Zhuo Cai

Electrochemical characterization of cast titanium alloys.

A reaction layer forms on cast titanium alloy surfaces due to the reaction of the molten metal with the investment. This surface layer may affect the corrosion of the alloy in the oral environment. The objective of this study was to characterize the in vitro corrosion behavior of cast titanium alloys. ASTM Grade 2 CP titanium, Ti-6Al-4V, Ti-6Al-7Nb and Ti-13Nb-13Zr alloys were cast into a MgO-based investment. Experiments were performed on castings (N=4) with three surface conditions: (A) as-cast surface after sandblasting, (B) polished surface after removal of the reaction layer, and (C) sandblasted surface after removal of the reaction layer. Open-circuit potential (OCP) measurement, linear polarization, and potentiodynamic cathodic polarization were performed in aerated (air+10% CO(2)) modified Tani-Zucchi synthetic saliva at 37 degrees C. Potentiodynamic anodic polarization was subsequently conducted in the same medium deaerated with N(2)+10% CO(2) gas 2 h before and during the experiment. Polarization resistance (R(P)) and corrosion rate (I(CORR)) were calculated. Numerical results were subjected to nonparametric statistical analysis at alpha=0.05. The OCP stabilized for all the specimens after 6 x 10(4)s. Apparent differences in anodic polarization were observed among the different surfaces for all the metals. A passivation region followed by breakdown and repassivation were seen on specimens with surfaces A and C. An extensive passive region was observed on all the metals with surface B. The Kruskal-Wallis test showed no significant differences in OCP, R(p), I(CORR) or break down potential for each of the three surfaces among all the metals. The Mann-Whitney test showed significantly lower R(P) and higher I(CORR) values for surface C compared to the other surfaces. Results indicate that the surface condition has more effect on corrosion of these alloys than the surface reaction layer. Within the oxidation potential range of the oral cavity, all the metal/surface combinations examined showed excellent corrosion resistance.

Mechanical properties and microstructures of cast Ti–Cu alloys

OBJECTIVES This study evaluated the mechanical properties of cast Ti-Cu alloys with the hope of developing an alloy for dental casting with better mechanical properties than unalloyed titanium. METHODS Ti-Cu alloys with five concentrations of copper (0.5, 1.0, 2.0, 5.0 and 10.0 mass%) were made in an argon-arc melting furnace. The alloys were cast into magnesia-based molds using a centrifugal casting machine. The microstructure, microhardness profile of the specimen cross section, tensile strength, yield strength, and elongation were determined for the castings. Scanning electron microscope fractography was undertaken for the fractured surfaces after tensile testing. XRD was performed on the polished specimens. Results were analyzed using one-way ANOVA and the Student-Newman-Keuls tests. RESULTS The mean tensile strengths of all the cast Ti-Cu alloys were significantly (p<0.05) higher than for cast commercially pure titanium (CP Ti). Of the Ti-Cu alloys tested, the 5 and 10% Cu alloys had significantly higher strength than the rest. The 10% Cu alloy exhibited the lowest mean elongation. CP Ti and the 0.5 and 1% Cu alloys showed higher ductility. The bulk hardness of all the cast Ti-Cu alloys, except for the 10% Cu alloy, and CP Ti was approximately the same. SIGNIFICANCE By alloying with copper, the cast titanium became stronger. Increases in the tensile strength (30%) and yield strength (40%) over CP Ti were obtained for the 5% Cu alloy. Elongation was approximately 3%, which was similar to cast Ti-6Al-4V. Ti-Cu alloys, such as the 5% Cu alloy, could be used for prosthetic dental applications if other properties necessary for dental castings are obtained.

In vitro corrosion resistance of titanium made using different fabrication methods.

