Direct oxygen removal technique for recycling titanium using molten MgCl2 salt.

Deoxidation of Ti, or direct removal of O dissolved in metallic Ti, is known to be extremely difficult when Mg is used as the deoxidizing agent. This difficulty arises because the chemical potential of O2, pO2, under Mg/MgO equilibrium is high (approximately 10(-41) atm at 1200 K) and is equivalent to that of Ti containing ∼2 mass% O at 1200 K. Therefore, when deoxidizing Ti to the commercial level of high-grade pure Ti (below 0.05 mass% O) using an Mg reductant at 1200 K, the activity of the reaction product MgO (aMgO) must be decreased to below ∼0.025, which is difficult in practice. In this study, the removal of O in Ti in molten MgCl2 salt using an electrochemical technique was examined at ∼1173 K with the objective of obtaining Ti containing less than 0.05 mass% O. Ti samples and graphite electrodes immersed in molten MgCl2 served as the cathode and anode, respectively. A constant voltage was applied between the electrodes using an external DC source. Molten MgCl2 was employed to produce the deoxidizing agent Mg and to facilitate deoxidation of Ti by decreasing the activity of the reaction product MgO. By applying a voltage of approximately 3.1 V between the electrodes, the chemical potential of Mg in the molten MgCl2 was increased at the surface of the Ti cathode, and the Ti samples were deoxidized. The resulting O species, mainly formed O(2-) dissolved in the molten MgCl2, was removed from the molten salt by reacting with the C anode to form CO (or CO2) gas. Ti wires containing 0.12 mass% O were deoxidized to less than 0.02 mass% O. In some cases, the O concentration in the Ti samples was reduced to the level of 0.01 mass%, which cannot be accomplished using the conventional Kroll process. The possible application of this deoxidation technique to practical industrial recycling processes is discussed.

Direct production of low-oxygen-concentration titanium from molten titanium.

Titanium (Ti) is an attractive material, abundant in nature and possessing superior mechanical and chemical properties. However, its widespread use is significantly hampered by the strong affinity between titanium and oxygen (O), resulting in elevated manufacturing costs during the refining, melting, and casting processes. The current work introduces a high-throughput technique that effectively reduces the oxygen content in molten titanium to a level suitable for structural material applications (1000 mass ppm, equivalent to 0.1 mass%). This technique aspires to streamline the mass production of titanium by seamlessly integrating the refining, melting, and casting processes. The developed method leverages the high affinity of rare-earth metals, such as yttrium (Y), for oxygen. This method utilizes the formation reaction of their oxyhalides (YOF) to directly remove oxygen from liquid titanium, resulting in titanium with a significantly reduced oxygen content of 200 mass ppm. This technique enables the direct conversion of titanium oxide feeds into low-oxygen titanium without requiring conversion into intermediate compounds. Additionally, this process offers a pathway for the upgrade recycling of high-oxygen-content titanium scrap directly into low-oxygen titanium. Consequently, this technology holds the potential to dramatically lower titanium production costs, thereby facilitating its more widespread utilization.

Fabrication of titanium removable dental prosthesis frameworks with a 2-step investment coating method.

STATEMENT OF PROBLEM: Although pure titanium is known to have good biocompatibility, a titanium alloy with better strength is needed for fabricating clinically acceptable, partial removable dental prosthesis (RDP) frameworks. PURPOSE: The mechanical properties of an experimental Ti-5Al-5Cu alloy cast with a 2-step investment technique were examined for RDP framework applications. MATERIAL AND METHODS: Patterns for tests for various properties and denture frameworks for a preliminary trial casting were invested with a 2-step coating method using 2 types of mold materials: a less reactive spinel compound (Al(2)O(3)·MgO) and a less expensive SiO(2)-based material. The yield and tensile strength (n=5), modulus of elasticity (n=5), elongation (n=5), and hardness (n=8) of the cast Ti-5Al-5Cu alloy were determined. The external appearance and internal porosities of the preliminary trial castings of denture frameworks (n=2) were examined with a conventional dental radiographic unit. Cast Ti-6Al-4V alloy and commercially pure titanium (CP Ti) were used as controls. The data for the mechanical properties were statistically analyzed with 1-way ANOVA (α=.05). RESULTS: The yield strength of the cast Ti-5Al-5Cu alloy was 851 MPa and the hardness was 356 HV. These properties were comparable to those of the cast Ti-6Al-4V and were higher than those of CP Ti (P<.05). One of the acrylic resin-retention areas of the Ti-5Al-5Cu frameworks was found to have been incompletely cast. CONCLUSIONS: The cast biocompatible experimental Ti-5Al-5Cu alloy exhibited high strength when cast with a 2-step coating method. With a dedicated study to determine the effect of sprue design on the quality of castings, biocompatible Ti-5Al-5Cu RDP frameworks for a clinical trial can be produced.

