Influence of stress-relieving heat treatments on the efficacy of Co-Cr-Mo-W alloy copings fabricated using selective laser melting.

Purpose This study aimed to evaluate the influence of stress-relieving heat treatments on the metal-ceramic bond strength and fitness accuracy of selective laser melting (SLM)-fabricated Co-Cr alloy copings.Methods SLM-manufactured Co-Cr samples were stress-relieved at 750 (Ht-750) and 1150 °C (Ht-1150). The microstructure, surface roughness, metal-ceramic bond strength, marginal and internal fit, Vickers hardness, and residual stress were then compared with those of the non-heat-treated group (As-built). The results were analyzed using one-way ANOVA and post-hoc tests (Tukey's or Student's t test) (P = 0.05).Results The microstructure of the Ht-1150 samples had a brittle oxide layer and lower surface roughness, resulting in significantly lower bond strength values than those of the other groups. The As-built group exhibited significantly lower marginal gap values than the Ht-750 and Ht-1150 groups. Therefore, the post-heat treatments degraded the marginal fitness. The surface residual stress in all sample groups were compressive because of the sandblasting effect. The compressive stresses were larger in Ht-1150 than in As-built and Ht-750 owing to their low hardness values.Conclusions Stress-relief annealing porcelain-fused-to-metal single crowns does not improve bond strength and degrades fitness accuracy because additional post-heat treatments induce thermal distortion. These findings are expected to facilitate the direct application of As-built SLM single crowns in dentistry to minimize post-manufacturing costs and time.

Effect of ultraviolet irradiation treatment on shear bond strength between polymethyl methacrylate and cobalt-chromium-molybdenum alloy.

We aimed to elucidate the effects of ultraviolet (UV) irradiation on the shear bond strength (SBS) between heat-cured polymethyl methacrylate (PMMA) and a Co-Cr-Mo alloy. Disk-shaped Co-Cr-Mo alloy prepared by casting were subjected to different UV treatment times (0, 15, and 30 min). To determine the effect of UV treatment on surface properties of the alloy, surface roughness, wettability, and chemical compositions were analyzed. To evaluate the SBS, cylindrical PMMA was bonded to the UV-treated alloy, and subsequently subjected to the SBS test after 24 h of storage at room temperature or following 10,000 thermal cycles (n=10/group). After the UV treatment, the surface roughness remained unchanged, but oxidation resulted in the surface exhibiting greater hydrophilic characteristics. The UV-treated group showed significantly higher SBS values than those of the non-treated group (p<0.001). These results suggested that UV treatment-mediated oxidation improved the bond strength between PMMA and Co-Cr-Mo alloy.

Effect of luting system with acidic primers on the durability of bonds with Ti-15Mo-5Zr-3Al titanium alloy and its component metals.

This study evaluated the effect of luting system with acidic primers on the durability of bonds with Ti-15Mo-5Zr-3Al titanium alloy (Ti-15Mo-5Zr-3Al) and its component metals. Adherend metals were Ti-15Mo-5Zr-3Al, Ti, Mo, Zr, and Al. Four primers were evaluated as adhesion promoters: Alloy Primer (ALP), Estenia Opaque Primer (EOP), M. L. Primer (MLP), and Super Bond liquid (SBL). An acrylic resin was used as the luting material. Pre- and post-thermocycling shear bond strength was determined to evaluate the bonding durability, and the results were compared using non-parametric statistical analyses (n=11/group). The post-thermocycling bond strength in MPa (median) associated with ALP, EOP, MLP, and SBL were 18.8, 19.8, 4.1, and 0.8, respectively, for Ti-15Mo-5Zr-3Al. The results showed that two primers containing 10-methacryloyloxydecyl dihydrogen phosphate (MDP) were effective for the durability of bonding of Ti-15Mo-5Zr-3Al to the resin. MDP enhanced the bonding durability of the resin bonded to either Ti, Zr, or Al.

Innovative design of bone quality-targeted intervertebral spacer: accelerated functional fusion guiding oriented collagen and apatite microstructure without autologous bone graft.

