Evaluation of interface characterization and adhesion of glass ceramics to commercially pure titanium and gold alloy after thermal- and mechanical-loading

Objectives. This study evaluated the effect of thermal- and mechanical-cycling on the shear bond strength of three low-fusing glassy matrix dental ceramics to commercial pure titanium (cpTi) when compared to conventional feldspathic ceramic fused to gold alloy.Methods. Metallic frameworks (diameter: 5 min, thickness: 4 mm) (N = 96, n = 12 per group) were cast in cpTi and gold alloy, airborne particle abraded with 150 mu m aluminum oxide. Low-fusing glassy matrix ceramics and a conventional feldspathic ceramic were fired onto the alloys (thickness: 4mm). Four experimental groups were formed; Gr1 (control group): Vita Omega 900-Au-Pd alloy; Gr2: Ticeram-cpTi; Gr3: Super Porcelain Ti-22-cpTi and G4: Vita Titankeramik-cpTi. While half of the specimens from each ceramic-metal combination were randomly tested without aging (water storage at 37 C for 24h only), the other half were first thermocycled (6000 cycles, between 5 and 55 C, dwell time: 13 s) and then mechanically loaded (20,000 cycles under SON load, immersion in distilled water at 37 C). The ceramic-alloy interfaces were loaded under shear in a universal test machine (cross-head speed: 0.5 mm/min) until failure occur-red. Failure types were noted and the interfaces of the representative fractured specimens from each group were examined with stereo microscope and scanning electron microscope (SEM). in an additional study (N = 16, n = 2 per group), energy dispersive X-ray spectroscopy (EDS) analysis was performed from ceramic-alloy interfaces. Data were analyzed using ANOVA and Tukey's test.Results. Both ceramic-metal combinations (p < 0.001) and aging conditions (p < 0,001) significantly affected the mean bond strength values. Thermal- and mechanical-cycling decreased the bond strength (MPa) results significantly for Gr3 (33.4 +/- 4.2) and Gr4 (32.1 +/- 4.8) when compared to the non-aged groups (42.9 +/- 8.9, 42.4 +/- 5.2, respectively). Gr1 was not affected significantly from aging conditions (61.3 +/- 8.4 for control, 60.7 +/- 13.7 after aging) (p > 0.05). Stereomicroscope images showed exclusively adhesive failure types at the opaque ceramic-cpTi interfacial zone with no presence of ceramic on the substrate surface but with a visible dark titanium oxide layer in Groups 2-4 except Gr1 where remnants of bonder ceramic was visible. EDS analysis from the interfacial zone for cpTi-ceramic groups showed predominantly 34.5-85.1% O(2) followed by 1.1-36.7% Aland 0-36.3% Si except for Super Porcelain Ti-22 where a small quantity of Ba (1.4-8.3%), S (0.7%) and Sn (35.3%) was found. In the Au-Pd alloy-ceramic interface, 56.4-69.9% O(2) followed by 15.6-26.2% Si, 3.9-10.9% K, 2.8-6% Na, 4.4-9.6% Al and 0-0.04% Mg was observed.Significance. After thermal-cycling for 6000 times and mechanical-cycling for 20,000 times, Triceram-cpTi combination presented the least decrease among other ceramic-alloy combinations when compared to the mean bond strength results with Au-Pd alloy-Vita Omega 900 combination. (c) 2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Surface degradation of glass ceramics after exposure to acidulated phosphate fluoride

