KR20220011299A - Manufacturing method of HA-coated dental implant using Ti-Nb-Ta alloy And dental implant - Google Patents

Abstract

The present invention relates to a manufacturing method of an HA coating-type dental implant using a Ti-Nb-Ta alloy and the dental implant manufactured thereby. Specifically, the present invention relates to the manufacturing method of an HA coating-type dental implant using a Ti-Nb-Ta alloy and the dental implant manufactured thereby, wherein, the present invention lowers a modulus of elasticity so as to reduce a stress shielding phenomenon with the bone, and to improve a corrosion resistance and biocompatibility by surface-treating a titanium alloy using a plasma electrolytic oxidation method after manufacturing the Ti-Nb-Ta alloy. The manufacturing method comprises: a step of preparing a titanium alloy; a step of forming an oxide film; and a step of forming an HA coating layer.

Description

Manufacturing method of HA-coated dental implant using Ti-Nb-Ta alloy And dental implant

The present invention relates to a method for manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy and to a dental implant. By treating it, it is possible to reduce the stress shielding phenomenon with bone by lowering the elastic modulus, and it is possible to improve corrosion resistance and biocompatibility. it's about

In general, dental implants are subjected to various surface treatment processes to improve intraosseous compatibility of implants after mechanically processing titanium or titanium alloy.

Conventional methods for surface treatment of dental implants include an acid etching method, plasma spray method, ion implantation method, heat oxidation method, sol-gel coating method, physical vapor deposition (PVD), and electrochemical vapor deposition method. have.

However, in the case of an implant surface-treated by an etching method using an acid, an inflammatory reaction occurs due to the acid remaining on the surface, or a clinical problem occurs due to corrosion on the surface of the implant.

In addition, the plasma spray method is currently mainly used for coating bioceramics on implants commercially, but micro-cracks, low bonding strength between the coating layer and the implant surface, phase change due to exposure to high temperature, non-uniform coating density, It has disadvantages such as irregular microstructure control.

In addition, in the electrochemical deposition method, the bonding force between the coating layer coated with calcium-phosphate, hydroxyapatite, etc. on titanium or titanium alloy and the implant (titanium or titanium alloy) is weak, so that it is peeled off from the implant, the interface between the implant and the coating layer, or the inside of the coating layer In this study, there was a problem in that chronic inflammation occurred in the bone tissue around the implant due to biodegradation and absorption by biological action.

That is, conventional implant surface treatment methods have a serious problem in that they are easily peeled off from the implant due to the weak bonding strength of the coating layer and lead to poor biocompatibility, resulting in implantation failure.

Accordingly, the present inventors have developed a method for surface treatment of dental implants using plasma electrolytic oxidation by themselves, which was disclosed through Korean Patent Registration No. 10-1737358.

In the conventional method for surface treatment of dental implants using plasma electrolytic oxidation, corrosion resistance and wear resistance are increased by surface treatment of dental implants by plasma electrolytic oxidation using a titanium-based alloy of Ti-6Al-4V as a main material. and has the advantage of improving biocompatibility.

However, in the conventional method for surface treatment of dental implants using plasma electrolytic oxidation, Ti-6Al-4V alloy is used as a titanium-based alloy, and this Ti-6Al-4V alloy is composed of cortical bone and In comparison, it has a modulus of elasticity of about 110 GPA, and still has a high modulus of elasticity compared to cortical bone. As the (stress shielding) phenomenon occurs, high stress is transmitted to the adjacent bone, and there is a problem that biocompatibility is greatly reduced or clinical failure occurs.

In addition, the conventional Ti-6Al-4V alloy contains vanadium and aluminum elements. In the case of aluminum element, it is known to cause Alzheimer's disease, and in the case of vanadium, it causes poisoning, digestive disorders, renal failure and hypoglycemia. There was a problem.

The present invention has been devised to solve this problem, by preparing a Ti-Nb-Ta alloy for the purpose of the present invention and then surface-treating the titanium-based alloy using a plasma electrolytic oxidation method, thereby increasing corrosion resistance and similar to bone An object of the present invention is to provide a method for manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy that has an elastic modulus and can reduce stress shielding with bone, and a dental implant.

Another object of the present invention is to use an electrolyte solution containing calcium and phosphorus ions during plasma conversion oxidation treatment to form calcium elements and phosphorus elements on the surface of a titanium-based alloy, thereby improving the biocompatibility of Ti To provide a method for manufacturing an HA-coated dental implant using a -Nb-Ta alloy and a dental implant.

Another object of the present invention is to perform plasma conversion oxidation treatment to form a porous oxide film on the surface, and then to form an HA (hydroxyapatite) coating layer by RF-magnetron sputtering, thereby improving biocompatibility. To provide a method for manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy and a dental implant.

Objects of the present invention are not limited to the objects mentioned above, and other objects not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the present invention includes a titanium-based alloy preparation step of preparing a titanium-based alloy; and an oxide film forming step of immersing the prepared titanium-based alloy in an electrolyte solution, and applying a pulse current to a plasma electrolytic oxidation device to form a porous oxide film on the surface of the titanium-based alloy. is Ti-25Nb-xTa, wherein x provides a method for manufacturing a dental implant using a Ti-Nb-Ta alloy, characterized in that 3 to 15.

In a preferred embodiment, the electrolyte solution contains calcium ions and phosphorus ions.

In a preferred embodiment, the electrolyte solution includes calcium acetate and calcium glycerophosphate.

In a preferred embodiment, in the step of forming the oxide film, the voltage applied to the plasma electrolytic oxidation device is 260 ~ 300V, and the available time is 2 minutes to 4 minutes.

In a preferred embodiment, after the oxide film forming step, a drying step of washing the titanium-based alloy on which the oxide film is formed with ethanol and distilled water and then drying; further comprises.

In addition, the present invention further provides a dental implant, characterized in that manufactured by the manufacturing method of the dental implant using the Ti-Nb-Ta alloy.

In a preferred embodiment, a porous oxide film containing _{TiO 2} , Ta ₂ O ₅ and Nb ₂ O ₅ is formed on the surface of the dental implant.

In a preferred embodiment, elemental calcium and elemental phosphorus are formed on the surface of the dental implant.

In addition, the present invention is a titanium-based alloy preparation step of preparing a titanium-based alloy; an oxide film forming step of immersing the prepared titanium-based alloy in an electrolyte solution and applying a pulse current to a plasma electrolytic oxidation device to form a porous oxide film on the surface of the titanium-based alloy; and an HA coating layer forming step of forming an HA (hydroxyapatite) coating layer on the surface of the titanium-based alloy on which the porous oxide film is formed, wherein the titanium-based alloy is Ti-25Nb-xTa, where x is 3 to 15 It further provides a method of manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy, characterized in that.

In a preferred embodiment, the electrolyte solution includes a phosphoric acid solution (H ₃ PO ₄ ).

In a preferred embodiment, in the step of forming the oxide film, the voltage applied to the plasma electrolytic oxidation device is 260 ~ 300V, and the available time is 2 minutes to 4 minutes.