BACKGROUND CONTEXT: Although autologous bone grafting is widely considered as an ideal source for interbody fusion, it still carries a risk of nonunion. The influence of the intervertebral device should not be overlooked. Requirements for artificial spinal devices are to join the vertebrae together and recover the original function of the spine rapidly. Ordered mineralization of apatite crystals on collagen accelerates bone functionalization during the healing process. Particularly, the stable spinal function requires the ingrowth of an ordered collagen and apatite matrix which mimics the intact intervertebral microstructure. This collagen and apatite ordering is imperative for functional bone regeneration, which has not been achieved using classical autologous grafting. PURPOSE: We developed an intervertebral body device to achieve high stability between the host bone and synthesized bone by controlling the ordered collagen and apatite microstructure. STUDY DESIGN: This was an in vivo animal study. METHODS: Intervertebral spacers with a through-pore grooved surface structure, referred to as a honeycomb tree structure, were produced using metal 3D printing. These spacers were implanted into normal sheep at the L2-L3 or L4-L5 disc levels. As a control group, grafting autologous bone was embedded. The mechanical integrity of the spacer/bone interface was evaluated through push-out tests. RESULTS: The spacer with honeycomb tree structure induced anisotropic trabecular bone growth with textured collagen and apatite orientation in the through-pore and groove directions. The push-out load of the spacer was significantly higher than that of the conventional autologous graft spacer. Moreover, the load was significantly correlated with the anisotropic texture of the newly formed bone matrix. CONCLUSIONS: The developed intervertebral spacer guided the regenerated bone matrix orientation of collagen and apatite, resulting in greater strength at the spacer/host bone interface than that obtained using a conventional gold-standard autologous bone graft. CLINICAL SIGNIFICANCE: Our results provide a foundation for designing future spacers for interbody fusion in human.

Effect of Rotational Modes on Torque/Force Generation and Canal Centering Ability during Rotary Root Canal Instrumentation with Differently Heat-Treated Nickel-Titanium Instruments.

This study aimed to evaluate how various rotational modes influence the torque/force production and shaping ability of ProTaper Universal (PTU; non-heat-treated) and ProTaper Gold (PTG; heat-treated) nickel−titanium instruments. J-shaped resin canals were instrumented with PTU or PTG using an automated instrumentation device operated with reciprocating rotation [150° clockwise and 30° counterclockwise (R150/30) or 240° clockwise and 120° counterclockwise (R240/120)], optimum torque reverse motion (OTR), or continuous rotation (CR) (n = 10 each). Maximum force and torque were recorded, and canal centering ratios were calculated. Statistical analysis was performed with two-way ANOVA and a Bonferroni test (α = 0.05). The results were considered with reference to previous studies on the microstructure of the instruments. The upward force generated by R240/120 and OTR was smaller than that generated by R150/30 and CR in PTG (p < 0.05). The clockwise torque produced by OTR was lower than that produced by R150/30 in PTU and R240/120 and CR in PTG (p < 0.05). R240/120 and OTR induced less canal deviation compared to CR in PTU at 0 mm from the apex (p < 0.05). In conclusion, R240/120 and OTR reduced the screw-in force in PTG and improved the canal centering ability in PTU, which may be associated with the heat treatment-induced microstructural difference of the two instruments.

Biocompatibility of titanium from the viewpoint of its surface.

Among metals, Ti and majority of its alloys exhibit excellent biocompatibility or tissue compatibility. Although their high corrosion resistance is a factor in the biocompatibility of Ti and Ti alloys, it is clear that other factors exist. In this review, the corrosion resistance and passive film of Ti are compared to those of other metallic biomaterials, and their band gap energies, Egs, are compared to discuss the role of Eg in the reactivity with living tissues. From the perspective of the material's surface, it is possible to explain the excellent biocompatibility of Ti by considering the following factors: Ti ions are immediately stabilized not to show toxicity if it is released to body fluids; good balance of positive and negative charges by the dissociation of surface hydroxyl groups on the passive film; low electrostatic force of the passive film inducing a natural adsorption of proteins maintaining their natural conformation; strong property as n-type semiconductor; lower band gap energy of the passive film on Ti generating optimal reactivity; and calcium phosphate formation is caused by this reactivity. The results suggest that due to the passive oxide film, the optimal balance between high corrosion resistance and appropriate reactivity of Ti is the predominate solution for the excellent biocompatibility of Ti.