Objective: This study evaluated the surface degradation effect of acidulated phosphate fluoride (APF) gel exposure on the glassy matrix ceramics as a function of time. Material and methods: Disc-shaped ceramic specimens (N = 120, 10/per ceramic material) were prepared in stainless steel molds (inner diameter: 5 mm, height: 2 mm) using 6 dental ceramics: 3 indicated for ceramic-fused-to-metal (Vita Omega 900, Carmen and Vita Titankeramik), 2 for all-ceramic (Vitadur Alpha and Finesse (R) Low Fusing) and 1 for both types of restorations (IPS d. SIGN). The specimens were wet ground finished, ultrasonically cleaned and auto-glazed. All specimens were subjected to calculation of percentage of mass loss, surface roughness analysis and topographical description by scanning electron microscopy (SEM) before (0 min) and after exposure to 1.23 % APF gel for 4 min and 60 min representing short-and long-term etching effect, respectively. The data were analyzed using two-way ANOVA with repeated measures and Tukey` s test (alpha=0.05). Results: Significant effect of the type of the ceramics (p=0.0000, p=0.0031) and exposure time (p=0.0000) was observed in both surface roughness and percentage of mass loss values, respectively. The interaction factor between both parameters was also significant for both parameters (p=0.0904, p=0.0258). Both 4 min (0.44 +/- 0.1-0.81 +/- 0.2 mu m) and 60 min (0.66 +/- 0.1 - 1.04 +/- 0.3 mu m) APF gel exposure created significantly more surface roughness for all groups when compared to the control groups (0.33 +/- 0.2-0.68 +/- 0.2 mu m) (p<0.05). There were no significant differences in percentage of mass loss between the ceramics at 4 min (p>0.05) but at 60 min exposure, IPS d. SIGN showed the highest percentage of mass loss (0.1151 +/- 0.11). The mean surface roughness for Vita Titankeramik (0.84 +/- 0.2 mu m) and Finesse (R) Low Fusing (0.74.+/- 0.2 mu m) was significantly higher than those of the other ceramics (0.59 +/- 0.1 mu m - 0.49 +/- 0.1 mu m) and Vita Titankeramik (p<0.05) regardless of the exposure time. A positive correlation was found between surface roughness and percentage of mass loss for all ceramic materials [(r=0.518 (Vitadur Alpha), r=0.405 (Vita Omega 900), r=0.580 (Carmen), r=0.687 (IPS d. SIGN), r=0.442 (Finesse (R) Low Fusing), r=0.572 (Vita Titankeramik), Pearson's correlation coefficient)]. The qualitative SEM analysis showed evidence of corrosive attack on all of ceramics at varying degrees. Conclusions: The ceramics indicated for either metal-ceramic or all-ceramic restorations were all vulnerable to surface texture changes and mass loss after short-term and long-term APF gel exposure.

Mechanical and thermal cycling effects on the flexural strength of glass ceramics fused to titanium

This study evaluated the effects of mechanical and thermal cycling on the flexural strength (ISO 9693) of three brands of ceramics fused to commercially pure titanium (cpTi). Metallic frameworks of 25 x 3 x 0.5 mm dimensions (N = 84) were cast in cpTi, followed by 150-mu m aluminum oxide airborne particle abrasion at a designated area of the frameworks (8 x 3 mm). Bonder and opaque ceramic were applied on the frameworks, and then the corresponding ceramic (Triceram, Super Porcelain Ti-22, Vita Titankeramik) was fired onto them (thickness: 1 mm). Half of the specimens from each ceramic-metal combination were randomly tested without aging (only water storage at 37 degrees C for 24 hours), while the other half were mechanically loaded (20,000 cycles under 10 N load, immersion in distilled water at 37 degrees C) and thermocycled (3,000 cycles, between 5-55 degrees C, dwell time of 13 seconds). After the flexural strength test, failure types were noted. Mechanical and thermal cycling decreased the mean flexural strength values significantly (p<0.05) for all the three ceramic-cpTi combinations tested when compared to the control group. In all the three groups, failure type was exclusively adhesive at the opaque ceramic-cpTi interfacial zone with no presence of ceramic on the substrate surface except for a visible oxide layer.

Structural Investigations of Glass Ceramics in the Ga2S3-GeS2-CsCl System

Transparent glass ceramics have been prepared in the Ga2S3-GeS2-CsCI pseudoternary system appropriate heat treatment time and temperature. In situ X-ray diffraction at the heat treatment temperature and Cs-133 and Ga-71 solid-state nuclear magnetic resonance have been performed in function of annealing time to understand the crystallization process. Both techniques have evidenced the nucleating agent role played by gallium with the formation of Ga2S3 nanocrystals. on the other hand, cesium is incorporated very much later into the crystallites during the ceramization. Moreover, the addition of CsCl, which is readily integrated into the glassy network, permits us to shift the optical band gap toward shorter wavelength. Thus, new glass ceramics transmitting in the whole visible range up to 11.5 mu m have been Successfully synthesized from the (Ga2S3)(35)-(GeS2)(25)-CsCl40 base glass composition.

Synthesis and Structural Studies of Er3+ Containing Lead Cadmium Fluoroborate Glasses and Glass-Ceramics

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

Er3+ and Eu3+ containing transparent glass ceramics in the system PbGeO3-PbF2-CdF2

Glasses with composition 60PbGeO(3)-10PbF(2)-30CdF(2) (mol%) have been obtained in the bulk form with a high stability against crystallization. After doping them with 0.5 mol% of Er3+ or Eu3+ and appropriate heat treatment transparent glass ceramics could be obtained. Electronic spectroscopy, X-ray diffraction and transmission electron microscopy measurements have been made. beta-PbF2: Er3+/Eu3+ Single crystals, 5-10 nm in size, are detected in the otherwise transparent composite medium, the size of the particles and absence of clustering allowing for the increased transparency of the final materials. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Synthesis and structural investigations on TeO2-PbF2-CdF2 glasses and transparent glass-ceramics

