups. The Bifluorid and Duofluorid groups released high fluoride amounts into the DE-RE, and statistically significant difference was noted between them. Conclusions. The anticaries effect showed no correlation with higher deposited fluoride amounts, resin type, or fluoride source. © 2012 John Wiley & Sons Ltd, BSPD and IAPD.

Effect of trimetaphosphate and fluoride association on hydroxyapatite dissolution and precipitation in vitro

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

The effect of monoalkyl phosphates and fluoride on dissolution of hydroxyapatite, and interactions with saliva

The aims were to investigate the effect of monoalkyl phosphates (MAPs) and fluoride on dissolution rate of native and saliva-coated hydroxyapatite (HA). Fluoride at 300 mg/l (as NaF) inhibited dissolution of native HA by 12%, while potassium and sodium dodecyl phosphates (PDP, SDP), at 0.1% or higher, inhibited dissolution by 26-34%. MAPs, but not fluoride, also showed persistence of action. MAPs at 0.5% and fluoride at 300 mg/l were then tested separately against HA pre-treated with human saliva for 2 or 18 h. Agents were applied with brushing to half the specimens, and without brushing to the other half. In control (water-treated) specimens, pre-treatment of HA with human saliva reduced dissolution rate on average by 41% (2 h) and 63% (18 h). Brushing did not have a statistically significant effect on dissolution rate of saliva-coated specimens. In brushed specimens, fluoride significantly increased the inhibition due to 2- or 18-hour saliva pre-treatment. It is hypothesised that brushing partially removes the salivary film and allows KOH-soluble calcium fluoride formation at the surfaces of HA particles. Inhibition was reduced by PDP in 2-hour/non-brushed specimens and in 18-hour/brushed specimens. PDP did not affect dissolution rates in the remaining groups and SDP did not affect dissolution rate in any group. Possible reasons for these variable results are discussed. The experiments show that pre-treatment with saliva can significantly modify results of tests on potential anti-erosive agents and it is recommended that saliva pre-treatment should be a routine part of testing such agents.

Dephosphorisation of Iron–Chrome Alloy with Ca–CaF2 Melt during Electro Slag Refining

Calcium-calcium fluoride melt was used to remove phosphorus from the ferro-chrome alloy (64.5 wt% Cr, 0.15 wt% P) during electro slag refining process. The effect of atmosphere and deoxidisers, viz. Al, Fe–Mo and misch metal were also studied during dephosphorisation reaction. The thermodynamic properties of Ca–CaF2 melt is calculated from a known phase diagram and these results are discussed in relation with the dephosphorisation reaction.

Some studies on a solid state sulphur probe for coal gasification system

Measurements on the solid electrolyte cell(Ar -b H2 ~ H2S/CaS + CaF2 ~- ( P t ) / / C a F 2 / / ( P t )-~- CaF2 ~ CaS/H2S ~- H2 ~- At) show that the emf of the cell is directly related through the Nernst equation to the difference in sulfur potentials established at the two Ar ~- H2 ~ H2S/electrode interfaces. The electrodes are designed to convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient with the aid of the reaction, CaF2(s) ~ 1~ S2(g)-e CaS(s) ~- F2(g). The response time of the probe varies from approximately 9 hr at 990~ to 2.5 hr at 1225~ The conversion of calcium sulfide and/or calcium fluoride into calcium oxide should not be a problem in anticipated commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.