Outstanding in vivo mechanical integrity of additively manufactured spinal cages with a novel "honeycomb tree structure" design via guiding bone matrix orientation.

BACKGROUND CONTEXT: Therapeutic devices for spinal disorders, such as spinal fusion cages, must be able to facilitate the maintenance and rapid recovery of spinal function. Therefore, it would be advantageous that future spinal fusion cages facilitate rapid recovery of spinal function without secondary surgery to harvest autologous bone. PURPOSE: This study investigated a novel spinal cage configuration that achieves in vivo mechanical integrity as a devise/bone complex by inducing bone that mimicked the sound trabecular bone, hierarchically and anisotropically structured trabeculae strengthened with a preferentially oriented extracellular matrix. STUDY DESIGN/SETTINGS: In vivo animal study. METHODS: A cage possessing an anisotropic through-pore with a grooved substrate, that we termed "honeycomb tree structure," was designed for guiding bone matrix orientation; it was manufactured using a laser beam powder bed fusion method through an additive manufacturing processes. The newly designed cages were implanted into sheep vertebral bodies for 8 and 16 weeks. An autologous bone was not installed in the newly designed cage. A pull-out test was performed to evaluate the mechanical integrity of the cage/bone interface. Additionally, the preferential orientation of bone matrix consisting of collagen and apatite was determined. RESULTS: The cage/host bone interface strength assessed by the maximum pull-out load for the novel cage without an autologous bone graft (3360±411 N) was significantly higher than that for the conventional cage using autologous bone (903±188 N) after only 8 weeks post-implantation. CONCLUSIONS: These results highlight the potential of this novel cage to achieve functional fusion between the cage and host bone. Our study provides insight into the design of highly functional spinal devices based on the anisotropic nature of bone. CLINICAL SIGNIFICANCE: The sheep spine is similar to the human spine in its stress condition and trabecular bone architecture and is widely recognized as a useful model for the human spine. The present design may be useful as a new spinal device for humans.

Band structures of passive films on titanium in simulated bioliquids determined by photoelectrochemical response: principle governing the biocompatibility.

The band structures and band gap energies, E g, of passive films formed on titanium (Ti) in simulated bioliquids, Hanks' solution (Hanks) and saline, were evaluated. Ti was polarized at 0, -0.1, and -0.2 VAg/AgCl, E f, for 1 h. After polarization, the surfaces were characterized using X-ray photoelectron spectroscopy, and the photoelectrochemical responses were evaluated. The current change during photoirradiation was recorded as a photocurrent transient at each measuring potential, E m, and by changing the wavelength of the incident light. Passive films consisted of a very thin TiO2 layer containing small amounts of Ti2O3 and TiO, hydroxyl groups, and water. During polarization in Hanks, calcium and phosphate ions were incorporated or formed calcium phosphate but not in saline. Calcium phosphate and hydroxyl groups influenced the band structure. E g was graded in Hanks but constant in saline, independent of E f and E m. The passive film on Ti behaved as an n-type semiconductor containing two layers: an inner oxide layer with a large E g and an outer hydroxide layer with a small E g. In Hanks, E g was 3.3-3.4 eV in the inner oxide layer and 2.9 eV in the outer hydroxide layer. In saline, E g was 3.3 eV in the inner layer and 2.7 eV in the outer layer. Calcium phosphate and hydroxyl groups influenced the band structure of the passive film. The E g of the outermost surface was smaller than that of TiO2 ceramics, which is probably one of the principles of the excellent biocompatibility of Ti among metals.

Evaluation of cytocompatibility and osteoconductivity of Zr-14Nb-5Ta-1Mo alloy with MC3T3-E1 cells.

The cytocompatibility and osteoconductivity of the Zr-14Nb-5Ta-1Mo alloy were investigated using a mouse osteoblastic cell line (MC3T3-E1) to promote the application of this newly developed alloy in dental/medical treatment. The initial cell-attached morphology was visualized by fluorescent staining, and cells cultured on the Zr alloy showed similar cell adhesion behavior to cells cultured on titanium (Ti). In our 5-day proliferation investigation, similar cell numbers were obtained with both Zr alloy and Ti. These results indicate that the cytocompatibility of Zr alloy is similar to that of Ti. In addition, the similar results in the evaluation of alkaline phosphatase (ALP) activity and staining of deposited calcium using alizarin red S with both Zr alloy and Ti indicated that the osteoconductivity of the Zr alloy is similar to that of Ti. Our results prove the good cytocompatibility and osteoconductivity of the Zr-14Nb-5Ta-1Mo alloy, enabling its promotion for use in dental/medical applications.

