Effect of ion exchange on strength and slow crack growth of a dental porcelain

Objectives. To determine the effect of ion exchange on slow crack growth (SCG) parameters (n, stress corrosion susceptibility coefficient, and sigma(f0), scaling parameter) and Weibull parameters (m, Weibull modulus, and sigma(0), characteristic strength) of a dental porcelain. Methods. 160 porcelain discs were fabricated according to manufacturer`s instructions, polished through 1 mu m and divided into two groups: GC (control) and GI (submitted to an ion exchange procedure using a KNO(3) paste at 470 degrees C for 15 min). SCG parameters were determined by biaxial flexural strength test in artificial saliva at 37 degrees C using five constant stress rates (n =10). 20 specimens of each group were tested at 1 MPa/s to determine Weibull parameters. The SPT diagram was constructed using the least-squares fit of the strength data versus probability of failure. Results. Mean values of m and sigma(0) (95% confidence interval), n and sigma(f0) (standard deviation) were, respectively: 13.8 (10.1-18.8) and 60.4 (58.5 - 62.2), 24.1 (2.5) and 58.1 (0.01) for GC and 7.4 (5.3 -10.0) and 136.8 (129.1-144.7), 36.7 (7.3) and 127.9 (0.01) for GI. Fracture stresses (MPa) calculated using the SPT diagram for lifetimes of 1 day, 1 year and 10 years (at a 5% failure probability) were, respectively, 31.8, 24.9 and 22.7 for GC and 71.2, 60.6 and 56.9 for GI. Significance. For the porcelain tested, the ion exchange process improved strength and resistance to SCG, however, the material`s reliability decreased. The predicted fracture stress at 5% failure probability for a lifetime of 10 years was also higher for the ion treated group. (C) 009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of leucite content on slow crack growth of dental porcelains

Objectives. To determine the stress corrosion susceptibility coefficient, n, of seven dental porcelains (A: Ceramco I; B: Ceramco-II; C: Ceramco-III; D: d.Sign; E: Cerabien; F: Vitadur-Alpha; and G: Ultropaline) after aging in air or artificial saliva, and correlate results with leucite content (LC). Methods. Bars were fired according to manufacturers` instructions and polished before induction of cracks by a Vickers indenter (19.6 N, 20 s). Four specimens were stored in air/room temperature, and three in saliva/37 degrees C. Five indentations were made per specimen and crack lengths measured at the following times: similar to 0; 1; 3; 10; 30; 100; 300; 1000 and 3000 h. The stress corrosion coefficient n was calculated by linear regression analysis after plotting crack length as a function of time, considering that the slope of the curve was (2/(3n + 2)]. Microstructural analysis was performed to determine LC. Results. LC of the porcelains were 22% (A and B); 6% (C); 15% (D); 0% (E and F); and 13% (G). Except for porcelains A and D, all materials showed a decrease in their n values when stored in artificial saliva. However, the decrease was more pronounced for porcelains B, F, and G. Ranking of materials varied according to storage media (in air, porcelain G showed higher n compared to A, while in saliva both showed similar coefficients). No correlation was found between n values and LC in air or saliva. Significance. Storage media influenced the n value obtained for most of the materials. LC did not affect resistance to slow crack growth regardless of the test environment. (c) 2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of Test Environment and Microstructure on the Flexural Strength of Dental Porcelains

Purpose: The objective of this study was to verify the influence of test environment on the flexural strength of dental porcelains with distinct microstructures. Material and Methods: Disk-shaped specimens from three dental porcelains with distinct leucite content (VM: zero; CE: 12; NS: 22 vol%) were manufactured and tested for biaxial flexural strength in air and immersed in artificial saliva. The results were analyzed by means of two-way ANOVA and Tukey`s test (alpha = 0.05). Results: The flexural strength (MPa) obtained for ambient air and artificial saliva environments, respectively, were: 110.0 +/- 16.0 and 81.5 +/- 10.8 for VM; 51.9 +/- 4.0 and 42.0 +/- 4.7 for CE; 72.0 +/- 11.5 and 63.6 +/- 5.8 for NS. A numerical decrease in the mean flexural strength was observed for all groups when specimens were tested under artificial saliva; however, the difference was only statistically significant for VM. Conclusions: The results indicate that the effect of water immersion on the flexural strength of dental porcelains varies according to their leucite content, as only the material without leucite in its microstructure (VM) showed significant strength degradation when tested under water.