Biofilm accumulation on additive manufactured Ti-6Al-4V alloy surfaces.

PURPOSE: This study investigated whether additive manufactured (AM) surfaces inhibit accumulation of bacterial biofilm on the surfaces of Ti-6Al-4V alloy dental implants. Bacterial biofilms are thought to cause peri-implant disease, which develops in mucosa surrounding titanium (Ti) and Ti alloy dental implants and can lead to bone loss and implant failure. METHODS: Accumulation of a Streptococcus mutans (ATCC 25175) biofilm on Ti-6Al-4V alloy was compared in relation to fabrication method, ie, AM using electron beam melting (EBM) or laser beam melting (LBM). Conventional lost-wax casting was used as positive control, and Teflon was used as negative control. Biofilm accumulation on the alloys and negative control (each n = 10) was conducted at 37°C under anaerobic conditions. After 4 h, the number of metabolically active S. mutans bacteria adhering to the alloy was determined with a bioluminescence assay. RESULTS: The quantitative roughness values of the specimens, before exposure to bacteria, ranked EBM > LBM > cast > Teflon. CONCLUSION: The amount of biofilm accumulation on the investigated AM metals and cast metal controls did not significantly differ.

Grindability of alpha-case formed on cast titanium.

The hardened alpha-case (alpha-case) layer inevitably forms on the surface of titanium castings when prepared by investment casting. Because the hardness of the alpha-case is incomparable to that of the interior structure, the perception exists that the alpha-case is difficult to remove during cutting, grinding and polishing. Grindability (ease of grinding) of cast cpTi and cast Ti-6Al-4V was evaluated by grinding cast specimens incrementally using a SiC abrasive wheel. The present study revealed that the presence of the brittle alpha-case with lower fracture toughness is beneficial in grinding titanium. The alpha-case on the ductile cpTi can be ground much easier than its bulk interior structure. In less ductile Ti-6Al-4V, the grinding rate is much higher than that of cpTi, and the alpha-case and its interior structure are at similar levels since the fracture toughness of its alpha-case and the bulk material is not large enough.

Grindability of cast Ti-6Al-4V alloyed with copper.

PURPOSE: This study investigated the grindability of cast Ti-6Al-4V alloyed with copper. MATERIALS AND METHODS: The metals tested were commercially pure titanium (CP Ti), Ti-6Al-4V, experimental Ti-6Al-4V-Cu (1, 4, and 10 wt% Cu), and Co-Cr alloy. Each metal was cast into five blocks (3.0 x 8.0 x 30.0 mm(3)). The 3.0-mm wide surface of each block was ground using a hand-piece engine with an SiC wheel at four circumferential speeds (500, 750, 1000, and 1250 m/min) at a grinding force of 100 g. The grindability index (G-index) was determined as volume loss (mm(3)) calculated from the weight loss after 1 minute of grinding and the density of each metal. The ratio of the metal volume loss and the wheel volume loss was also calculated (G-ratio, %). Data (n = 5) were statistically analyzed using ANOVA (alpha= 0.05). RESULTS: Ti-6Al-4V and the experimental Ti-6Al-4V-Cu alloys exhibited significantly (p < 0.05) higher G-indexes compared with CP Ti and Co-Cr at any rotational speed except for the lowest speed (500 m/min). At 500 m/min, the G-index of Ti-6Al-4V-Cu increased as the amount of alloyed copper increased. The 4% Cu and 10% Cu alloys had significantly greater G-indexes than did 1% Cu and Ti-6Al-4V at the highest rotational speed (1250 m/min). Increasing the percentage of alloyed copper and the circumferential speed also increased the G-ratio. CONCLUSIONS: A slight reduction in ductility due to alloying Ti-6Al-4V with copper improved the grindability of some of the resultant Ti-6Al-4V-Cu alloys.