In a preferred embodiment, after the oxide film forming step, a drying step of washing the titanium-based alloy on which the oxide film is formed with ethanol and distilled water and then drying; further comprises.

In a preferred embodiment, in the step of forming the HA coating layer, an HA (hydroxyapatite) coating layer is formed by RF-magnetron sputtering.

In addition, the present invention further provides a dental implant, characterized in that produced by the manufacturing method of the HA coated dental implant using the Ti-Nb-Ta alloy.

In a preferred embodiment, a porous oxide film containing _{TiO 2} , Ta ₂ O ₅ and Nb ₂ O ₅ is formed on the surface of the dental implant.

In a preferred embodiment, HA (hydroxyapatite) particles are formed on the surface of the dental implant.

The present invention has the following excellent effects.

According to the method for manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy of the present invention and a dental implant, a Ti-Nb-Ta alloy is prepared and then the titanium-based alloy is surface-treated using a plasma electrolytic oxidation method. By doing so, there is an effect of increasing corrosion resistance and preventing stress shielding with bone by having a modulus of elasticity similar to that of bone.

In addition, according to the method for manufacturing an HA-coated dental implant using the Ti-Nb-Ta alloy of the present invention and the dental implant, a titanium-based electrolyte solution containing calcium and phosphorus ions is used during plasma conversion oxidation treatment. By allowing elemental calcium and elemental phosphorus to be formed on the surface of the alloy, it has the advantage of inducing bone bonding and promoting bone cell adhesion and bone bond growth to improve biocompatibility.

In addition, according to the method for manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy of the present invention and the dental implant, plasma conversion oxidation treatment is performed to form a porous oxide film on the surface, and then, RF-magnetron By allowing the HA (hydroxyapatite) coating layer to be formed by sputtering, biocompatibility can be improved.

1 is a step diagram for explaining a method of manufacturing a dental implant using a Ti-Nb-Ta alloy according to an embodiment of the present invention.
2 is a step diagram for explaining a method of manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy according to another embodiment of the present invention.
3 is an image showing results using an X-ray fluorescence analyzer (XRF, Olympus, Japn) to analyze a chemical composition after manufacturing a Ti-25Nb-xTa alloy according to an embodiment of the present invention.
4 shows the microstructure of a Ti-25Nb-xTa alloy quenched in water at 0 °C after heat treatment at 1050 °C for 1 hour in an Ar gas atmosphere according to an embodiment of the present invention.
5 is a Ti-25Nb-xTa alloy in which x is 0, 3, 7, and 15, respectively, after heat treatment at 1050° C. for 1 hour in an Ar gas atmosphere and then quenching with water at 0° C. according to an embodiment of the present invention. It shows the XRD pattern.
6 shows the nanoindentation test results of Ti-25Nb-xTa alloy quenched in water at 0 °C after heat treatment at 1050 °C for 1 hour in an Ar gas atmosphere according to an embodiment of the present invention.
7 is a graph confirming the elastic modulus and Vickers hardness of the Ti-25Nb-xTa alloy quenched in water at 0 °C after heat treatment at 1050 °C for 1 hour in an Ar gas atmosphere according to an embodiment of the present invention.
8 is a surface morphology observed by FE-SEM after PEO treatment in an electrolyte containing Ca and P according to an embodiment of the present invention.
9 shows (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta, and (d) after PEO treatment in an electrolyte containing Ca and P according to an embodiment of the present invention; ) shows the EDS results for Ti-25Nb-15Ta.
10 shows (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta, and (d) after PEO treatment in an electrolyte containing Ca and P according to an embodiment of the present invention; A cross-sectional FE-SEM image of Ti-25Nb-15Ta is shown.
11 shows (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta, and (d) after PEO treatment in an electrolyte containing Ca and P according to an embodiment of the present invention; The cross-sectional EDS-line file results of Ti-25Nb-15Ta are shown.
12 is after PEO treatment in an electrolyte containing Ca and P according to an embodiment of the present invention (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta and (d) The XRD pattern of Ti-25Nb-15Ta is shown.
13 shows the nanoindentation test results for Ti-25Nb-xTa alloy after PEO treatment in Ca and P-containing electrolyte according to an embodiment of the present invention.
14 is a surface morphology observed by FE-SEM after PEO treatment in _{1M H 3} PO ₄ electrolyte according to an embodiment of the present invention.
_{15 is after PEO treatment in 1M H 3} PO ₄ electrolyte according to an embodiment of the present invention (a) is Ti-25Nb, (b) is Ti-25Nb-3Ta, (c) is Ti-25Nb-7Ta, and (d) shows the XRD results of Ti-25Nb-15Ta.
Figure 16 is an HA-coated FE-SEM image by RF-sputtering after PEO treatment in _{1M H 3} PO ₄ electrolyte according to an embodiment of the present invention.
17 is an EDS analysis result coated with HA by RF-sputtering after PEO treatment in _{1M H 3} PO ₄ electrolyte according to an embodiment of the present invention.
18 shows the XRD results of HA coating by RF-sputtering after PEO treatment in _{1M H 3} PO ₄ electrolyte according to an embodiment of the present invention.
19 shows the wettability contact angle of HA coated by RF-sputtering after PEO treatment in an electrolyte containing Ca and P and PEO treatment in an electrolyte containing 1M H ₃ PO _{4 according to an embodiment of the present invention.}
20 shows an atomic probe microscope (AFM) image coated with HA by RF-sputtering after PEO treatment in an electrolyte containing Ca and P and PEO treatment in 1M H ₃ PO _{4 electrolyte according to an embodiment of the present invention} .
21 is (a, a-1) Ti-25Nb, (b, b-1) Ti-25Nb grown SBF for 3 days after PEO treatment in an electrolyte containing Ca and P according to an embodiment of the present invention; -3Ta, (c, c-1) Ti-25Nb-7Ta and (d, d-1) Ti-25Nb-15Ta FE-SEM images.
_{22 is a HA coating by RF-sputtering after PEO treatment in 1M H 3} PO ₄ electrolyte according to an embodiment of the present invention to grow SBF for 3 days (a, a-1) Ti-25Nb, (b, b-1) Ti-25Nb-3Ta, (c, c-1) Ti-25Nb-7Ta, and (d, d-1) Ti-25Nb-15Ta FE-SEM images.
23 is an FE-SEM image showing the morphology of MC3T3-E1 osteoblasts cultured for 24 hours on the surface of a Ti-25Nb-xTa alloy treated with PEO in an electrolyte containing Ca and P.
24 is a FE-SEM image showing the morphology of MC3T3-E1 osteoblasts cultured for 24 hours after being treated with PEO _{in 1M H 3} PO _{4 electrolyte and coated with HA by RF-sputtering.}

As for the terms used in the present invention, general terms that are currently widely used are selected as possible, but in certain cases, there are also terms arbitrarily selected by the applicant. So the meaning should be understood.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to preferred embodiments shown in the accompanying drawings.

