Calcium Tungstate Doped with Rare Earth Ions Synthesized at Low Temperatures for Photoactive Composite and Anti-Counterfeiting Applications

A precursor was prepared using a co-precipitation method to synthesize crystalline calcium tungstate. The prepared precursor was dried in an oven at 80 °C for 18 h. The dried powders, prepared without a heat treatment process, were observed in XRD analysis to be a crystalline CaWO4 phase, confirming that the synthesis of crystalline CaWO4 is possible even at low temperature. To use this crystalline CaWO4 as a light emitting material, rare earth ions were added when preparing the precursor. The CaWO4 powders doped with terbium (Tb3+) and europium (Eu3+) ions, respectively, were also observed to be crystalline in XRD analysis. The luminescence of the undoped CaWO4 sample exhibited a wide range of 300 ~ 600 nm and blue emission with a central peak of 420 nm. The Tb3+-doped sample showed green light emission at 488, 545, 585, and 620 nm, and the Eu3+-doped sample showed red light emission at 592, 614, 651, and 699 nm. Blue, green, and red CaWO4 powders with various luminescence properties were mixed with glass powder and heat-treated at 600 °C to fabricate a blue luminescent PiG disk. In addition, a flexible green and red light-emitting composite was prepared by mixing it with a silicone-based polymer. An anti-counterfeiting application was prepared by using the phosphor in an ink, which could not be identified with the naked eye but can be identified under UV light.

Thermal Evolutions to Glass-Ceramics Bearing Calcium Tungstate Crystals in Borate Glasses Doped with Photoluminescent Eu3+ Ions

Thermal evolutions of calcium-tungstate-borate glasses were investigated for the development of luminescent glass-ceramics by using Eu3+ dopant in a borate glass matrix with calcium tungstate, which was expected to have a combined character of glass and ceramics. This study revealed that single-phase precipitation of CaWO4 crystals in borate glass matrix was possible by heat-treatment at a temperature higher than glass transition temperature Tg for (100−x) (33CaO-67B2O3)−xCa3WO6 (x = 8−15 mol%). Additionally, the crystallization of CaWO4 was found by Raman spectroscopy due to the formation of W=O double bondings of WO4 tetrahedra in the pristine glass despite starting with the higher calcium content of Ca3WO6. Eu3+ ions were excluded from the CaWO4 crystals and positioned in the borate glass phase as a stable site for them, which provided local environments in higher symmetry around Eu3+ ions.

Tooth Discoloration Using Calcium Silicate-Based Cements For Simulated Revascularization in Vitro

The endodontic revascularization may be an alternative treatment for necrotic immature teeth, however, several treatment steps may cause tooth discoloration. This study evaluated the use of three calcium silicate-based cements with different radiopacifying agents on the color alteration (∆E) of extracted premolars after simulation of revascularization. Forty single rooted extracted premolars were shaped with #1-6 gates Glidden drills, rinsed with sodium hypochlorite, and filled with fresh human blood. Three calcium silicate-based cements with different radiopacifying agents (bismuth oxide - CSBi, calcium tungstate - CSW, and zirconium oxide - CSZr) were applied over the blood clot (n=10). The control group received the application of a temporary zinc oxide-based cement (TFZn) (n=10). ∆E was measured with a spectrophotometer, using the L*a*b* color system of the International Commission on Illumination (CIELab), in different times: prior to the preparation of the access cavity (t0); right after treatment (t1); and after one (t2), two (t3), three (t4) and four (t5) months. The tooth site for color evaluation was standardized by silicon matrix, the color reading was performed 3 times per tooth, and the teeth were stored in 37º water between evaluations. ∆E, whiteness (WID index) and yellowness (b*) were evaluated. Data were subjected to one-way ANOVA and repeated measures ANOVA, followed by Tukey’s post hoc test (α=0.05). All groups were similar in ∆E1 (t0-t1). The ∆E was the lowest and constant in the control group. In all evaluation times, CSBi presented the highest ∆E (p<0.01). CSW and CSZr were similar in all evaluated times and presented intermediate ∆E values. WID index from CSBi and CSW presented more distancing from ‘white’ reference. CSBi presented the greatest decrease in yellowness (b* value). The cement containing bismuth oxide presented the highest color alteration values. All tested calcium silicate-based cements presented clinically perceptible discoloration. Calcium tungstate and zirconium oxide may be used as alternative radiopacifiers to decrease tooth discoloration after endodontic tooth revascularization.