Tetragonal to monoclinic phase transition observed during Zr anodisation

Plasma electrolytic oxidation (PEO) is a coating procedure that utilises anodic oxidation in aqueous electrolytes above the dielectric breakdown voltage to produce oxide coatings that have specific properties. These conditions facilitate oxide formation under localised high temperatures and pressures that originate from short-lived microdischarges at sites over the metal surface and have fast oxide volume expansion. Anodic ZrO2 films were prepared by subjecting metallic zirconium to PEO in acid solutions (H2C 2O4 and H3PO4) using a galvanostatic DC regime. The ZrO2 microstructure was investigated in films that were prepared at different charge densities. During the anodic breakdown, an important change in the amplitude of the voltage oscillations at a specific charge density was observed (i.e., the transition charge density (Q T)). We verified that this transition charge is a monotonic function of both the current density and temperature applied during the anodisation, which indicated that Q T is an intrinsic response of this system. The oxide morphology and microstructure were characterised using SEM and X-ray diffraction experiments (XRD) techniques. X-ray diffraction analysis revealed that the change in voltage oscillation was correlated with oxide microstructure changes during the breakdown process. © 2012 Springer-Verlag Berlin Heidelberg.

Monoclinic-tetragonal phase transition in Pb(Zr1-xTix)O-3 studied by infrared spectroscopy

The discovery of a new monoclinic phase in the PbZr1-xTixO3 (PZT) system in the vicinity of the morphotropic phase boundary (MPB), previously considered as a region where the rhombohedral and tetragonal phases of PZT coexist, was recently reported. Investigations of this new phase were reported using different techniques such as high-resolution synchrotron x-ray powder diffraction and Raman spectroscopy. The main objective has been to define a new phase diagram of PZT. In this context, infrared spectroscopic studies were performed in the vicinity of the MPB and studies were initially centred on a PZT sample with x = 0.49 mol% Ti content. Results suggested that the monoclinic --> tetragonal phase transition occurs at 237 K, confirming the use of IR as a useful technique to investigate this phase transition.

Infrared studies of the monoclinic-tetragonal phase transition in Pb(Zr, Ti)O-3 ceramics

Recently, the observation of a new monoclinic phase in the PbZr1-xTixO3 (PZT) system in the vicinity of the morphotropic phase boundary was reported. Investigations of this new phase were reported using different techniques such as high-resolution synchrotron x-ray powder diffraction and Raman spectroscopy. In this work, the monoclinic --> tetragonal phase transition in PbZr0.50Ti0.50O3 ceramics was studied using infrared spectroscopy between 1000 and 400 cm(-1). The four possible nu(1)-stretching modes (Ti-O and Zr-O stretch) in the BO6 octahedron in the ABO(3) structure of PZT in this region were monitored as a function of temperature. The lower-frequency mode nu(1)-(Zr-O) remains practically unaltered, while both intermediate nu(1)-(Ti-O) modes decrease linearly as temperature increases from 89 to 263 K. In contrast, the higher-frequency nu(1)-(Ti-O) and nu(1)-(Zr-O) modes present anomalous behaviour around 178 K. The singularity observed at this mode was associated with the monoclinic --> tetragonal phase transition in PbZr0.50Ti0.50O3 ceramics.

Evidence for the monoclinic-tetragonal phase coexistence in Pb(Zr(0.53)Ti(0.47))O(3) thin films

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

Structural phase transitions of PbZr0.52Ti0.48O3 ceramic: An infrared spectroscopy study

The recent discovery of a ferroelectric monoclinic phase in the PbZr1-xTixO3 (PZT) system attained the attention of several researchers due to the possibility of understanding the relationships between structural features and piezoelectric properties. The nature of the monoclinic phase in some PZT compositions remains controversial and unclear. In this work, structural phase transitions of PbZr0.52Ti0.48O3 ceramic were investigated by infrared spectroscopy as a function of temperature. Studies were centered on nu(1)-stretching modes and corresponding half width Wi as a function of temperature. The occurrence of the anomalies in the infrared spectra as a function of temperature suggests the following monoclinic ( LT) -> monoclinic ( HT) -> tetragonal phase transition were observed at 183 K and at 263 K.