However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like reference numerals refer to like elements throughout.

1 is a step diagram for explaining a method of manufacturing a dental implant using a Ti-Nb-Ta alloy according to a first embodiment of the present invention.

Referring to FIG. 1 , in the method for manufacturing a dental implant using a Ti-Nb-Ta alloy according to a first embodiment of the present invention, a Ti-Nb-Ta alloy is prepared and then a titanium-based alloy is used using plasma electrolytic oxidation. As a method of manufacturing a dental implant that has a similar elastic modulus to bone and can reduce stress shielding with bone and improve biocompatibility, first prepare a titanium-based alloy (S110).

Here, the titanium-based alloy is produced using a vacuum arc melting furnace, Ti-Nb-Ta alloy.

In this case, the Ti-Nb-Ta alloy may be expressed as Ti-25Nb-xTa, where x is preferably 3 to 15.

Next, an oxide film forming step (S120) of forming a porous oxide film on the surface of the Ti-Ta-Nb alloy is performed.

In the oxide film forming step (S120), a porous oxide film is formed on the surface of the titanium-based alloy by immersing the produced Ti-Ta-Nb alloy in a first electrolyte solution, and applying a pulse current to a plasma electrolytic oxidation device. do.

Here, the first electrolyte solution is preferably a solution containing calcium ions and phosphorus ions.

This is to increase biocompatibility by allowing the oxide film formed on the surface of the implant to contain calcium and phosphorus ions that induce bone-bonding.

More specifically, the first electrolyte solution may be a solution containing calcium acetate and calcium glycerophosphate, and the calcium acetate is 26.69 g/L, the calcium glycerophosphate. (Calcium glycerophosphate) may be used at a concentration of 4.29 g/L.

In addition, in the oxide film forming step (S120), the voltage applied to the plasma electrolytic oxidation device is 260 ~ 300V, and it is preferable that the available time is 2 minutes to 4 minutes.

In addition, after the oxide film forming step (S120), a drying step (S130) of washing the titanium-based alloy on which the porous oxide film is formed with ethanol and distilled water and then drying it may be further performed.

That is, in the method of manufacturing a dental implant using a Ti-Nb-Ta alloy according to the first embodiment of the present invention, a Ti-Nb-Ta alloy is prepared and then the Ti-Nb-Ta alloy is formed by using a plasma electrolytic oxidation method. It is a technology to form a porous oxide film containing calcium ions and phosphorus ions on the surface of the Ti-Nb-Ta alloy by surface treatment.

This is because by using a Ti-Nb-Ta alloy prepared in an optimal weight ratio, the elastic modulus is lowered compared to the conventional Ti-6Al-4V alloy and has a similar elastic modulus to that of the bone, so it is possible to reduce the stress shielding phenomenon with the bone. and can improve corrosion resistance, biocompatibility and blood compatibility.

In addition, the present invention further provides a dental implant manufactured by the method for manufacturing a dental implant using a Ti-Nb-Ta alloy according to the first embodiment of the present invention.

_{A porous oxide film including TiO 2} , Ta ₂ O ₅ and Nb ₂ O ₅ , elemental calcium, and elemental phosphorus are formed on the surface of the dental implant.

2 is a step diagram for explaining a method of manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy according to a second embodiment of the present invention.

Referring to FIG. 2 , in the method for manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy according to a second embodiment of the present invention, a Ti-Nb-Ta alloy is prepared and titanium using plasma electrolytic oxidation. By surface-treating the alloy-based alloy to form a porous oxide film and then forming an HA (hydroxyapatite) coating layer, it has an elastic modulus similar to that of bone to reduce stress shielding with bone and improve biocompatibility. As a method of manufacturing a dental implant, first, a titanium-based alloy preparation step (S210) of preparing a titanium-based alloy is performed.

Here, since the titanium-based alloy preparation step (S210) has substantially the same configuration as the titanium-based alloy preparation step (S110) of the first embodiment of the present invention, the overlapping description will be omitted.

Next, an oxide film forming step (S220) of forming a porous oxide film on the surface of the Ti-Nb-Ta alloy is performed.

In the oxide film forming step (S220), a porous oxide film is formed on the surface of the titanium-based alloy by immersing the produced Ti-Nb-Ta alloy in a second electrolyte solution, and applying a pulse current to a plasma electrolytic oxidation device. do.

Here, the second electrolyte solution is preferably a solution containing a _{phosphoric acid solution (H 3} PO _{4 ).}

In addition, in the oxide film forming step (S220), the voltage applied to the plasma electrolytic oxidation device is 260 ~ 300V, and it is preferable that the available time is 2 minutes to 4 minutes.

In addition, after the oxide film forming step (S220), a drying step (S230) of washing the titanium-based alloy on which the porous oxide film is formed with ethanol and distilled water and then drying it may be further performed.

Next, the HA coating layer forming step (S240) of forming an HA (hydroxyapatite) coating layer on the surface of the titanium-based alloy on which the porous oxide film is formed is performed.

In this case, in the HA coating layer forming step (S240), the HA (hydroxyapatite) coating layer is preferably formed by RF-magnetron sputtering using an HA (hydroxyapatite) target.

That is, in the method of manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy according to the second embodiment of the present invention, a Ti-Nb-Ta alloy is prepared and then Ti-Nb- It is a technology of surface treatment of Ta alloy and forming an HA (hydroxyapatite) coating layer by RF-magnetron sputtering.

In addition, the present invention further provides a dental implant manufactured by the method for manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy according to a second embodiment of the present invention.

_{A porous oxide film including TiO 2} , Ta ₂ O ₅ and Nb ₂ O ₅ is formed on the surface of the dental implant, and HA (hydroxyapatite) particles are formed on the surface of the porous oxide film.

Example 1 (Preparation of Ti-Nb-Ta alloy)

In the present invention, a Ti-25Nb-xTa (x=0, 3, 7, and 15 wt.%) alloy was designed and manufactured.

For alloy manufacturing, CP-Ti (G&S Titanium, Grade 4, USA) was first melted 5 to 10 times to minimize oxidation of the designed alloy. Each designed alloy was melted 10 times in button shape and ingot shape to improve homogenization of each alloy.

For subsequent experiments, each alloy in the shape of an ingot was cut to a thickness of 3 mm using a high-speed diamond cutting machine (Accutom-5, Struers, Denmark) at a speed of 2000 rpm.

After homogenization, heat treatment was performed at 1050° C. for 1 hour in a high-purity argon atmosphere, followed by rapid cooling in water at 0° C.

A sample with a thickness of 3 mm was polished with 100-2000 grit sandpaper and then polished with 0.3-μm alumina powder (Al ₂ O ₃ ) for microstructure observation. The polished samples were ultrasonically washed with distilled water and ethyl-alcohol and dried at room temperature. After the alloy was prepared, it was measured by an X-ray fluorescence analyzer (XRF, DE-2000, Olympus, Japan) to determine the composition of the alloy.