Modeling wear of cast Ti alloys.

The wear behavior of Ti-based alloys was analyzed by considering the elastic-plastic fracture of individual alloys in response to the relevant contact stress field. Using the contact stresses as the process driving force, wear was computed as the wear rate or volume loss as a function of hardness and tensile ductility for Ti-based cast alloys containing an alpha, alpha+beta or beta microstructure with or without the intermetallic precipitates. Model predictions indicated that wear of Ti alloys increases with increasing hardness but with decreasing fracture toughness or tensile ductility. The theoretical results are compared with experimental data to elucidate the roles of microstructure in wear and contrasted against those in grindability.

Posterior amalgam restorations--usage, regulation, and longevity.

The use of dental amalgam has declined, but in most of the world, amalgam is the most widely used and widely taught direct restorative material for load-bearing posterior restorations. There are few national regulations on the use of amalgam; however, there are several nations where few amalgam restorations are placed. Long-term studies have shown that under optimum conditions, posterior restorations of amalgam and resin composite last longer than reported previously and that amalgam restorations outlast composite restorations. In general practice settings, posterior amalgam and composite restorations both have lower longevities.

Cross-sectional TEM analysis of porcelain fused to gold-coated titanium.

This study investigated the interfacial microstructure between gold-coated titanium and low-fusing porcelain. The square surfaces of cast titanium split rods were sputter-coated with gold using a sputter coater at 40 mA for 1,000 seconds. Specimens were prepared for transmission electron microscopy (TEM) by cutting and polishing two pieces of the gold-coated split-rod specimens, which were glued and embedded in Cu tubes with an epoxy adhesive. TEM observation was also conducted for the gold-coated specimens after degassing and porcelain fusing. Due to the gold coating, intermetallic compounds of Au-Ti formed under the sputtered gold layer after degassing and porcelain fusing. Ti3Au and Ti3Al layers were also observed beneath the Au-Ti intermetallic compound layer. There was good adhesion of porcelain to the Au-Ti compound and Ti oxides without any gaps or formation of a Ti-deficient intermediate layer, which is normally observed at the titanium-porcelain interface. The results of this TEM study suggested that gold-sputter-coating the cast titanium surface produced a Ti-Au intermetallic compound and suppressed the formation of a Ti-deficient intermediate layer, resulting in improved adherence between porcelain and titanium.

Grindability of cast Ti-Hf alloys.

As part of our systematic studies characterizing the properties of titanium alloys, we investigated the grindability of a series of cast Ti-Hf alloys. Alloy buttons with hafnium concentrations up to 40 mass% were made using an argon-arc melting furnace. Each button was cast into a magnesia-based mold using a dental titanium casting machine; three specimens were made for each metal. Prior to testing, the hardened surface layer was removed. The specimens were ground at five different speeds for 1 min at 0.98 N using a carborundum wheel on an electric dental handpiece. Grindability was evaluated as the volume of metal removed per minute (grinding rate) and the volume ratio of metal removed compared to the wheel material lost (grinding ratio). The data were analyzed using ANOVA. A trend of increasing grindability was found with increasing amounts of hafnium, although there was no statistical difference in the grindability with increasing hafnium contents. We also found that hafnium may be used to harden or strengthen titanium without deteriorating the grindability.

Electrochemical behavior of cast Ti-Ag alloys.

Anodic polarization tests were performed in 0.9% NaCl and 1% lactic acid solutions to characterize the relationship between the corrosion behavior and the microstructures of cast Ti-Ag (5-40% Ag) alloys. The anodic polarization curves for the Ti-Ag alloys up to 17.5% Ag were similar to those for pure titanium in both solutions. On the other hand, an abrupt increase in the current density was observed for the alloys with more than 20% Ag in the NaCl solution and with more than 27.5% Ag in the lactic acid solution. The microstructures of the corroded alloy surfaces indicated the deterioration of precipitated intermetallic compounds along the grain boundaries. The Ti-Ag alloys up to 17.5% Ag had excellent corrosion resistance similar to that of pure titanium. The alloys with 20-25% Ag may be also used as dental alloys, since they passivated again immediately after preferential dissolution in the NaCl solution.