The corrosion of cast or milled ASTM Grade II CP titanium with different surface conditions was studied by potentiodynamic anodic polarization and immersion testing. Specimens were fabricated using three dental titanium casting systems and from machined titanium. Three surface conditions were tested: (1) sandblasted with surface reaction layers remaining; (2) polished surface without surface reaction layers; and (3) sandblasted surface without surface reaction layers. An acidic saline solution (0.1 M lactic acid/0.1 M NaC1 [pH = 2]) and an artificial saliva were used as the corrosion media. Anodic polarization was performed starting at 50 mV below the rest potential and terminating at +2250 mV vs Ag/AgCl. Two surface conditions (sandblasted with the surface reaction layers and polished without such layers) were examined in the immersion test. Specimens were immersed in the corrosion media at 37 degrees C for six months. The recovered solution was analyzed by an atomic absorption spectrophotometer for titanium dissolution. A distinctive passive region on the polarization diagram, ranging from approximately 0 to approximately +1300 mV, was observed for all specimens in both media. Great similarity was observed for all the sandblasted specimens which had larger primary passive current densities and passive regions compared to the polished ones. A current density peak at approximately +1600 mV seen for all the specimens with sandblasted surfaces was less well defined for the polished specimens. Immersion testing in the acidic saline solution revealed no significant differences among the polished specimens. A significant increase (P < 0.05) in titanium dissolution was found for the sandblasted specimens with surface reaction layers remaining on the surfaces made with phosphate-bonded SiO2/Al2O3 investment compared to the polished ones. Significant differences were also found between sandblasted specimens with the surface reaction layers resulting from different investment materials and different casting methods. Measurable amounts of titanium were not found for all specimens in the artificial saliva after six months. It is evident that the corrosion behavior of cast CP titanium is similar to that of machined titanium. The surface roughness appears to be a more prominent factor than do the surface reaction layers on the polarization behavior of the CP titanium under the present experimental conditions. Surface roughness and the presence of the surface reaction layers both affect the dissolution of titanium.

Porcelain adherence to dental cast CP titanium: effects of surface modifications.

OBJECTIVES A reaction layer forms on cast titanium surfaces due to the reaction of the molten titanium with the investment material. Such a layer prevents strong adhesion between titanium and porcelain. This study characterized the effects of surface modifications on cast titanium surfaces and titanium-ceramic adhesion. METHODS ASTM grade II CP titanium was cast into an MgO-based mold. Castings were devested by sandblasting with alumina particles, and subjected to surface modification by immersion in one of the following solutions: (1) 35% HNO3-5% HF at room temperature for 1min; (2) 50% NaOH-10% CuSO4 x 5H2O at 105 degreesC for 10min; (3) the NaOH-CuSO4 solution followed by the HNO3-HF solution; (4) 50% NaOH-10% NaSO4 at 105 degreesC for 10 min; (5) the NaOH-NaSO4 solution followed by the HNO3-HF solution; and (6) 50% NaOH solution at 105 degreesC for 10min. Surfaces only sandblasted with alumina were used as controls. Specimen surfaces were characterized by XRD and SEM/EDS, and hardness-depth profiles were determined. All specimens were sandblasted with 110 microm alumina particles before porcelain firing. An ultra-low-fusing porcelain (Vita Titankeramik) was fused on the titanium surfaces. The titanium-ceramic adhesion was characterized by a biaxial flexure test, and area fraction of adherent porcelain (AFAP) was determined by X-ray spectroscopy. RESULTS EDS analyses revealed a substantial amount (13-17 wt%) of Al on the control, and specimens modified with Methods 2, 4, and 6. XRD revealed residual stress in the titanium surfaces and corundum on the control, and Methods 2, 4, and 6 specimens. A new Ti(Cu, Al)2 phase was identified on the titanium surfaces modified by immersion in 50% NaOH-10% CuSO4 x 5H2O aqueous solution. Reduced residual stress was observed on Method 1, 3, and 5 specimens. No corundum peaks were detected on these specimens. Compared to the control, significantly lower (P < 0.05) hardness values were found for Methods 1-3 and Method 5 specimens at 20 microm below the surfaces and for Method 1-5 specimens at 50 microm below the surfaces. Significantly higher (P < 0.05) AFAP values were found for surfaces modified with Methods 2-6 compared to the control and Method 1, and no significant differences were found among Methods 1-6, and between control and Method 1. SIGNIFICANCE Based on the results from the present study, porcelain adherence to cast CP titanium can be improved by the caustic baths used in the study.

Corrosion behavior of cast titanium with reduced surface reaction layer made by a face-coating method

This study characterized the corrosion behavior of cast CP titanium made with a face-coating method. Wax patterns were coated with oxide slurry of Y(2)O(3) or ZrO(2) before investing with a MgO-based investment. Three surface preparations were tested: ground, sandblasted, and as-cast. Uncoated castings served as controls. Sixteen-hour open circuit potential (OCP) measurement, linear polarization and potentiodynamic cathodic polarization were performed in an aerated modified Tani-Zucchi synthetic saliva at 37 degrees C. Anodic polarization was conducted in the same deaerated medium. Polarization resistance (R(p)) and Tafel slopes were determined. Corrosion current density was calculated for each specimen. Results (n=4) were subjected to nonparametric statistical analysis (alpha=0.05). Cross sections of cast specimens were examined by optical microscopy. Energy dispersive spectroscopy (EDS) spot analysis was performed at various depths below the surface. The OCP stabilized within several hours for all the specimens. Apparent differences in anodic polarization behavior were observed among the different surfaces. A distinctive wide passive region followed by breakdown was seen on specimens with ground and sandblasted surfaces. There were no significant differences in the corrosion resistance among the control and the two face-coating groups for each group. The Mann-Whitney test showed significantly lower OCP and higher R(p) values for ground surfaces. The surface condition significantly affected the corrosion behavior more than the face coating methods. In most cases, specimens with as-cast surfaces exhibited the least corrosion resistance during the potentiodynamic anodic polarization.