Example 2 (plasma electrolytic oxidation treatment)

The PEO treatment on the Ti-25Nb-xTa alloy surface was polished using sandpaper up to 2000 grit, and then washed with ethyl-alcohol and distilled water to prepare a sample. Then, the sample washed using a DC power source (KEYSIGHT Co., Ltd., USA) was used as an anode, and a carbon rod was set as a cathode. Then, the applied voltage was 280V and the treatment time was 3 minutes. After the end of the experiment, the PEO-treated sample was washed with ethyl-alcohol and distilled water and then dried in the air.

The detailed concentration of the electrolyte is shown in Table 1 below, and the electrolyte for PEO treatment is calcium acetate monohydrate (Ca (CH ₃ COO) ₂ H ₂ O) + calcium glycerophosphate (C ₃ H ₇ CaO ₆ P) and 1M H ₃ Two electrolytes were used as PO ₄ (phosphoric acid 85.0%, H ₃ PO _{4 = 98.00).}

[Table 1]

Example 3 (RF-magnetron sputtering coating)

_{Samples PEO-treated with 1M H 3} P0 ₄ electrolyte for sputtering coating were washed with ethyl-alcohol and distilled water to minimize errors, and then dried. HA (tooth ash powder, 99.99%) target was coated by RF-magnetron sputtering system.

The distance between the substrate and the target was 80 mm, and a diameter of 2 inches was used for RF-sputtering. To form the plasma, the initial vacuum was ^{lowered to 10 -3} torr with a rotary pump, and then the vacuum level was dropped to 10 ^-6 torr using an oil diffusion pump.

Then, the amount of 40-sccm Ar gas into the chamber was maintained and controlled using a mass flowmeter. In order to increase the ion activity, the temperature of the substrate was set to 150 °C. RF power was set to a power of 50 W, and pre-sputtering was performed for 20 minutes before coating. After that, in this experiment, the deposition time was set to 60 minutes, and it was deposited on the surface of the sample treated with PEO _{with H 3} P0 _{4 electrolyte.} Detailed conditions of RF-sputtering using the HA target are shown in Table 2 below.

[Table 2]

Experimental Example 1 (Observation of microstructure and phase analysis of Ti-25Nb-xTa alloy)

TI-25Nb-xTa alloy _{was chemically etched in Keller's solution of 190 mL of H 2} O + 3 mL of HCl + 5 mL of HNO ₃ + 2 mL of HF, followed by optical microscopy (OM, Olympus BM60M, Japan). ) and a field emission scanning electron microscope (FE-SEM, S-4800 Hitachi, Japan) were used to observe the microstructure of each alloy.

FIG. 3 is an image showing the result using an X-ray fluorescence analyzer (XRF, Olympus, Japn) to analyze the chemical composition after preparing a Ti-25Nb-xTa alloy. 3 (a) shows Ti-25Nb, FIG. 3 (b) shows Ti-25Nb-3Ta, FIG. 3 (c) shows Ti-25Nb-7Ta, and FIG. 3 (d) shows Ti-25Nb-15Ta alloys. .

It can be confirmed that the chemical composition of all homogenized alloys is almost similar to the designed alloy, which indicates that the alloy was well prepared.

Figure 4 shows the microstructure of Ti-25Nb-xTa alloy quenched in water at 0 °C after heat treatment at 1050 °C for 1 hour in an Ar gas atmosphere. 4(a, e) is Ti-25Nb, FIG. 4(b, f) is Ti-25Nb-3Ta, FIG. 4(c, g) Ti-25Nb-7Ta, FIG. 4(d, h) is Ti-25Nb-15T.

As shown in Fig. 4(a), the Ti-25Nb alloy exhibited a martensitic phase (α'') structure. As the Ta content increased, grain formation improved and the martensitic structure decreased.

In addition, as shown in Fig. 4 (d, h), a martensitic structure was not observed in the Ti-25Nb-15Ta alloy. The grain size of Ti-25Nb-xTa alloy increased with Ta content, whereas the microstructure exhibited an equiaxed (β) structure.

It can be seen that the Nb and Ta elements affected the formation of martensite in the Ti alloy.

The beta phase was maintained because the martensite starting temperature (Ms) of Ti-25Nb-15Ta alloy was lower than room temperature. Therefore, it can be seen that Nb and Ta acted as β-stabilizing elements in the Ti alloy. The β phase can be stabilized by reducing the precipitation temperature of α from β. The EDS results of Ti-25Nb-xTa alloy show good agreement with the chemical composition of the designed alloy and uniform structure.

EDS results of Ti-25Nb-xTa alloy are shown in Table 3 below.

[Table 3]

Fig. 5 shows the XRD patterns of Ti-25Nb-xTa alloys with x of 0, 3, 7, and 15, respectively, after heat treatment at 1050 °C in Ar gas atmosphere for 1 hour and then quenching with water at 0 °C. Fig. 5 (a) shows Ti-25Nb, Fig. 5 (b) shows Ti-25Nb-3Ta, Fig. 5 (c) shows Ti-25Nb-7Ta, and Fig. 5 (d) shows Ti-25Nb-15Ta alloys. .

All peaks were detected in α″ (orthorhombic) and β (body-centered cubic (BCC)) phases. Martensitic α-phase peaks were observed at 2θ = 34, 36, 39, 41, 68, 70 and 73°, and equiaxed β-phase peaks were observed at 2θ = 38, 54, 70 and 83°. The martensitic α" phase peak decreased mainly with increasing Ta content. The equiaxed β-phase peak increased with Ta content. The martensitic transformation temperature decreased in proportion to the increase in the stabilizing element content of the alloy. Therefore, Nb and The β volume fraction increased because Ta acts as a β-stabilizing element of the Ti alloy.The XRD results in Fig. 5 are consistent with the microstructure revealed by OM and FE-SEM in Fig. 4.

Experimental Example 2 (Measurement of elastic modulus and hardness of Ti-25Nb-xTa alloy)

The elastic modulus and hardness of each alloy were measured using nanoindentation (TTX-NHT3, Anton Paar, Austria). The maximum load of the sample was set to 50N, the load application time and the load removal time were set to 30 seconds each, and the stop time was set to 5 seconds. Each sample was measured three times to obtain the minimum/maximum value, and the mean and standard deviation were obtained.

6 is a nanoindentation test result of Ti-25Nb-xTa alloy quenched in 0 °C water after heat treatment at 1050 °C for 1 hour in Ar gas atmosphere, and Figure 7 is 1050 °C for 1 hour in Ar gas atmosphere. It is a graph confirming the elastic modulus and Vickers hardness of Ti-25Nb-xTa alloy quenched in water at 0 ℃ after heat treatment at

The load-displacement curve of Ti-25Nb-3Ta shifted to the left and the load-displacement curve of Ti-25Nb-15Ta shifted to the right. The modulus of elasticity and hardness can be obtained from the curve. Detailed values of the elastic modulus and Vickers hardness are shown in Table 4 below.