Impaired dental implant osseointegration in rat with streptozotocin-induced diabetes.

OBJECTIVE: Few studies have reported on the impact of oxidative stress on the dental implant failure. The aim of this study was to investigate the impact of hyperglycemia-induced oxidative stress on dental implant osseointegration in diabetes mellitus (DM). METHODS: Acid-treated titanium implants were bilaterally placed in the maxillary alveolar ridge of streptozotocin-induced diabetic (DM group) and control rats after extraction of first molars. Histological analysis and micro-push-out test were performed 4 weeks after surgery. Oxidative stress and osteogenic markers in the surrounding bone were quantified by real-time polymerase chain reaction. In the in vitro study, rat bone marrow-derived mesenchymal stem cells (BMMSCs) were cultured on acid-treated titanium discs in a high-glucose (HG) or normal environment. Intracellular reactive oxygen species (ROS), cell proliferation, alkaline phosphatase (ALP) activity, and extracellular calcification were evaluated following antioxidant treatment with N-acetyl-L-cysteine (NAC). RESULTS: The implant survival rate was 92.9% and 75.0% in control and DM group, respectively. Bone-implant contact and push-out loads were significantly lower in the DM group. Expression of superoxide dismutase 1 at the mRNA level and on immunohistochemistry was significantly lower in the DM group. In vitro experiments revealed that the HG condition significantly increased ROS expression and suppressed the proliferation and extracellular calcification of BMMSCs, while NAC treatment significantly restored ROS expression, cell proliferation, and calcification. The ALP activity of both groups was not significantly different. CONCLUSION: In diabetes, high-glucose-induced oxidative stress downregulates proliferation and calcification of BMMSCs, impairing osseointegration and leading to implant failure.

Comparison of microstructures and mechanical properties of 3 cobalt-chromium alloys fabricated with soft metal milling technology.

STATEMENT OF PROBLEM: Although several manufacturers market soft metal milling blanks and systems, comprehensive comparative studies of differences in properties across commercially available soft metal milling alloys are lacking. PURPOSE: The purpose of this in vitro study was to compare the microstructures and mechanical properties of 3 soft metal milling cobalt-chromium (Co-Cr) alloys (Ceramill Sintron, Soft Metal, and Sintermetall). MATERIAL AND METHODS: Disk-shaped specimens (for surface characterization and hardness test) and dumbbell-shaped specimens (for tensile test as per International Organization for Standardization (ISO) 22674) were prepared by following each soft metal milling manufacturer's instructions. The crystal structures and microstructures of the 3 alloys were evaluated with optical microscopy, X-ray diffractometry (XRD), and scanning electron microscopy with electron backscattered diffraction (EBSD). The mechanical properties were investigated with a tensile test and Vickers hardness test (n=6). The results of the mechanical (tensile and hardness) tests were analyzed with 1-way ANOVA and the post hoc Tukey multiple comparison test (α=.05). RESULTS: The Sintermetall specimen showed a finer microstructure and more porosity than the other 2 alloys. The XRD and EBSD analyses showed that the γ (face-centered cubic, fcc) matrix phase was predominant in the Ceramill Sintron alloy and the ε (hexagonal close-packed, hcp) matrix phase was predominant in the Soft Metal alloy. The Sintermetall alloy showed a slightly higher amount of ε phase than γ phase, with more chromium carbide formation than the other 2 alloys. The Ceramill Sintron alloy showed a significantly higher tensile strength than the other 2 alloys (P<.05), but a significantly lower 2% offset yield strength than the other 2 alloys (P<.05). The highest elongation was found in the Ceramill Sintron alloy, followed by the Sintermetall and Soft Metal alloys. The elastic modulus was the highest in the Sintermetall alloy, followed by the Soft Metal and Ceramill Sintron alloys. No significant differences in Vickers hardness values were detected among the 3 alloys (P=.263). CONCLUSIONS: The different commercially available soft metal milling blanks and systems produced dissimilar alloys in terms of crystal structures and microstructures and, as a result, different mechanical properties.