Structural Phase Transition Studies on PMN-0.35PT using Infrared Spectroscopy

The purpose of the present work is to report studies on structural phase transition for PMN-xPT ferroelectric, with melt PbTiO3 composition around the MPB (x = 0.35 mol %), using infrared spectroscopy technique. The study was centered on monitoring the behavior of the 1-(NbO), 1-(TiO) and 1-(MgO) stretching modes as a function of temperature. The increasing as a function of temperature for 1-(TiO) and 1-(MgO) modes, observed between 230 and 300 K, can be related to the monoclinic (MC) + tetragonal (T) phase coexistence in the PMN-PT.

Effect of air-particle abrasion protocols on the biaxial flexural strength, surface characteristics and phase transformation of zirconia after cyclic loading

This study evaluated the effect of air-particle abrasion protocols on the biaxial flexural strength, surface characteristics and phase transformation of zirconia after cyclic loading. Disc-shaped zirconia specimens (Ø: 15mm, thickness: 1.2mm) (N=32) were submitted to one of the air-particle abrasion protocols (n=8 per group): (a) 50μm Al2O3 particles, (b) 110μm Al2O3 particles coated with silica (Rocatec Plus), (c) 30μm Al2O3 particles coated with silica (CoJet Sand) for 20s at 2.8bar pressure. Control group received no air-abrasion. All specimens were initially cyclic loaded (×20,000, 50N, 1Hz) in water at 37°C and then subjected to biaxial flexural strength testing where the conditioned surface was under tension. Zirconia surfaces were characterized and roughness was measured with 3D surface profilometer. Phase transformation from tetragonal to monoclinic was determined by Raman spectroscopy. The relative amount of transformed monoclinic zirconia (FM) and transformed zone depth (TZD) were measured using XRD. The data (MPa) were analyzed using ANOVA, Tukey's tests and Weibull modulus (m) were calculated for each group (95% CI). The biaxial flexural strength (MPa) of CoJet treated group (1266.3±158A) was not significantly different than that of Rocatec Plus group (1179±216.4A,B) but was significantly higher than the other groups (Control: 942.3±74.6C; 50μm Al2O3: 915.2±185.7B,C). Weibull modulus was higher for control (m=13.79) than those of other groups (m=4.95, m=5.64, m=9.13 for group a, b and c, respectively). Surface roughness (Ra) was the highest with 50μm Al2O3 (0.261μm) than those of other groups (0.15-0.195μm). After all air-abrasion protocols, FM increased (15.02%-19.25%) compared to control group (11.12%). TZD also showed increase after air-abrasion protocols (0.83-1.07μm) compared to control group (0.59μm). Air-abrasion protocols increased the roughness and monoclinic phase but in turn abrasion with 30μm Al2O3 particles coated with silica has increased the biaxial flexural strength of the tested zirconia. © 2013 Elsevier Ltd.

Quantitative phase analysis from X-ray diffraction in Y-TZP dental ceramics: A critical evaluation

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

Effect of surface and heat treatments on the biaxial flexural strength and phase transformation of a Y-TZP ceramic