[Table 4]

Ti-25Nb-3Ta alloy showed the highest Vickers hardness of 537.57 HV, and the Vickers hardness of Ti-25Nb-15Ta was 292.71 HV. When Ta is added to the titanium alloy (Ti-xTa), the yield strength and Vickers hardness gradually increase, and when x = 40 or more, the yield strength and Vickers hardness decrease. 4 and 5 suggest that the internal stress generated by the formation of the martensitic structure was reduced. In addition, metastable BCC structures were formed with increasing Ta content.

Ti-25Nb-15Ta alloy showed the lowest modulus of elasticity of 66.24 GPa, whereas the modulus of elasticity of Ti-25Nb alloy was relatively high (99.58 GPa). The modulus of elasticity of Ti-25Nb-xTa is significantly lower than that of conventional commercially pure Ti and Ti-6Al-4V alloys (about 125 GPa), which may reduce the stress shielding effect. The modulus of elasticity is related not only to the crystal structure, but also to the distance between atoms in the crystal lattice. Therefore, the modulus of elasticity decreased when β-phase stable elements such as Nb and Ta were added.

Experimental Example 3 (Surface properties of Ti-25Nb-xTa alloy treated with PEO)

The surface properties of the surface-treated samples were analyzed using scanning electron microscopy (FE-SEM) and energy-dispersive X-ray spectroscopy (EDS, Inca program, Oxford, UK).

The microstructure of each alloy was observed with an optical microscope and FE-SEM.

The minimum/maximum size and surface area of pores in the surface-treated Ti-25Nb-xTa alloy were measured using an image analyzer (Image J, Wayne Pasband, USA).

The crystal structure of the surface was analyzed using X-ray diffraction (XRD, X'pert Philips, Netherlands) in the diffraction angle range of 10 °C to 90 °C. The crystal structure of each characteristic peak was confirmed by comparison with the Joint Committee on Power Diffraction Standards (JCPDS, PCPDFWIN) card #21-1272.

Experimental Example 3-1: Analysis of surface properties of Ti-25Nb-xTa alloy treated with PEO in Ca and P electrolytes

Figure 8 is the surface morphology observed by FE-SEM after PEO treatment in the electrolyte containing Ca and P. (a, a-1) is Ti-25Nb, (b, b-1) is Ti-25Nb-3Ta, (c, c-1) is Ti-25Nb-7Ta, (d, d-1) is Ti-25Nb-15Ta.

All samples showed porous surfaces and irregularly shaped pores. As the Ta content increases, the size of the pores appears to decrease while their number increases. Based on previous studies, the PEO time was set to 3 min. In addition, at voltages above 350 V, a voltage of 280 V was used because surface cracks occur with increasing time due to thermal stress. The porous structure exhibited a very rough surface due to the microscopic exhaust channels formed in the process. When the applied voltage exceeds the threshold required to penetrate the barrier layer, many sparks were observed on the coating surface, confirming the formation of an oxide film, and then the sparks gradually disappeared.

In particular, no microcracks were observed in the alloy. Chemical bonds can be formed in the microemission channels, which _{form oxides such as TiO 2} , Nb ₂ O ₅ and Ta ₂ O ₅ , improving biocompatibility and corrosion resistance.

To analyze the number of pores on the PEO surface, the specific surface area was measured using an image analyzer (Image J, Wayne Rasband, USA). The analysis results are shown in Table 5 below.

[Table 5]

Ti-25Nb, Ti-25Nb-3Ta, Ti-25Nb-7Ta and Ti-25Nb-15Ta showed porosity of 7.07, 7.37, 7.16 and 9.09% of the PEO surface. The maximum pore sizes are 1.31, 1.23, 1.209 and 1.14 μm, and the minimum pore sizes are 0.59, 0.60, 0.61 and 0.69 μm, respectively. Therefore, the minimum pore size and number of pores were larger in Ti-25Nb-15Ta alloy, while the maximum pore size was smaller than that of other alloys.

This indicates that the pore size and number can be adjusted according to the Ta content. In general, the shape of the pores formed on the surface depends on the type of oxide formed on the surface.

Figure 9 shows the results of (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta, and (d) Ti-25Nb-15Ta after PEO treatment in an electrolyte containing Ca and P. EDS results are displayed.

EDS was performed outside and inside the stoma. EDS analysis results are shown in Table 6 below.

[Table 6]

In all alloys, higher Ca and P contents were measured in the pores than the surface, and a large oxygen element content was detected at the surface due to oxide film formation. Considering the stoichiometry, the ideal Ca:P ratio for HA formation is 1.67. The Ca/P ratios inside the pores were 1.61, 1.41, 1.60 and 1.71, respectively, which are relatively close to 1.67.

Therefore, the rate of cell deposition and growth can be increased inside the pores of the PEO-treated surface, promoting higher bioactivity between bone and dental implants.

Figure 10 shows cross-sectional FEs of (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta and (d) Ti-25Nb-15Ta after PEO treatment in an electrolyte containing Ca and P. -SEM images are shown.

The PEO coating adhered well to all alloys. Since specimen cutting uses a relatively physical method, it may cause damage to the specimen, so it should be considered. Therefore, it is suggested that all PEO coatings exhibit good bonding strength. The phase composition (amorphous and/or crystalline) of the PEO oxide film on titanium depends on the processing conditions. The thickness and porosity of the obtained oxide layer depend on the applied voltage and current density. The layer thickness generally increases with voltage. In addition, as the Ta content increased, the crater structure flattened and the thickness of the coating increased.

Ti-25Nb, Ti-25Nb-3Ta, Ti-25Nb-7Ta and Ti-25Nb-15Ta showed coating thicknesses of 2.32, 2.59, 2.73 and 3.5 μm, respectively, as measured using Image J. The analysis results are shown in Table 7 below.

[Table 7]

Figure 10 (c) shows the pore shape in cross section. The pores were large inside the film and their shape changed depending on the type of oxide formed on the surface. The maximum pore size decreased according to the Ta content, and the minimum pore size increased. These results _{indicate that the oxide film of Ta 2} O ₅ contributed to the formation of pores.

Figure 11 shows the cross-sectional EDS of (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta and (d) Ti-25Nb-15Ta after PEO treatment in an electrolyte containing Ca and P. -line Display the file result.

Table 7 shows the observed PEO thickness in Fig. 11. The concentrations of O, Ca, and P were higher in the PEO film, indicating that Ca and P were well doped in the PEO coating layer. In addition, a P peak was also detected outside the interface of the coating layer, which is thought to be due to polishing.

12 is an XRD pattern of (a) Ti-25Nb, (b) Ti-25Nb-3Ta, (c) Ti-25Nb-7Ta, and (d) Ti-25Nb-15Ta after PEO treatment in an electrolyte containing Ca and P. indicates

The peak can be attributed to the locally formed anatase phase (25 °C) at high temperature by a spark discharge that promotes the nucleation of crystals in the amorphous material. TiO ₂ has three forms: rutile, anatase and brookite. In general, anatase is the most preferred form. The stress field generated by anatase favors fatigue behavior and may improve bone implant bonding, including its ability to reduce the negative effects of brittle oxide coatings, accelerate the formation of HA, and consequently enhance bone fusion. Anatase is known to be more suitable for apatite formation than other Ti oxide phases because of the crystallographic agreement between the (0001) plane of biomimetic apatite and the (110) plane of anatase [33]. As the Ta content increased, the TiO ₂ phase content decreased, while the Ta ₂ O ₅ phase content gradually increased.