Surface properties and biocompatibility of sandblasted and acid-etched titanium-zirconium binary alloys with various compositions.

Ti-Zr alloys have been investigated as an alternative to commercially pure Ti (c.p.Ti). According to our previous studies on the mechanical properties of Ti-Zr alloys, a Zr proportion in the range of 30-50 mol% has competitive advantages over Ti-10Zr and c.p.Ti. The aim of this study is to evaluate the biological response to Ti-Zr alloys with different compositions and their surface characteristics. Alloy surfaces are modified by sandblasting and sulfuric acid etching. As a result, similar surface structures are observed for c.p.Ti, Ti-10Zr, and Ti-30Zr, whereas Ti-50Zr does not form a micro-rough structure by the same treatment process. No significant difference is found in the viability of cells on c.p.Ti, Ti-10Zr, and Ti-30Zr, whereas lower cell attachment levels are detected on Ti-50Zr. In summary, Ti-30Zr reliably forms a micro-rough structure, which provides one evidence for its application in a new dental implant material.

Time Transient of Calcium and Phosphate Ion Adsorption by Rutile Crystal Facets in Hanks' Solution Characterized by XPS.

For the elucidation of the mechanism of calcium phosphate formation on commercially pure titanium (CP Ti) in the human body, rutile TiO2 single crystal plates with (001), (110), and (111) facets, namely, TiO2(001), TiO2(110), and TiO2(111), and polycrystalline plates (TiO2(poly)) were immersed in a simulated body fluid, Hanks' solution (Hanks), for 100-105 s, and the adsorption of calcium and phosphate ions was precisely characterized employing X-ray photoelectron spectroscopy (XPS). Previously published CP Ti data were used for comparison. Prior to immersion in Hanks, oxygen content was more than twice as high as that of titanium due to the existence of hydroxyl groups and water on the oxides. After immersion in Hanks, the composition and chemical state of the TiO2 substrates remained unchanged. Among the electrolytes contained in Hanks, only calcium and phosphate ions were adsorbed by and incorporated onto TiO2 surfaces. Adsorption of calcium ions onto rutile did not exhibit any systematic increase of calcium with immersion time except TiO2(poly). Adsorption of phosphate ions was initially constant, followed by an increase with the logarithm of immersion time. The adsorption rate of phosphate ions decreased in the following order: TiO2(001), TiO2(poly), TiO2(111), CP Ti, and TiO2(110). The coordination number and band gap of each crystal facet of rutile is important for the adsorption and incorporation of phosphate ions. Regular calcium phosphate formation on CP Ti is possibly enabled by the surface oxide film, which consists chiefly of amorphous TiO2. However, calcium phosphate formation kinetics on CP Ti differed from those on the TiO2 crystalline phase. These findings may further the understanding of CP Ti hard tissue compatibility.

Enhancement of antibacterial property of titanium by two-step micro arc oxidation treatment.

A customized micro arc oxidation (MAO) treatment technique was developed to obtain desirable antibacterial properties on titanium surfaces. The two-step MAO treatment was applied to fabricate a specimen containing both Ag and Zn in its surface oxide layer. Surface analyses and metal-ion release tests were performed to evaluate the presence of Ag and Zn and the ion release behavior for simulating practical usage, respectively. Additionally, the antibacterial properties of the specimens were also evaluated using gram-negative facultative anaerobic bacteria. The MAO-treated specimens containing both Ag and Zn showed excellent antibacterial properties against Escherichia coli, and the properties were sustained even after 28 days of immersion in physiological saline to simulate the living environment.

Reduction in anisotropic response of corrosion properties of selective laser melted Co-Cr-Mo alloys by post-heat treatment.