Grindability of cast Ti -Cu alloys

OBJECTIVE The purpose of the present study was to evaluate the grindability of a series of cast Ti-Cu alloys in order to develop a titanium alloy with better grindability than commercially pure titanium (CP Ti), which is considered to be one of the most difficult metals to machine. METHODS Experimental Ti-Cu alloys (0.5, 1.0, 2.0, 5.0, and 10.0 mass% Cu) were made in an argon-arc melting furnace. Each alloy was cast into a magnesia mold using a centrifugal casting machine. Cast alloy slabs (3.5 mm x 8.5 mm x 30.5 mm), from which the hardened surface layer (250 microm) was removed, were ground using a SiC abrasive wheel on an electric handpiece at four circumferential speeds (500, 750, 1000, or 1250 m/min) at 0.98 N (100 gf). Grindability was evaluated by measuring the amount of metal volume removed after grinding for 1min. Data were compared to those for CP Ti and Ti-6Al-4V. RESULTS For all speeds, Ti-10% Cu alloy exhibited the highest grindability. For the Ti-Cu alloys with a Cu content of 2% or less, the highest grindability corresponded to an intermediate speed. It was observed that the grindability increased with an increase in the Cu concentration compared to CP Ti, particularly for the 5 or 10% Cu alloys at a circumferential speed of 1000 m/min or above. SIGNIFICANCE By alloying with copper, the cast titanium exhibited better grindability at high speed. The continuous precipitation of Ti(2)Cu among the alpha-matrix grains made this material less ductile and facilitated more effective grinding because small broken segments more readily formed.

X-ray diffraction studies of oxidized high-palladium alloys.

OBJECTIVE The purpose of this study was to use x-ray diffraction (XRD) to obtain new information about the oxide layers on four representative oxidized high-palladium alloys. METHODS Cast specimens of two Pd-Cu-Ga alloys and two Pd-Ga alloys, with both polished and etched surfaces and air-abraded surfaces, were subjected to oxidation procedures recommended by the manufacturers. The specimens were analyzed by x-ray diffraction using CuK alpha radiation, and the peaks were compared to appropriate Joint Committee on Powder Diffraction Standards (JCPDS). RESULTS The surface preparation procedure had a profound effect on the phases present in the oxide layers. For the specimens that had been polished and etched, CuGa2O4 and beta-Ga2O3 were detected on the 79Pd-10Cu-9Ga-2Au alloy, whereas SnO2 and CuGa2O4 were detected on the 76Pd-10Cu-5.5Ga-6Sn-2Au alloy. The oxide layers on both Pd-Cu-Ga alloys contained Cu2O1 and the oxide layer on the 76Pd-10Cu-5.5Ga-6Sn-2Au alloy may contain beta-Ga2O3. The principal phase in the oxide layers on both Pd-Ga alloys that had been polished and etched was ln2O3, which exhibited extreme preferred orientation. No other phase was detected in the oxide layer on the 85Pd-10Ga-2Au-1Ag-1 ln alloy, whereas beta-Ga2O3 was found in the oxide layer on the 75Pd-6Ga-6Au-6Ag-6.5ln alloy. For the air-abraded specimens, beta-Ga2O2 was not present in the oxide layers on the Pd-Cu-Ga alloys, and beta-Ga2O3 was the major phase in the oxide layers on the Pd-Ga alloys. Palladium oxide(s) in varying amounts were detected for both surface preparations of the Pd-Cu-Ga alloys and for the air-abraded Pd-Ga alloys. Except for the 76Pd-10Cu-5.5Ga-6Sn-2Au alloy, the oxide layer caused minimal change in the lattice parameter of the palladium solid solution compared to that for the as-cast alloy. SIGNIFICANCE Knowledge of the phases found in the oxide layers on these high-palladium alloys is of fundamental importance for interpreting differences in the adherence of dental porcelain to the metal substrates under static and dynamic conditions, and may provide guidance in the development of new high-palladium alloys with improved metal-ceramic bonding.