13 shows the nanoindentation test results for Ti-25Nb-xTa alloys after PEO treatment in Ca and P-containing electrolytes.

Their modulus of elasticity and Vickers hardness are shown in Table 8 below.

[Table 8]

In general, PEO coatings of Ca and P-containing electrolytes on Ti-25Nb-xTa alloys showed low modulus of elasticity. Ti-25Nb-7Ta alloy showed the lowest elastic modulus of 63.08 GPa. Because it is relatively close to human cortical bone (30 GPa), the bone weakening effect and bone resorption can be minimized. The hardness of the PEO surface can be directly affected by the hardness of the bulk material and is difficult to measure due to the porosity of the surface. Therefore, the modulus of elasticity of the PEO-treated surface depends on the type and number of pores on the surface.

Experimental Example 3-2: Analysis of surface properties of Ti-25Nb-xTa alloy treated with PEO in _{1M H 3} PO _{4 electrolyte}

14 is a surface morphology observed by FE-SEM after PEO treatment in _{1M H 3} PO _{4 electrolyte.} 14, (a, a-1) is Ti-25Nb, (b, b-1) is Ti-25Nb-3Ta, (c, c-1) is Ti-25Nb-7Ta, (d, d-1) is Ti-25Nb-15Ta.

It can be seen that all the surfaces had a porous surface, and no cracks were found on the surface. According to a previously reported study, charge density is important for PEO growth, and the shape of the coating surface is first formed into an elongated earthworm-like shape, and then changes to a porous shape when the current density is increased.

As shown in FIG. 14 , it can be seen that as the Ta content increases, many small pores are formed on the surface, and a slightly elliptical or irregular shape appears. The porosity of the PEO surface of Ti-25Nb, Ti-25Nb-3Ta, Ti-25Nb-7Ta, and Ti-25Nb-15Ta was 2.8, 1.11, 1.46, and 1.7. The maximum pore sizes are 0.97, 0.80, 070, and 0.73 μm, and the minimum pore sizes are 0.30, 0.29, 0.30, and 0.35 μm. It can be seen that the porosity of the Ti-25Nb alloy is relatively high. However, it can be seen that the number of pores gradually increases when Ta is added.

Detailed porosity and maximum/minimum pore size, and number of pores are shown in Table 9.

[Table 9]

As shown in Table 9, it can be seen that the minimum pore size and the number of pores increase as the Ta content increases. In the case of Ti-25Nb-15Ta alloy, it can be seen that the number of pores is slightly reduced compared to Ti-25Nb-3Ta and Ti-25Nb-7Ta, which is thought to be due to the increase in the maximum pore size and the minimum pore size.

15 is _{after PEO treatment in 1M H 3} PO ₄ electrolyte (a) is Ti-25Nb, (b) is Ti-25Nb-3Ta, (c) is Ti-25Nb-7Ta, and (d) is Ti-25Nb- The XRD result of 15Ta is shown.

_{Various Nb 2} O ₅ , Ta ₂ O ₅ , and TiO ₂ phases were detected on the PEO-treated surface. For all peaks, an anatase phase of 25° and a rutile phase of 27°, which are Ti crystal phases, were detected. It is formed by the reaction between ^{Ti 4+} and hydroxyl (OH ^- ) when the oxide film is formed in the initial stage of the PEO process. Compared with rutile, it can absorb more OH - and PO ₄ ^{3 - which} is favorable for Ca and P compound deposition. As described in FIG. 12 , as the Ta content increases, the TiO ₂ phase decreases, which can be seen to be in good agreement with the design of the alloy.

Experimental Example 3-3: Analysis of surface properties of Ti-25Nb-xTa alloy coated with HA by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte}

16 is a FE-SEM image of HA coated by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte.} 16 (a - a-2) is Ti-25Nb, (b - b-2) is Ti-25Nb-3Ta, (c - c-2) is Ti-25Nb-7Ta, and (d - d-2) ) is Ti-25Nb-15Ta.

16 (a ~ d-1), it can be confirmed that only the shape of the PEO is maintained. In (a-2 to d-2) of FIG. 16, circular particles were formed on the surface and pores, and it can be confirmed that the HA particles were uniformly coated on the surface by coating the HA. In sputtering, frequency (RF), power (W), bias voltage (V), sputtering temperature (C), processing time, etc. are important, and the HA coating improves bone formation and improves the bond strength between the biomaterial and its surrounding bones. make it In addition, since the initial surface roughness of the substrate can be maintained, the coating is advantageous in clinical trials where the initial surface roughness of the implant should not be significantly affected.

17 is an EDS analysis result of HA coating by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte.} Fig. 17 (a) shows Ti-25Nb, Fig. 17 (b) shows Ti-25Nb-3Ta, Fig. 17 (c) shows Ti-25Nb-7Ta, and Fig. 17 (d) shows Ti-25Nb-15Ta.

It can be seen that Ca, P, and O elements were detected in all alloys. This indicates that the HA-sputtering was successful in the deposition. Detailed result values are shown in Table 10 below.

[Table 10]

O was detected more outside the pores than inside the pores. In addition, the content of P was detected to be higher than that of Ca, which can be sputtered again from the growing film by ions that are lost during deposition or are pushed back before reaching the substrate surface.

18 shows the XRD results of HA coating by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte.} Fig. 18 (a) shows Ti-25Nb, Fig. 18 (b) shows Ti-25Nb-3Ta, Fig. 18 (c) shows Ti-25Nb-7Ta, and Fig. 18 (d) shows Ti-25Nb-15Ta.

All peaks indicated anatase (25°) and rutile (27°) on Ti. In addition, HA peaks were detected near (25°) and (38°). It has a peak similar to that of FIG. 12 and shows a stronger peak.

Experimental Example 4 (biocompatibility of Ti-25Nb-xTa alloy)

Experimental Example 4-1: Wettability measurement result of Ti-25Nb-xTa alloy

The wettability of the surface was measured using a moisture contact angle meter (wettability, Kruss DSA100, Germany), and samples were measured using a 6 μl needle in distilled water droplet mode. Sterile distilled water was used as the probe solution for measuring the sample. The contact angle was measured using a static droplet method and automatically falling water droplets with a video camera and a contact angle meter.

Figure 19 shows the HA-coated wetting contact angles by RF-sputtering after PEO treatment in an electrolyte containing Ca and P and PEO treatment in an electrolyte containing 1M H ₃ PO _{4 .} Figure 19 (a ~ d) is an etched surface, Figure 19 (a-1 ~ d-1) is a PEO-treated surface in an electrolyte containing Ca and P, Figure 19 (a-2 ~ d-2) is 1M H ₃ PO ₄ is a PEO-treated surface in an electrolyte, and Figure 19 (a-3 ~ d-3) shows the HA-coated surface by RF-sputtering after PEO treatment in an electrolyte containing _{1M H 3} PO ₄ indicates. The contact angles are shown in Table 11 below.