OBJECTIVES: The application of selective laser melting (SLM) to dentistry has been rapidly expanding; however, SLM-processed parts possess orientation-dependent properties (i.e., anisotropy) that can affect the long-term reliability of the dental prostheses. This study aimed to evaluate the anisotropic corrosion response of SLM-processed Co-Cr-Mo alloys under various heat treatments. METHODS: Samples fabricated via SLM along the horizontal plane (x-y plane) and vertical plane (x-z plane), with respect to the build direction, were subjected to various heat treatments. The resulting microstructures of the samples were characterized, and their corrosion properties were evaluated using anodic polarization and immersion tests. RESULTS: All samples showed similar transpassive behavior of the polarization curves. However, the immersion tests showed that the as-built x-z plane samples released significantly more metal ions than those fabricated on the x-y plane because of the larger area of preferentially corroded molten pool boundaries (MPBs) in the x-z plane samples. Our results further demonstrated that the heat treatments eliminated the MPBs, resulting in isotropic corrosion properties. However, excessive heat treatment at high temperatures induces the formation of coarse precipitates, resulting in a less-protective passive film. SIGNIFICANCE: The post-build heat treatments at temperatures that eliminate the MPBs are effective in reducing anisotropic corrosion behavior, and the lowest possible temperature is suitable for reducing the amount of released metal ions. These findings are expected to facilitate the application of SLM in dentistry to allow fast and precise production of prosthetic devices.

Reduction in nickel content of the surface oxide layer on Ni-Ti alloy by electrolytic treatment.

PURPOSE: Ni-Ti alloy has been increasingly applied to dental and medical devices, however, it contains nickel, which is known to have adverse effects on the human body. The purpose of this study was to form a nickel-free surface oxide layer on Ni-Ti alloy by electrolytic treatment for better biocompatibility. METHODS: Ni-49.15Ti (mol%) alloy was used, and the electrolytic treatment was performed in the electrolytes under 50 V for 30 minutes. The electrolytes were composed of lactic acid, water, and glycerol with different compositions. Surface analysis and characterization of Ni-Ti alloy were carried out by means of X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). RESULTS: Results indicated that the outmost surface oxide layer was nickel-free when using an electrolyte comprising 7.1% lactic acid, 57.2% water, and 35.7% glycerol by volume. The composition of this nickel-free surface oxide layer was determined as TiO1.92(OH)1.35 ∙ 0.43H2O by XPS, similar to that of unalloyed titanium. The thickness of this nickel-free layer was estimated at 6.4 nm by AES. CONCLUSION: The nickel-free surface oxide layer produced on Ni-Ti alloy is considered to improve the biocompatibility of medical and dental devices having shape memory effect and/or super-elasticity.

Investigation of different electrochemical cleaning methods on contaminated healing abutments in vitro: an approach for metal surface decontamination.

BACKGROUND: To evaluate the effects of electrolysis on cleaning the contaminated healing abutment surface and to detect the optimal condition for cleaning the contaminated healing abutment. METHODS: Ninety healing abutments removed from patients were placed in 1% sodium dodecyl sulfate solution and randomly divided for electrolysis with 7.5% sodium bicarbonate in the following three different apparatuses (N = 30): two stainless steel electrodes (group I), a copper electrode and a carbon electrode (group II), and two carbon electrodes (group III). The samples were placed on cathode or anode with different electric current (0.5, 1, and 1.5 A) under constant 10 V for 5 min. Electrolyte pH before and after electrolysis were measured. Then, the samples were stained with phloxine B and photographed. The proportion of stained areas was calculated. The surface was examined with a scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDS). RESULTS: Electrolyte pH decreased after electrolysis at 1 A and 1.5 A in group I and II. Applying cathode at 1 A in group III, the amount of residual contamination was the lowest in all the conditions examined in the present study. SEM images revealed that applying cathode at 1.5 A in group I induced a rough surface from the smooth surface before the treatment. EDS analysis confirmed that the surfaces treated on cathode at 1 A in group III revealed no signs of organic contamination. CONCLUSION: Electrolysis of using carbon as electrodes, placing the contaminated healing abutments on cathode, and applying the electric current of 1 A at constant 10 V in 7.5% sodium bicarbonate could completely remove organic contaminants from the surfaces. This optimized electrochemical cleaning method seems to be well worth investigation for the clinical management of peri-implant infections.

Zirconium-based metallic glass and zirconia coatings to inhibit bone formation on titanium.