New glasses have been prepared in the oxifluoride mixed system TeO2-PbF2-CdF2. Starting from pure TeO2 the addition of the fluorides leads to a decrease in the glasses characteristic temperatures. Also from Raman scattering results a structural evolution was observed where the number of structural units described as [TeO3] trigonal pyramids and [TeO3+1] polyhedra increases at the expense of the [TeO4] trigonal bipyramids supposed to exist in the TeO2, rich samples. Transparent glass ceramics were obtained from the glass with composition 80TeO(2)-10PbF(2)-10CdF(2), (mol%) with the PbTe3O7 crystalline phase being identified by X-ray diffraction and EXAFS measurements performed at the Te K, Cd K and Pb L-III edges. Also from Exafs measurements it is proposed that cadmium ions are preferentially surrounded by oxygen atoms although they were in a fluoride anion environment in the starting material. (C) 2002 Published by Elsevier B.V. Ltd.

Lead-cadmium oxyfluoride glasses and glass-ceramics

Glasses and glass-ceramics have been obtained in oxyfluoride systems involving lead and cadmium fluorides and one of the well-known glass former oxides SiO2, B2O3 and TeO2. Vitreous domains were established and a wide range of compositions including high heavy metal contents lead to stable glasses. Amorphous structures have been studied by short-range order spectroscopy techniques (Raman scattering and x-ray absorption) and molecular basic structures have been identified. Besides the usual oxides, the role of glass former could also be proposed for cadmium ions. Special attention has been paid for crystallization process. Cubic lead fluoride, cubic lead tellurite, tetragonal tellurium oxide and a solid solution of the type Pb1-xCdxF2 are obtained as crystallization products depending on the composition and temperature of heat treatments. Pb1-xCdxF2 solid solutions are well known superionic materials and obtaining this solid solution as a crystal phase could be very interesting for applications concerning ionic electrical conduction properties. The addition of rare earth ions led to the control of the crystallization process. In the presence of the nucleating ion only the cubic form beta-PbF2 was identified. Rare earth ions are present in the crystal phase and crystal-like spectroscopic properties were observed suggesting interesting applications for these perfectly transparent glass ceramics in photonics.

Upconversion luminescence in transparent glass ceramics containing beta-PbF2 nanocrystals doped with erbium

Frequency upconversion luminescence in erbium-doped PbGeO3-PbF2-CdF2-based transparent glass ceramics (TGC) under 980 nm infrared excitation is investigated. Upconversion emission signals around 410, 525, 550, 660, and 850 nm were generated and identified as due to the H-2(9/2) H-2(11/2), S-4(3/2), and F-4(9/2) transitions to the I-4(15/2) ground-state, and S-4(3/2)-I-4(13/2), respectively. The erbium ions excited-state emitting levels were populated via a combination of stepwise ground-state absorption (GSA), excited-state absorption (ESA), and cross-relaxation processes. The results also disclosed that both blue (410 nm) and red (660 nm) upconversion emission signals in the transparent glass ceramic sample presented twice as much intensity as compared to its vitreous counterpart. (C) 2003 Elsevier B.V. All rights reserved.

SiO2-PbF2-CdF2 glasses and glass ceramics

Lead-Cadmium fluorosilicate stable glasses were prepared and the vitreous domain region determined in the composition diagram. Characteristic temperatures were obtained from thermal analysis and the structural studies performed illustrate clearly the role played by lead atoms in the glasses crystallization behavior and the glass-forming ability of cadmium atoms. The occurrence of either a cubic lead fluoride or a lead-cadmium fluoride solid solution in crystallizing samples was found to be dependent on Er3+ doping. The optically active ions were found to concentrate in the crystalline phase and in fact play the role of nucleating agent as suggested from X-ray diffraction and EXAFS measurements. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Conductivity and F-19 NMR in PbGeO3-PbF2-CdF2 glasses and glass-ceramics

The temperature dependence of the electrical conductivity and the F-19 nuclear magnetic resonance (NMR) of PbGeO3-PbF2CdF, glasses and glass ceramics are investigated. The measured conductivity values of the glasses are above 10(-5) Skin at 500 K, and increase with increasing lead fluoride content. Activation energies extracted from the conductivity data are in the range 0.59-0.73 eV. Results are consistent with the hypothesis that in these oxyfluoride glasses lead fluoride rich clusters are dispersed in a metagermanate based matrix providing increasing mobility pathways for conducting ions. The conductivity of a sample of the glass ceramic of composition (mol%) 60PbGeO(3-)20PbF(2)-20CdF(2) was found to be smaller than that in the corresponding glass, suggesting that there are poor ionic conducting regions in the interface between the nanometer sized crystals. The temperature dependence of the F-19 relaxation times, measured in the range 100-800 K, exhibit the qualitative features associated with high fluorine mobility in both, glass and glass ceramics materials. We suggest that de-convolution of the spin-lattice relaxation rates observed in the glass ceramics shows that the observed high temperature rate maximum is associated with the diffusional motions of the fluorine ions in beta-PbF2 crystals. (c) 2005 Elsevier B.V. All rights reserved.