To evaluate the effect of grinding and airborne-particle abrasion on the biaxial flexural strength (BFS) and phase transformation of a Y-TZP ceramic, and examine whether sintering the veneering porcelain renders the previous heat treatment recommended by the manufacturer unnecessary. Materials and Methods: Lava zirconia specimens (N = 108) were obtained with the following dimensions: 14.0 mm diameter × 1.3 mm thickness (n = 36) and 14.0 mm × 1.6 mm (n = 72). The thicker specimens were ground with diamond burs under irrigation and received (heat-treated groups) or not (non-heat-treated groups) a heat treatment (1000°C for 30 min) prior to the four firing cycles applied to simulate the sintering of the veneering porcelain. All specimens were air abraded as follows (n = 12): 1) 30-μm silica-modified Al2O3 particles (Rocatec Soft); 2) 110-μm silica-modified Al2O3 particles (Rocatec Plus); and 3) 120-μm Al2O3 particles, followed by Rocatec Plus. Three specimens of each group were analyzed by x-ray diffraction (XRD) to assess the monoclinic phase content (%). The BFS test was performed in a mechanical testing machine (Instron 8874). Data (MPa) were analyzed by two-way ANOVA (grinding × airborne-particle abrasion and heat treatment × airborne-particle abrasion) and Tukey's post-hoc test (α = 0.05). The strength reliability was analyzed using the Weibull distribution. Results: Grinding significantly decreased the BFS of the non-heat-treated groups (p < 0.01). Within the ground groups, the previous heat treatment did not influence the BFS (p > 0.05). Air abrasion only influenced the BFS of the ground/heat-treated groups (p < 0.01). For the non-heat-treated groups, the grinding did not decrease the Weibull modulus (m), but it did decrease the characteristic strength (σ0). For Rocatec Soft and 120-μm Al2O3 particles + Rocatec Plus, the heat-treated groups presented lower m and higher σ0 than the ground/non-heat-treated groups. The independent variables did not seem to influence phase transformation. Air-abraded surfaces presented higher monoclinic zirconia content than the as-sintered and ground surfaces, which exhibited similar content. Conclusion: Even under irrigation, grinding compromised the Y-TZP ceramic strength. The sintering of the veneering porcelain rendered the previous heat treatment recommended by the manufacturer unnecessary. Airborneparticle abrasion influenced the strength of heat-treated zirconia.

Effect of surface and heat treatments on the biaxial flexural strength and phase transformation of a y-tzp ceramic

To evaluate the effect of grinding and airborne-particle abrasion on the biaxial flexural strength (BFS) and phase transformation of a Y-TZP ceramic, and examine whether sintering the veneering porcelain renders the previous heat treatment recommended by the manufacturer unnecessary. Materials and Methods: Lava zirconia specimens (N = 108) were obtained with the following dimensions: 14.0 mm diameter × 1.3 mm thickness (n = 36) and 14.0 mm × 1.6 mm (n = 72). The thicker specimens were ground with diamond burs under irrigation and received (heat-treated groups) or not (non-heat-treated groups) a heat treatment (1000°C for 30 min) prior to the four firing cycles applied to simulate the sintering of the veneering porcelain. All specimens were air abraded as follows (n = 12): 1) 30-μm silica-modified Al2O3 particles (Rocatec Soft); 2) 110-μm silica-modified Al2O3 particles (Rocatec Plus); and 3) 120-μm Al2O3 particles, followed by Rocatec Plus. Three specimens of each group were analyzed by x-ray diffraction (XRD) to assess the monoclinic phase content (%). The BFS test was performed in a mechanical testing machine (Instron 8874). Data (MPa) were analyzed by two-way ANOVA (grinding × airborne-particle abrasion and heat treatment × airborne-particle abrasion) and Tukey's post-hoc test (α = 0.05). The strength reliability was analyzed using the Weibull distribution. Results: Grinding significantly decreased the BFS of the non-heat-treated groups (p < 0.01). Within the ground groups, the previous heat treatment did not influence the BFS (p > 0.05). Air abrasion only influenced the BFS of the ground/heat-treated groups (p < 0.01). For the non-heat-treated groups, the grinding did not decrease the Weibull modulus (m), but it did decrease the characteristic strength (σ0). For Rocatec Soft and 120-μm Al2O3 particles + Rocatec Plus, the heat-treated groups presented lower m and higher σ0 than the ground/non-heat-treated groups. The independent variables did not seem to influence phase transformation. Air-abraded surfaces presented higher monoclinic zirconia content than the as-sintered and ground surfaces, which exhibited similar content. Conclusion: Even under irrigation, grinding compromised the Y-TZP ceramic strength. The sintering of the veneering porcelain rendered the previous heat treatment recommended by the manufacturer unnecessary. Airborneparticle abrasion influenced the strength of heat-treated zirconia.