Mechanical properties of cast Ti-Hf alloys.

This study examined the mechanical properties of a series of Ti-Hf alloys. Titanium alloys with 10 to 40 mass % Hf were made with titanium and hafnium sponge in an argon-arc melting furnace. Specimens cast into magnesia-based investment molds were tested for yield strength, tensile strength, percentage elongation, and modulus of elasticity. Vickers microhardness was determined at 25 to 600 microm from the cast surface. X-ray diffractometry was also performed. Commercially pure Ti (CP Ti) and pure Ti prepared from titanium sponge were used as controls. The data (n = 5) were analyzed with a one-way ANOVA and the Student-Newman-Keuls test (alpha = 0.05). The diffraction peaks of all the metals matched those for alpha Ti; no beta phase peaks were found. Alloys with Hf > or = 25% had significantly (p < 0.05) higher yield and tensile strength compared to the CP Ti and pure Ti. There were no significant differences (p > 0.05) in elongation among all the Ti-Hf alloys and CP Ti, whereas the elongation of alloys with Hf > or = 30% was significantly (p < 0.05) lower than that of the pure Ti. The cast Ti-Hf alloys tested can be considered viable alternatives to CP Ti because they were stronger than CP Ti and had similar elongation.

Corrosion behavior of cast Ti-6Al-4V alloyed with Cu.

It has recently been found that alloying with copper improved the inherently poor grindability and wear resistance of titanium. This study characterized the corrosion behavior of cast Ti-6Al-4V alloyed with copper. Alloys (0.9 or 3.5 mass % Cu) were cast with the use of a magnesia-based investment in a centrifugal casting machine. Three specimen surfaces were tested: ground, sandblasted, and as cast. Commercially pure titanium and Ti-6Al-4V served as controls. Open-circuit potential 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 conducted in the same medium deaerated by N(2) + 10% CO(2). Polarization resistance (R(p)), Tafel slopes, and corrosion current density (I(corr)) were determined. A passive region occurred for the alloy specimens with ground and sandblasted surfaces, as for CP Ti. However, no passivation was observed on the as-cast alloys or on CP Ti. There were significant differences among all metals tested for R(p) and I(corr) and significantly higher R(p) and lower I(corr) values for CP Ti compared to Ti-6Al-4V or the alloys with Cu. Alloying up to 3.5 mass % Cu to Ti-6Al-4V did not change the corrosion behavior. Specimens with ground or sandblasted surfaces were superior to specimens with as-cast surfaces.

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.

Optimizing mechanical properties of laser-welded gold alloy through heat treatment.

OBJECTIVE: The goal of this work was to improve the mechanical strength of laser-welded gold alloy with age-hardenability at intraoral temperature. METHODS: The gold alloy was cast conventionally in plate patterns (0.5 mm x 3.0 mm x 20 mm). After bench-cooling the mold to room temperature (as-cast state), transverse sections of the plate were made at mid-span. They were butted against one another and welded using Nd:YAG laser (current: 320 A; time: 10 ms; spot diameter: 1 mm). Three laser pulses were applied from both sides to cover the joint width (3.0 mm) of the specimens before or after solution heat treatment at 700 degrees C/5 min. Uncut control specimens (non-welded) were also prepared. After solution treatment, two different heat treatments were given the laser-welded specimens: high-temperature aging at 250 degrees C/15 min, or intraoral aging at 37 degrees C/3 days. Control specimens underwent all of the heat treatments after solution treatment. Tensile testing was conducted at a crosshead speed of 2 mm/min and a gauge length of 10 mm. RESULTS: Solution treatment of the gold alloy before laser-welding did not improve the mechanical strength of laser-welded gold alloy after high-temperature aging or intraoral aging. The joint strengths of laser-welded gold alloy were improved only by solution heat treatments after laser-welding and subsequent aging treatment at high or intraoral temperatures. SIGNIFICANCE: The results of this study indicated that laser-welded cast gold alloy prostheses aged at high or intraoral temperatures produce high strength when they are solution-treated after laser-welding.

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.

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.