[Table 11]

The contact angle of the etched surface gradually decreased with increasing Ta content, and the contact angle of Ti-25Nb-15Ta slightly increased. As can be seen in Fig. 4, the gradual decrease of the contact angle was attributed to the martensitic α '' structure of the corroded surface, whereas it showed a slightly increasing trend due to the formation of the equiaxed β structure of the Ti-25Nb-15Ta alloy. However, there was almost no significant change depending on the Ta content.

Wetting can affect protein adsorption and activation, platelet adhesion, cell adhesion and blood clotting. In addition, the surface wettability (hydrophilicity or hydrophobicity) determined through contact angle measurement is an important parameter influencing the biological response to the injected biomaterial.

The contact angle of alloys treated with PEO in electrolytes containing Ca and P ions was relatively small and decreased with increasing Ta content. It is thought that the contact angle decreased as the area of pores increased and the small number of pores increased. The contact angle is related to the shape of the surface and also to the surface energy of the solid. The higher surface energy of the solid results in higher wettability and smaller contact angle, and it is considered that the surface morphology of the solid also contributed to this.

The PEO-treated alloy in 1M H ₃ PO ₄ electrolyte also showed a lower contact angle, and a slightly increased contact angle in the Ti-25Nb-15Ta alloy. This appears differently depending on the shape of the surface, and it is thought that the shape of the pores formed on the surface affected the increase or decrease.

1M H ₃ PO ₄ and then processed in the electrolyte PEO contact angle of the HA-coated surface by RF- sputtering is there seen that the contact angle increased slightly compared with the result of processing in the PEO 1M H ₃ PO ₄ electrolyte, which has a surface HA It is judged that the effect of increasing the contact angle by coating was exhibited. In conclusion, it can be seen that the surface roughness and the phase forming the texture affect the contact angle, and the influence of alloying elements _{is that the surface energy by the oxide film (Nb 2} O ₅ and Ta ₂ O ₅ ) affected the wettability of the surface. It is thought that High wettability surfaces promote cell differentiation and cell growth and improve biocompatibility than hydrophobic surfaces.

Experimental Example 4-2: Measurement of surface roughness of Ti-25Nb-xTa alloy

Surface roughness was measured using atomic force microscopy (AFM, Park XE-100, Park Systems, Korea). In the surface roughness measurement, each sample was measured using a scan size of 20.00 μm and a scan rate of 0.20 Hz.

20 shows atomic probe microscopy (AFM) images of HA coated by RF-sputtering after PEO treatment in Ca and P-containing electrolyte and PEO treatment in 1M H ₃ PO _{4 electrolyte.}

Fig. 20 (a-d) is a PEO-treated surface in an electrolyte containing Ca and P, Fig. 20 (a-1 to d-1) is _{a PEO-treated surface in a 1M H 3} PO ₄ electrolyte, and Fig. 20 (a- 2~d-2) show the HA-coated surface by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte.} In addition, the average Ra value is shown in Table 12.

[Table 12]

All PEO-treated surfaces showed crater structures with micropores as observed by FE-SEM. The surface area of the raised crater gradually decreased and became flat as the Ta content increased. The micro-scale surface roughness (Ra) values of the samples were 262, 239, 271, and 235 nm in the PEO treatment in the electrolyte containing Ca and P, and 0.257, 0.289, 0.370, and 0.25 in the PEO treatment in the _{1M H 3} PO _{4 electrolyte.} 0.224 μm, and 0.258, 0.267, 0.273, and 0.259 μm on the HA-coated surface by RF-sputtering after PEO treatment in _{1 M H 3} PO _{4 electrolyte.} The roughness of the surface appears differently depending on the shape and structure of the surface, and it is thought to be affected by the size and number of pores formed on the surface.

The reason why the roughness was higher in the case of PEO treatment in 1M H ₃ PO ₄ electrolyte than in the case of treatment in the electrolyte containing Ca and P is thought to be because there are relatively more raised craters. This may have had an effect on the contact angle measurement as well.

In addition, the roughness of the HA-coated surface was slightly increased by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte.} It seems that the HA coating layer was accumulated on the surface during the HA deposition process after PEO treatment, indicating a higher crater structure.

In general, the addition of Ta decreased the roughness of the PEO surface. However, in Ti-25Nb-7Ta, the surface area is different and tends to increase slightly due to the relatively large and small pores. A randomly rough surface is more advantageous than a regularly rough or smooth surface because it promotes the deposition of proteins required for osteoblast adhesion and cell adhesion between the implant and bone tissue. Therefore, the PEO-treated Ti-25Nb-xTa alloy shows a rough surface on the oxide film, which is advantageous for implant work healing and implant stability.

Experimental Example 4-3: Formation of hydroxyapatite in surface-treated Ti-25Nb-xTa alloy

To investigate the biological activity (hydroxyapatite-forming ability) of PEO (H ₃ PO ₄ and Ca+P)-treated specimens, they were immersed in simulated body fluid for 3 days. The ion concentration of SBF is shown in Table 13 below.

[Table 13]

The solution, almost identical to the concentration of human plasma, maintained a temperature of 36.5 ° C ± 1 and a pH concentration of 7.4 ± 0.5. The pH of SBF was adjusted to pH 7.4 using tris (hydroxymethyl) aminomethane, 99.0% (C ₄ H ₁₁ NO ₃ = 121.14) and 1:9 HCl (hydrochloric acid, 36.46 g/mol).

Figure 21 shows (a, a-1) Ti-25Nb, (b, b-1) Ti-25Nb-3Ta, (c, c-) grown SBF for 3 days after PEO treatment in an electrolyte containing Ca and P. 1) Ti-25Nb-7Ta and (d, d-1) Ti-25Nb-15Ta FE-SEM images.

It can be seen that hydroxyapatite was formed on all surfaces. The SBF growth time was set to 3 days, and in Fig. 21 (ac), it was shown that hydroxyapatite took the place of the pores and was well formed overall. In the Ti-25Nb-xTa alloy, the growth of hydroxyapatite was well nucleated in the pores. It shows a sincere aspect. As shown in FIG. 21 (a-1 - d-1), the hydroxyapatite formation is initially formed inside the pores, settles on the surface, grows around the surface over time, and eventually covers the surface when exposed for a long time. . It is confirmed that _{this apatite layer is related to the CaTiO 3} hydrolysis occurring in the SBF solution, in which _{OH) 2,} Ca ²⁺ and OH ⁻ ions are present in the SBF solution, as expressed by the following chemical formula.

[Formula]

CaTiO ₃ + 2H ₂ O → Ca ²⁺ + 2OH ^- + TiO(OH) ₂

Table 14 below shows the EDS results of Ti-25Nb-XTa alloys in which SBF was grown for 3 days after PEO treatment in an electrolyte containing Ca and P.