Surface-modified commercially pure titanium (Cp-Ti) with zirconium (Zr)-based thin film metallic glasses (Zr-TFMGs) and ZrO2 thin films were surgically implanted into the tibiae of rats; the bone formation was analyzed to examine the performance of the coatings as a biomaterial. Zr-TFMGs and ZrO2 thin films were coated on Cp-Ti substrates to monitor the control of assimilation in vitro and in vivo. The microstructural and elemental analyses were carried out for the as deposited thin films by x-ray diffraction (XRD), transmission electron microscopy and x-ray photoelectron spectroscopy. TFMG- and ZrO2-coated Ti specimens were immersed in simulated body fluid (SBF) for a period of 21 days to evaluate the calcium phosphate precipitation in vitro. XRD, x-ray photoelectron spectroscopy and scanning electron microscopy/energy dispersive x-ray spectroscopy were used to quantify the mineralization on the coated Zr-TFMG and ZrO2. In vitro corrosion studies showed that the Zr-based TFMG and ZrO2 coatings sustained in the SBF, exhibited superior corrosion resistance to the bare crystalline Ti substrate. Wettability studies showed TFMG and ZrO2 coatings with a hydrophobic nature, and the TFMG-coated SBF-submerged specimens showed a hydrophilic nature. The in vitro cell viability of MC3T3-E1 cells showed good cell proliferation and low cytotoxicity. The calcification deposits were evaluated by staining with alizarin red S, which showed a lower calcium formation on Zr-TFMG compared to ZrO2. The present work also aims to assess the assimilation behavior of Cp-Ti, Zr-TFMG and ZrO2 in vivo by inserting the coated specimen in the femur of rats. After post-implantation of 8 weeks, specimens were examined by micro-CT evaluation. The bone contact ratios as calculated were 72.75%, 15.32% and 38.79%. Consequently, the bone affinity was Cp-Ti wire >ZrO2-coated Ti wire >Zr48Cu36Ag8Al8-coated Ti wire.

Time-Transient Effects of Silver and Copper in the Porous Titanium Dioxide Layer on Antibacterial Properties.

Recently, silver (Ag) and copper (Cu) have been incorporated into a titanium (Ti) surface to realize their antibacterial property. This study investigated both the durability of the antibacterial effect and the surface change of the Ag- and Cu-incorporated porous titanium dioxide (TiO2) layer. Ag- and Cu-incorporated TiO2 layers were formed by micro-arc oxidation (MAO) treatment using the electrolyte with Ag and Cu ions. Ag- and Cu-incorporated specimens were incubated in saline during a period of 0-28 days. The changes in both the concentrations and chemical states of the Ag and Cu were characterized using X-ray photoelectron spectroscopy (XPS). The durability of the antibacterial effects against Escherichia coli (E. coli) were evaluated by the international organization for standardization (ISO) method. As a result, the Ag- and Cu-incorporated porous TiO2 layers were formed on a Ti surface by MAO. The chemical state of Ag changed from Ag2O to metallic Ag, whilst that of Cu did not change by incubation in saline for up to 28 days. Cu existed as a stable Cu2O compound in the TiO2 layer during the 28 days of incubation in saline. The concentrations of Ag and Cu were dramatically decreased by incubation for up to 7 days, and remained a slight amount until 28 days. The antibacterial effect of Ag-incorporated specimens diminished, and that of Cu was maintained even after incubation in saline. Our study suggests the importance of the time-transient effects of Ag and Cu on develop their antibacterial effects.

Investigation of antibacterial effect of copper introduced titanium surface by electrochemical treatment against facultative anaerobic bacteria.

This study investigated the efficacy of copper (Cu) as an antibacterial element incorporated on titanium (Ti) surface by electrochemical treatment. Cu was incorporated onto Ti surface by micro-arc oxidation (MAO). A small amount of Cu was incorporated into the oxide layer and was found to be in oxidized states. Cu-incorporated samples exhibited no-harmful effect on the proliferation of osteoblastlike cells. Moreover, the difference in antibacterial property between fresh and incubated samples was evaluated using gram-positive and gram-negative facultative anaerobic bacteria. The specific antibacterial property of Cu incorporated into the Ti surface were confirmed. The antibacterial property prolonged upon immersion in physiological saline for 28 days. In other words, MAO-treated Ti containing Cu in this study is expected to achieve long-term antibacterial property in practical usage.