Understanding the impact of divalent cation substitution on hydroxyapatite: An in vitro multiparametric study on biocompatibility

Hydroxyapatite (HA), a stable and biocompatible material for bone tissue therapy, may present a variable stoichiometry and accept a large number of cationic substitutions. Such substitutions may modify the chemical activity of HA surface, with possible impact on biocompatibility. In this work, we assessed the effects of calcium substitution with diverse divalent cations (Pb(2+), Sr(2+), Co(2+), Zn(2+), Fe(2+), Cu(2+), or Mg(2+)) on the biological behavior of HA. Physicochemical analyses revealed that apatite characteristics related to crystallinity and calcium dissolution/uptake rates are very sensitive to the nature of cationic substitution. Cytocompatibility was evaluated by mitochondrial activity, membrane integrity, cell density, proapoptotic potential, and adhesion tests. With the exception of Zn-HA, all the substituted HAs induced some level of apoptosis. The highest apoptosis levels were observed for Mg-HA and Co-HA. Cu-HA was the only material to impair simultaneously mitochondrial activity, membrane integrity, and cell density. The highest relative cell densities after exposure to the modified HAs were observed for Mg-HA and Zn-HA, while Co-HA significantly improved cell adhesion onto HA surface. These results show that changes on surface dissolution caused by cationic substitution, as well as the increase of metal species released to biological media, were the main responsible factors related to alterations on HA biocompatibility. (C) 2011 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 98A: 351-358, 2011.

Fatigue life and failure modes of crowns systems with a modified framework design

Objectives: To evaluate the effect of framework design on the fatigue life and failure modes of metal ceramic (MC, Ni-Cr alloy core, VMK 95 porcelain veneer), glass-infiltrated alumina (ICA, In-Ceram Alumina/VM7), and veneered yttria-stabilized tetragonal zirconia polycrystals (Y-TZP, IPSe.max ZirCAD/IPS e.max,) crowns. Methods: Sixty composite resin tooth replicas of a prepared maxillary first molar were produced to receive crowns systems of a standard (MCs, ICAs, and Y-TZPs, n = 10 each) or a modified framework design (MCm, ICAm, and Y-TZPm, n = 10 each). Fatigue loading was delivered with a spherical steel indenter (3.18 mm radius) on the center of the occlusal surface using r-ratio fatigue (30-300 N) until completion of 10(6) cycles or failure. Fatigue was interrupted every 125,000 cycles for damage evaluation. Weibull distribution fits and contour plots were used for examining differences between groups. Failure mode was evaluated by light polarized and SEM microscopy. Results: Weibull analysis showed the highest fatigue life for MC crowns regardless of framework design. No significant difference (confidence bound overlaps) was observed between ICA and Y-TZP with or without framework design modification. Y-TZPm crowns presented fatigue life in the range of MC crowns. No porcelain veneer fracture was observed in the MC groups, whereas ICAs presented bulk fracture and ICAm failed mainly through the veneer. Y-TZP crowns failed through chipping within the veneer, without core fractures. Conclusions: Framework design modification did not improve the fatigue life of the crown systems investigated. Y-TZPm crowns showed comparable fatigue life to MC groups. Failure mode varied according to crown system. (C) 2010 Elsevier Ltd. All rights reserved.

Investigation of electrical conductivity as a function of dopant-ion radius in the systems Zr0.75Ce0.08M0.17O1.92 (M=Nd, Sm, Gd, Dy, Ho, Y, Er, Yb, Sc)

Electrical conductivity versus dopant ionic radius studies in zirconia- and ceria-based, solid oxide fuel cell (SOFC) electrolyte systems have shown that oxygen-ion conductivity is highest when the host and dopant ions are similar in size [J. Am. Ceram. Soc. 48 (1965) 286; Solid State Ionics 37 (1989) 67; Solid State Ionics 5 (1981) 547]. Under these conditions, it is thought that the conduction paths within the crystal lattice become less distorted [Solid State Ionics 8 (1983) 201]. In this study, binary ZrO2-M2O3 unit cells were expanded, via the partial substitution of Ce+4 for Zr+4 into the lattice, in an attempt to identify new, ternary, zirconia/ceria-based electrolyte systems with enhanced electrical conductivity. The compositions Zr0.75Ce0.08M0.17O1.92 (M = Nd, Sm, Gd, Dy, Ho, Y, Yb, Sc) were prepared using traditional solid state techniques. Bulk phase characterisation and precise lattice parameter measurements were performed with X-ray diffraction techniques. Four-probe DC conductivity measurements between 400 and 900 degreesC showed that the dopant-ion radius influenced electrical conductivity. The conductivity versus dopant-ion radius trends previously observed in zirconia-based, binary systems are clearly apparent in the ternary systems investigated in this study. The addition of ceria was found to have a negative influence on the electrical conductivity over the temperature range 400-900 degreesC. It is suggested that distortion of the oxygen-ion conduction path by the presence of the larger M+3 and Ce+4 species (relative to Zr+4) is the reason for the decreasing electrical conductivity as a function of increasing dopant size and ceria addition, respectively. (C) 2002 Elsevier Science B.V. All rights reserved.