[Table 14]

The PEO-treated CA/P ratios of each alloy were 1.19, 1.38, 1.29, and 1.36, which is very close to the CA/P 1.67 of HA. The porous micro- and nano-size can significantly promote the deposition of HA in SBF. This is because OH ^- can combine with Ti ⁺ of TiO ₂ to form Ti-OH in the SBF solution, and the negatively charged Ti-OH ^- surface can selectively absorb positively charged Ca ²⁺ to form calcium titanate. As Ca ²⁺ increases, it _{can attract PO 4} ^{3 -} to form CaP crystals.

22 is (a, a-1) Ti-25Nb, (b, b-1) Ti-25Nb- which was coated with HA by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte and grown SBF for 3 days;} 3Ta, (c, c-1) Ti-25Nb-7Ta and (d, d-1) Ti-25Nb-15Ta FE-SEM images.

22, it can be seen that all surfaces are covered with hydroxyapatite. 22 also shows that the initial growth of hydroxyapatite is formed in the pores and is located as a precipitate on the surface, and it can be seen that it is well formed on all surfaces. This helps to preserve the nucleation site for apatite, such as bone, due to the relatively high surface roughness and porosity due to the PEO process, thereby allowing fixation between the bone and the pore.

Below, Table 15 shows the EDS results of Ti-25Nb-xTa alloy in which SBF was grown for 3 days by HA coating by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte.}

[Table 15]

As shown in Table 15, it can be seen that all elements were detected, but the content of P was high overall. This is thought to have influenced the HA formation during the process of competitive doping ^{of Ca 2+} and PO ₄ ^3- ions during PEO treatment.

Experimental Example 4-4: Cell culture of Ti-25Nb-xTa alloy

The osteoblast cell line MC3T3-E1 was extracted from the mouse skull and appropriately distributed at a concentration of ^{1x10 5 cells/well.} It was cultured using α-minimum essential medium (MEM, without L-ascorbic acid) containing 10% of FBS and 10U/ml of penicillin/streptomycin.

The cell monolayer was washed with phosphate buffered saline (PBS) and incubated for 10 minutes in a trypsin-DTA solution (0.05% trypsin, 0.53 mM EDTA·4Na, phenol red in HBSS) at 37 °C to separate the cells. ^{Cells were seeded on a Ti alloy at a concentration of 1.5 x 10 5} cells/well on a 12-well plate and grown on the coated surface for 24 hours. The treated samples were washed with PBS and fixed with 10% formaldehyde at 4°C for 12 hours. After fixation, the samples were dehydrated with ethanol. The morphology of the fixed cells was observed using FE-SEM.

23 is an FE-SEM image showing the morphology of MC3T3-E1 osteoblasts cultured for 24 hours on the surface of a Ti-25Nb-xTa alloy treated with PEO in an electrolyte containing Ca and P. 23 (a, a-1) Ti-25Nb, (b, b-1) Ti-25Nb-3Ta, (c, c-1) Ti-25Nb-7Ta and (d, d-1) Ti-25Nb- 15Ta.

It can be seen that all surfaces are well covered by the growth of Lamellipodia as a whole. Ti-25Nb-xTa alloy cells adhered well and grew, showing results consistent with wettability, roughness, and SBF experiments.

In addition, Lamellipodia continued to adhere to each other, and the cells spread and grew in the form of a thin film on the surface of the substrate material, consistent with the biocompatibility of the implant material.

24 is a FE-SEM image showing the morphology of MC3T3-E1 osteoblasts cultured for 24 hours after being coated with HA by RF-sputtering after PEO treatment in _{1M H 3} PO _{4 electrolyte.} Figure 24 (a, a-1) Ti-25Nb, (b, b-1) Ti-25Nb-3Ta, (c, c-1) Ti-25Nb-7Ta and (d, d-1) Ti-25Nb- 15Ta.

24 also shows that cells are well distributed on all surfaces. Also, as the Ta content increases, the cell distribution seems to increase. Therefore, in both conditions, Ti-25Nb-xTa alloy can have excellent cell proliferation and biocompatibility as a dental implant material after micropore formation.

As described above, according to the method for manufacturing a dental implant using a Ti-Nb-Ta alloy and the dental implant according to the present invention, since the Ti-Nb-Ta alloy is used, the conventional Ti-6Al-4V alloy is used. In comparison, it has the primary effect of reducing the elastic modulus to prevent stress shielding with the bone.

In addition, during plasma conversion oxidation treatment, an electrolyte solution containing calcium and phosphorus ions is used to form elements calcium and phosphorus on the surface of the titanium-based alloy, thereby inducing bonding with bone, and bone cell adhesion and bone bonding. It has the advantage of promoting growth and improving biocompatibility.

In addition, by performing plasma conversion oxidation treatment to form a porous oxide film on the surface, and then allowing HA (hydroxyapatite) particles to be formed on the surface of the porous oxide film by RF-magnetron sputtering, biocompatibility can be improved. have an advantage

As described above, the present invention has been illustrated and described with reference to preferred embodiments, but it is not limited to the above-described embodiments, and those of ordinary skill in the art to which the present invention pertains within the scope not departing from the spirit of the present invention Various changes and modifications will be possible.

Claims (8)

A titanium-based alloy preparation step of preparing a titanium-based alloy;
an oxide film forming step of immersing the prepared titanium-based alloy in an electrolyte solution and applying a pulse current to a plasma electrolytic oxidation device to form a porous oxide film on the surface of the titanium-based alloy; and
HA coating layer forming step of forming an HA (hydroxyapatite) coating layer on the surface of the titanium-based alloy on which the porous oxide film is formed;
The titanium-based alloy is Ti-25Nb-xTa, wherein x is a method of manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy, characterized in that 3 to 15.
The method of claim 1,
The electrolyte solution is
A method of manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy, comprising a phosphoric acid solution (H ₃ PO _{4 ).}
The method of claim 1,
In the oxide film forming step,
The voltage applied to the plasma electrolytic oxidation device is 260 ~ 300V, and the use time is 2 minutes to 4 minutes.
The method of claim 1,
After the oxide film forming step,
A method of manufacturing an HA-coated dental implant using a Ti-Nb-Ta alloy, characterized in that it further comprises; a drying step of washing the titanium-based alloy having an oxide film formed thereon with ethanol and distilled water and then drying it.
The method of claim 1,
The HA coating layer forming step is
An HA (hydroxyapatite) coating layer is formed by RF-magnetron sputtering.
A dental implant, characterized in that it is manufactured by the manufacturing method of the HA-coated dental implant using the Ti-Nb-Ta alloy according to any one of claims 1 to 5.
7. The method of claim 6,
On the surface of the dental implant
A dental implant comprising a porous oxide film comprising TiO ₂ , Ta ₂ O ₅ and Nb ₂ O _{5 .}
8. The method of claim 7,
On the surface of the dental implant
Dental implant, characterized in that HA (hydroxyapatite) particles are formed.

Images