Effect of particle size on the flexural strength and phase transformation of an airborne-particle abraded yttria-stabilized tetragonal zirconia polycrystal ceramic.

Statement of problem Because airborne-particle abrasion is an efficient method of improving the bond at the zirconia-cement interface, understanding its effect on the strength of yttria-stabilized tetragonal zirconia polycrystal is important. Purpose The purpose of this study was to evaluate the effect of the particle size used for airborne-particle abrasion on the flexural strength and phase transformation of a commercially available yttria-stabilized tetragonal zirconia polycrystal ceramic. Material and Methods For both flexural strength (20.0 × 4.0 × 1.2 mm) (n=14) and phase transformation (14.0-mm diameter × 1.3-mm thickness) (n=4), the zirconia specimens were made from Lava, and their surfaces were treated in the following ways: as-sintered (control); with 50-μm aluminum oxide (Al2O3) particles; with 120-μm Al2O3 particles; with 250-μm Al2O3 particles; with 30-μm silica-modified Al2O3 particles (Cojet Sand); with 120-μm Al2O3 particles, followed by 110-μm silica-modified Al2O3 particles (Rocatec Plus); and with Rocatec Plus. The phase transformation (%) was assessed by x-ray diffraction analysis. The 3-point flexural strength test was conducted in artificial saliva at 37°C in a mechanical testing machine. The data were analyzed by 1-way ANOVA and the Tukey honestly significant difference post hoc test (α=.05). Results Except for the Cojet Sand group, which exhibited statistically similar flexural strength to that of the as-sintered group and for the group abraded with 250-μm Al2O3 particles, which presented the lowest strength, airborne-particle abrasion with the other particle sizes provided the highest values, with no significant difference among them. The as-sintered specimens presented no monoclinic phase. The groups abraded with smaller particles (30 μm and 50 μm) and those treated with the larger ones (110 μm and/or 120 μm particles and 250 μm) exhibited percentages of monoclinic phase that varied from 4% to 5% and from 8.7% to 10%. Conclusions Except for abrasion with Cojet Sand, depending on the particle size, zirconia exhibited an increase or a decrease in its flexural strength. Airborne-particle abrasion promoted phase transformation (tetragonal to monoclinic), and the percentage of monoclinic phase varied according to the particle size.

Application of Micro-Raman Spectroscopy to the Study of Yttria-Stabilized Tetragonal Zirconia Polycrystal (Y-TZP) Phase Transformation

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

Physical properties of self-polarized PZT thin films at compositions around the morphotropic phase boundary

The physical properties of self-polarized PbZr1-xTixO3 thin films with no preferential orientation in a range of compositions 0.46 <= x <= 0.50 were investigated. Structural analysis revealed the coexistence of monoclinic-tetragonal and monoclinic-rhombohedral phases at compositions 0.46 <= x <= 0.49, where the monoclinic phase was in the majority and both the tetragonal and the rhombohedral phases in the minority. The dielectric permittivity (epsilon'= 447) reached its maximum at around composition x = 0.48. Asymmetries in the macroscopic and local hysteresis loops confirmed the existence of the self-polarization effect in the studied films.

New features of the morphotropic phase boundary in the PbZrO 3-PbTiO3 system: A Raman spectroscopy study

In this work we present a Raman study of PbZr1-xTi xO3 ceramics with composition values close to the morphotropic phase boundary region. The analysis of the Raman spectra leads to the determination of the monoclinic phase extension at different temperatures in a very good agreement with those determined by diffraction techniques. Therefore the obtained results show that Raman spectroscopy is a powerful and suitable technique to study structural phase transitions in PbZr 1-xTixO3. © 2002 Taylor & Francis.

Deposition and characterization of BiVO4 thin films and evaluation as photoanodes for methylene blue degradation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)