Structural and spectroscopic study of oxyfluoride glasses and glass-ceramics using europium ion as a structural probe

Transparent oxyfluoride glasses and beta-PbF(2) nanocrystals containing glass-ceramics were prepared with varying Eu(3+) content (0.3, 0.4, 0.5 and 0.6%). The effect of Eu(3+) content on the preparation of glass-ceramics was investigated. From differential scanning calorimetry, the T(x)-T(g)(T(x)-temperature of the onset of crystallization; T(g)-glass transition temperature) parameter for glasses has shown slight variation, and an exothermic peak near T(g) called the ceramization temperature (T(c)) has been observed. Heat treatments were performed at this temperature to obtain transparent glass-ceramics containing beta-PbF(2) nanocrystals, identified by x-ray diffraction. Heat treatments for different periods of time were performed and were observed to be very important in the control of the crystal size and of the crystallization rate. Based upon the absorption spectra, the scattering level due to the presence of beta-PbF(2) nanocrystals in the glass-ceramics was observed to be similar to that for the mother glasses. Detailed analysis of emission spectra and decay time measurements led to the identification of Eu(3+) ions as the beta-PbF(2) crystalline phase. Excitation spectra at 70 K show the interaction of Eu(3+) ions with the fluorogermanate network.

Innovating transparent glass ceramics based on Ga2S3-GeS2-CsCl

In this paper, we describe the preparation of glass ceramics in the Ga2S3 - GeS2 - CsCl system Visible and infrared transmitting glass ceramics were reproducibly obtained by appropriated heat treatment of the base glass Crystals with controllable size of about 40 nm were homogeneously generated in the glassy matrix X-ray diffraction characterizations have shown that gallium acts as nucleating agent in this material, giving rise to alpha-Ga2S3 crystals Improved thermo-mechanical properties such as dilatation coefficient and resistance to fracture propagation have been observed in the prepared glass ceramics

Transparent Er3+-activated lead fluorogermanate glass ceramics

Transparent glass ceramics containing β-PbF2:Er 3+ nanocrystals were obtained through appropriate thermal treatments of a glass of molar composition 60PbGeO3-10PbF2-30CdF 2 doped with 0.5 mol% Er3+. Their optical properties, as well as upconversion processes among erbium ions in the glass and glass ceramic matrix were studied. From absorption spectra, Judd-Ofelt parameters and radiative transition rates for several excited levels were calculated. Emission spectra in the visible and NIR regions were collected, and stimulated emission cross sections were obtained by McCumber theory for the 4F 13/2→4I15/2 transition at 1.5 μm. Red and green upconversion emissions were measured in glass and glass ceramics upon excitation at 980 nm; lifetimes were measured in order to assess the upconversion mechanisms.

Infrared-to-visible frequency upconversion in transparent glass ceramics containing trivalent-rare-earth-doped nanocrystals

In this work we report on visible upconversion emission in Er 3+-, and Ho3+-doped PbGeO3-PbF 2-CdF2-based transparent glass ceramics under 980 nm infrared excitation. In erbium-doped vitroceramic samples, blue(410 ran), green(530, and 550 nm) and red(660 nm) emission signals were generated, which were identified as due to the 2H9/2, 2H 11/2, 4S3/2, and 4F9/2 transitions to the 4I15/2 ground-state, respectively. Intense red(650 nm) upconversion emission corresponding to the 5F5 - 5I8 transition and very small blue(490 nm) and green(540 nm) signals assigned to the 5F 2,3 - 5I8 and 4S2, 5F4 - 5I8 transitions, respectively, were observed in the holmium-doped samples. The 540 nm is the dominant upconversion signal in Ho3+-doped vitroceramics under 850 nm excitation. The dependence of the upconversion processes upon pump power and doping concentration are also investigated, and the main routes for the upconversion excitation processes are also identified. The comparison of the upconversion process in transparent glass ceramics and the precursor glass was also examined and the results revealed that the former present higher upconversion efficiencies.