Influence of nano-structure on electrolytic properties in CeO2 based system

Doped ceria (CeO2) compounds are fluorite type oxides that show oxygen ionic conductivity higher than yttria stabilized zirconia, in oxidizing atmosphere. In order to improve the conductivity, the effective index was suggested to maximize the oxygen ionic conductivity in doped CeO2 based oxides. In addition, the true microstructure of doped CeO2 was observed at atomic scale for conclusion of conduction mechanism. Doped CeO2 had small domains (10-50 nm) with ordered structure in a grain. It is found that the electrolytic properties strongly depended on the nano-structural feature at atomic scale in doped CeO2 electrolyte.

Surface-active phospholipid in total hip arthroplasty

This is the first report of surface-active phospholipid as the boundary lubricant in total hip arthroplasty. Aspirate and rinsings from the bearing surfaces of 25 revision operations and one primary surgery were analyzed from 3 weeks to 26 years postoperatively. All samples contained substantial amounts of surface-active phospholipids ranging from 14 to 4186 μg. These findings indicate that synoviocytes continue producing the lubricant in significant quantities after arthroplasty surgery independent of the type of joint replacement and its fixation. Surface-active phospholipid was found on all bearing surfaces analyzed including polyethylene, stainless steel, chrome cobalt, alumina, zirconia, and titanium.

Conductivity/microstructure study of a pyrochlore-type ordered phase in the compound Zr0.75Ce0.08Nd0.17O1.92

The compound Zr0.75Ce0.08Nd0.17O1.92 was investigated as part of a much larger electrical conductivity/microstructure study of the systems ZrO2-CeO2-M2O3 (where M=Nd, Sm, ..., Yb) [Solid State Ionics (2002)]. Electrical conductivity measurements performed in air at 800 degreesC showed significant conductivity degradation over a period of 200 h. Investigation of the annealed and as-fired specimens by ATEM revealed the presence of an emerging, ordered pyrochlore-type phase within the Zr0.75Ce0.08Nd0.17O1.92 defect-fluorite solid solution at much lower dopant levels than observed previously for zirconia binary systems. (C) 2002 Elsevier Science B.V. All rights reserved.

Electrolytic properties and nanostructural features in the La2O3-CeO2 system

Doped ceria (CeO2) compounds are fluorite-type oxides which show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, considerable interest has been shown in applications of these materials for low or intermediate temperature operation of solid-oxide fuel cells (SOFCs). In this study, the effective index was suggested to maximize the ionic conductivity in La2O3-CeO2 based oxides. The index considers the fluorite structure, and combines the expected oxygen vacancy level with the ionic radius mismatch between host and dopant cations. Using this approach, the ionic conductivity of this system has been optimized and tested under operating conditions of SOFCs. LaxCe1-xO2-delta (x = 0.125, 0.15, 0.175, and 0.20), (LaxSr1-x)(0.175)Ce0.825O2-delta (x = 0.1, 0.2, and 0.4), and (La1-xSr0.2Bax)(0.175)Ce0.825O2-delta (x 5 0.03, 0.05, and 0.07) were prepared and characterized as the specimens with low, intermediate, and high index, respectively. The ionic conductivity was increased with increasing suggested index. The transmission electron microscopy analysis suggested that partial substitution of alkaline earth elements in place of La into Ce site contributes to a decrease of microdomain size and an improvement of conductivity. (La0.75Sr0.2Ba0.05)(0.175)Ce0.825O1.891 with high index and small microdomains exhibited the highest conductivity, wide ionic domain, and good performance in SOFCs. (C) 2003 The Electrochemical Society.

A-scan ultrasound system for real-time puncture safety assessment during percutaneous nephrolithotomy

Background: Kidney stone is a major universal health problem, affecting 10% of the population worldwide. Percutaneous nephrolithotomy is a first-line and established procedure for disintegration and removal of renal stones. Its surgical success depends on the precise needle puncture of renal calyces, which remains the most challenging task for surgeons. This work describes and tests a new ultrasound based system to alert the surgeon when undesirable anatomical structures are in between the puncture path defined through a tracked needle. Methods: Two circular ultrasound transducers were built with a single 3.3-MHz piezoelectric ceramic PZT SN8, 25.4 mm of radius and resin-epoxy matching and backing layers. One matching layer was designed with a concave curvature to work as an acoustic lens with long focusing. The A-scan signals were filtered and processed to automatically detect reflected echoes. Results: The transducers were mapped in water tank and tested in a study involving 45 phantoms. Each phantom mimics different needle insertion trajectories with a percutaneous path length between 80 and 150 mm. Results showed that the beam cross-sectional area oscillates around the ceramics radius and it was possible to automatically detect echo signals in phantoms with length higher than 80 mm. Conclusions: This new solution may alert the surgeon about anatomical tissues changes during needle insertion, which may decrease the need of X-Ray radiation exposure and ultrasound image evaluation during percutaneous puncture.