Integrin mediated attachment of periodontal ligament to titanium surfaces

OBJECTIVE Reducing the force between the implant and the bone by recapitulating a similar matrix has the potential to reduce implant failure. To begin to pursue the goal of creating a periodontal ligament interface between a dental implant and bone, the mechanism of cellular attachment to dental implant surfaces must be characterized. METHODS In this study we examined the role of integrin receptors in the attachment of periodontal ligament fibroblasts to titanium surfaces utilized on dental implants; those surfaces included smooth polished titanium, acid pickled titanium, ground titanium, sandblasted and acid etched titanium, non-oxidized titanium that has been sandblasted and acid etched, hydroxyapatite coated titanium, titanium plasma sprayed or uncoated titanium. For these studies integrin mediated fibroblast attachment was blocked by the integrin blocking peptide GRGDSP or anti-integrin beta1 antibody or a combination of the two. Quantitation of periodontal ligament fibroblast attachment was completed by counting cells on the various implant surfaces after culturing in vitro for 24h with and without the integrin receptor blockers. RESULTS Antibody and peptide treatment significantly reduced the number of fibroblasts cells attached to the various implant surfaces but this effect varied significantly depending on the surface. Moreover, increased levels of peptide further decreased fibroblasts attachment in a dose dependent manner. SIGNIFICANCE Blocking studies suggest first, that integrin receptors function in periodontal ligament attachment to titanium surfaces and second, that different integrin subunits are important in attachment to a particular surface.

Effect of heat treatment on mechanical properties of age-hardenable gold alloy at intraoral temperature

OBJECTIVE The aim of this study was to investigate the effect of various heat treatments on the mechanical properties of gold alloys capable of age-hardening at intraoral temperature. METHODS Dumbbell-shaped patterns (ISO 6871) were cast with three gold alloys (Sofard; NC Type-IV; Aurum Cast, NihombashiTokuriki Co.). The Sofard alloy is age-hardenable at intraoral temperature. The castings underwent various heat treatments [as-cast (AC); solution treatment (ST); high-temperature aging (HA); intraoral aging (IA)]. After these heat treatments, ultimate tensile strength (UTS), 0.2% offset yield strength (YS), and elongation (EL) were measured at a strain rate of 1.7x10(-4)/s. Fracture surfaces of the specimens after tensile testing were observed using SEM. Vickers hardness was also measured after heat treating. RESULTS After IA, the hardness values of the Sofard alloy increased and reached values similar to the hardness of the Sofard specimens aged at high temperature (HA). The hardness values of the NC Type-IV and Aurum Cast specimens slightly increased after IA, but did not reach the values of the specimens after HA. All the Sofard, NC Type-IV and Aurum Cast specimens showed significantly (P<0.05) greater hardness values after HA, compared with the values after any other heat treatments (AC, ST and IA). The UTS and YS of the specimens indicated a tendency similar to the results obtained for hardness. The Sofard specimens with ST showed the greatest elongation compared to the corresponding NC Type-IV and Aurum Cast specimens. However, the elongation of the Sofard specimens was abruptly reduced after intraoral aging. CONCLUSION Intraoral aging significantly improved the mechanical properties and hardness of the Sofard alloy.

Transmission electron microscopic investigation of high-palladium dental casting alloys

OBJECTIVE The purpose of this study was to use transmission electron microscopy to examine four representative high-palladium alloys and gain insight into possible strengthening mechanisms. METHODS Castings of two Pd-Cu-Ga alloys and two Pd-Ga alloys were thinned by jet polishing and ion milling, followed by plasma cleaning, to yield foil specimens. Multiple specimens were prepared for each alloy. Bright-field images, dark-field images and selected-area electron diffraction patterns for the alloys in the as-cast condition, after simulated porcelain-firing heat treatment, and after annealing at 980 degrees C were analyzed by standard transmission electron microscope (TEM) techniques. The overall compositions of the ultrastructures for the specimen foils were determined by conventional standardless energy-dispersive spectroscopic analyses with the TEM, and mean values of the elemental compositions were compared to the nominal alloy compositions provided by the manufacturers. RESULTS There was generally good agreement (differences less than 2 wt%) between the overall ultrastructure composition and each nominal alloy composition, except for Protocol from which in may have been lost during casting or formed intermetallic compounds that were not detected by TEM. The same fine-scale tweed structure within parallel bands of approximately 100-200 nm width was observed for all four alloys in the as-cast condition and after simulated porcelain-firing heat treatment. The persistence of the ultrastructure in the specimens of the two Pd-Cu-Ga alloys annealed at 980 degrees C and quenched in ice water indicated very rapid formation from the palladium solid solution. The presence of ¿100¿ and ¿110¿ forbidden reflections for the <001> zone suggested that the tweed structure is ordered, although further research is necessary to establish this conclusion. SIGNIFICANCE The presence of a similar tweed structure in both the Pd-Cu-Ga alloys and the Pd-Ga alloys of substantially lower hardness shows that some other strengthening mechanism accounts for the high hardness and strength generally observed for Pd-Cu-Ga alloys.