Cristalização de Biomateriais Vitrocerâmicos e Mineralização em Meio Fisiológico Simulado

We propose new theoretical models, which generalize the classical Avrami-Nakamura models. These models are suitable to describe the kinetics of nucleation and growth in transient regime, and/or with overlapping of nucleation and growth. Simulations and predictions were performed for lithium disilicate based on data reported in the literature. One re-examined the limitations of the models currently used to interpret DTA or DSC results, and to extract the relevant kinetic parameters. Glasses and glass-ceramics with molar formulation 0.45SiO2? (0.45-x)MgO?xK2O?0.1(3CaO.P2O5) (0?x?0.090) were prepared, crystallized and studied as potential materials for biomedical applications. Substitution of K+ for Mg2+ were used to prevent devritification on cooling, to adjust the kinetics of crystallization and to modify the in vitro behaviour of resulting biomaterials. The crystallization of the glass frits was studied by DTA, XRD and SEM. Exothermic peaks were detected corresponding to bulk crystallization of whitlockite-type phosphate, Ca9MgK(PO4)7, at approximately 900ºC, and surface crystallization of a predominant forsterite phase (Mg2SiO4) at higher temperatures. XRD also revealed the presence of diopside (CaMgSi2O6 in some samples. The predominant microstructure of the phosphate phase is of the plate-type, seemingly crystallizing by a 2-dimensional growth mechanism. Impedance spectroscopy revealed significant changes in electrical behaviour, associated to crystallization of the phosphate phase. This showed that electrical measurements can be used to study the kinetics of crystallization for cases when DTA or DSC experiments reveal limitations, and to extract estimates of relevant parameters from the dependence of crystallization peak temperature, and its width at half height. In vitro studies of glasses and glass-ceramics in acelular SBF media showed bioactivity and the development of apatite layers The morphology, composition and adhesion of the apatite layer could be changed by substitution of Mg2+ by K+. Apatite layers were deposited on the surface of glass-ceramics of the nominal compositions with x=0 and 0.09, in contact with SBF at 37ºC. The adhesion of the apatite layer was quantified by the scratch test technique, having been related with SBF?s immersion time, with composition and structure of the glass phase, and with the morphology of the crystalline phase of the glass-ceramics. The structure of three glasses (x=0, 0.045 and 0.090) were investigated by MAS-NMR ( 29Si and 31P), showing that the fraction of Q3 structural units increases with the contents of Mg, and that the structure of these glasses includes orthophosphate groups (PO43-) preferentially connected to Ca2+ ions. Mg2+ ions show preference towards the silicate network. Substitution of Mg2+ by K+ allowed one to change the bioactivity. FTIR data revealed octacalcium phosphate precipitation (Ca8H2(PO4)6.5H2O) in the glass without K, while the morphology of the layer acquires the shape of partially superimposed hemispheres, spread over the surface. The glasses with K present a layer of acicular hidroxyapatite, whose crystallinity and needles thickness tend to increase along with K content.

Wetting behaviour of femtosecond laser textured Ti-6Al-4V surfaces

The aim of the present work was to investigate the wetting behaviour of biomedical grade Ti-6Al-4V alloy surfaces textured by a femtosecond laser treatment. The material was treated in ambient atmosphere using an Yb: KYW chirped-pulse-regenerative amplification laser with a wavelength of 1030 nm and a pulse duration of 500 fs. Four main types of surface textures were obtained depending on the processing parameters and laser treatment method. These textures consist of: (1) nanoscale laser-induced periodic surface structures (LIPSS); (2) nanopillars; (3) a bimodal roughness distribution texture formed of LIPSS overlapping microcolumns; (4) a complex texture formed of LIPSS overlapping microcolumns with a periodic variation of the columns size in the laser scanning direction. The wettability of the surfaces was evaluated by the sessile drop method using distilled-deionized (DD) water and Hank's balanced salt solution (HBSS) as testing liquids. The laser treated surfaces present a hydrophilic behaviour as well as a high affinity for the saline solution, with equilibrium contact angles in the ranges 24.1-76.2. for DD water and 8.4-61.8. for HBSS. The wetting behaviour is anisotropic, reflecting the anisotropy of the surface textures. (c) 2012 Elsevier B.V. All rights reserved.

Produção de biodiesel por catálise heterogénea

Mestrado em Engenharia Química. Ramo optimização energética na indústria química.