KR102442704B1 - Method of producing a biocompatible titanium base alloy increased by using a titanium-based alloy - Google Patents

Abstract

The present invention relates to a method of producing a titanium-based alloy with increased biocompatibility by using a titanium-based alloy, and more specifically, to a method of producing a titanium-based alloy with increased biocompatibility by using a titanium-based alloy, in which the biocompatibility is increased by forming a porous oxide film containing Ca ions and P ions and a Sr coating layer on a titanium alloy.

Description

Method of producing a biocompatible titanium base alloy increased by using a titanium-based alloy}

The present invention relates to a method for manufacturing a biocompatibility-enhancing titanium-based alloy using a titanium-based alloy, and more specifically, to a titanium-based alloy by forming a porous oxide film and Sr coating layer containing Ca ions and P ions on the titanium-based alloy, It relates to a method for producing a biocompatibility-enhancing titanium-based alloy using a titanium-based alloy that can increase the

In general, biomaterials should be composed of biomaterials without cytotoxicity, side effects or rejection by the human body when used physiologically, and should be chemically stable. In addition, mechanical properties such as strength, modulus of elasticity, abrasion resistance, etc. must be good, and corrosion resistance must be good to withstand the corrosive environment in the human body.

Conventional biomaterials are made of pure titanium and Ti-6Al-4V alloy. These pure titanium and Ti-6Al-4V alloys have excellent properties such as high strength, fracture toughness, corrosion resistance and biocompatibility, so that damaged bone Or, it is used in dentistry and orthopedics as a biomaterial to replace joints.

However, conventional pure titanium and Ti-6Al-4V cannot naturally form sufficient osseointegration with bone tissue due to their biological inertness, and in particular, it is difficult for an implant made of pure titanium to directly connect with bone.

In addition, the elastic modulus of pure titanium and Ti-6Al-4V alloy is about 110 GPa, and the elastic modulus of cortical bone is about 30 GPa, which shields stress due to the difference in elastic modulus between pure titanium and Ti-6Al-4V alloy and cortical bone. This phenomenon causes bone resorption around the cortical bone after implant placement, which ultimately leads to the failure of implant surgery.

In addition, when implants made of Ti-6Al-4V alloy are used for a long time in a physiological environment, vanadium ions have carcinogenic properties due to cytotoxicity, and aluminum has neurotoxicity, which affects behavior or nerve function. There was a problem of causing disability or causing Alzheimer's disease.

The present invention has been devised to solve this problem, and an object of the present invention is to use a Ti-Nb-Ta alloy, which does not have cytotoxicity and neurotoxicity, and has an elastic modulus similar to that of cortical bone. It is to provide a method for manufacturing a biocompatibility-enhancing titanium-based alloy capable of reducing the stress shielding phenomenon.

Another object of the present invention is to form a porous oxide film containing Ca ions and P ions on the surface of the Ti-Nb-Ta alloy by plasma electrolytic oxidation, thereby increasing the biocompatibility of titanium with increased osseointegration with cortical bone. It is intended to provide a method for manufacturing an alloy based alloy.

Another object of the present invention is to further form an Sr coating layer using RF-magnetron sputtering on a Ti-Nb-Ta alloy having a porous oxide film, thereby inhibiting osteoclast proliferation and stimulating osteoblast differentiation, thereby reducing healing time. It is to provide a method for producing a biocompatibility enhancement type titanium-based alloy that can be

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 manufacturing step of preparing a titanium-based alloy; A porous 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; including, the titanium-based alloy is Ti-35Nb-xTa, wherein x is 3 to 15.

In a preferred embodiment, after the step of forming the porous oxide film, the Sr coating layer forming step of further forming an Sr coating layer by using an RF-magnetron sputtering device on the surface of the titanium-based alloy on which the porous oxide film is formed. It provides a method for producing a biocompatibility-enhancing titanium-based alloy, characterized in that.

In a preferred embodiment, the electrolyte solution contains Ca ions, P ions and Sr ions, more preferably calcium acetate monohydrate [CaH ₃ COO) ₂ ·H ₂ O], calcium glycerophosphate [C ₃ H ₇ CaO ₆ P] and strontium acetate [Sr(CH ₃ COO) ₂ ·0.5H ₂ O] are preferred.

In a preferred embodiment, the electrolyte solution contains Ca and P ions, more preferably calcium acetate monohydrate [CaH ₃ COO) ₂ ·H ₂ O] and calcium glycerophosphate [C ₃ H ₇ CaO ₆ P ] is preferred.

In a preferred embodiment, in the step of forming the porous oxide film, a voltage of 250V to 280V is preferably applied for 2 minutes 30 seconds to 3 minutes 30 seconds.

In a preferred embodiment, in the Sr coating layer forming step, the RF-power of the magnetron sputtering device is preferably applied in a range of 40W to 60W.

In a preferred embodiment, the titanium alloy manufacturing step comprises: a first polishing step of grinding the titanium-based alloy to 100, 600, 1000 and 2000 grit using a silicon carbide abrasive; and a second polishing step of micropolishing the polished titanium-based alloy into a powder (Al ₂ O ₃ ).

In addition, the present invention further provides a titanium-based alloy prepared by the method for manufacturing the biocompatibility-enhancing titanium-based alloy.

In a preferred embodiment, the titanium-based alloy includes a titanium-based alloy, a surface of the titanium-based alloy is formed, a porous oxide film containing Ca ions and P ions, and an Sr coating layer formed on the porous oxide film, and the The titanium-based alloy is Ti-35Nb-xTa, where x is 3 to 15.

In addition, the present invention further provides a dental implant made of the titanium-based alloy.

The present invention has the following excellent effects.

According to the manufacturing method of the biocompatibility-enhancing titanium-based alloy of the present invention, since Ti-Nb-Ta alloy is used, it does not have cytotoxicity and neurotoxicity, and has an elastic modulus similar to that of cortical bone, thereby shielding stress with cortical bone. It has the effect of reducing the phenomenon.

In addition, according to the manufacturing method of the biocompatibility-enhancing titanium alloy of the present invention, a porous oxide film containing Ca ions and P ions is formed on the surface of the Ti-Nb-Ta alloy, so that it is chemically and structurally similar to the bone of a living body. It has the advantage of improving osseointegration by helping bone nucleation and growth in the human body, and increasing the surface roughness to promote the adhesion of osteocytes and proteins necessary for the adhesion of osteocytes.

In addition, according to the manufacturing method of the biocompatibility-enhancing titanium-based alloy of the present invention, by further forming an Sr coating layer through RF-magnetron sputtering on the Ti-Nb-Ta alloy having a porous oxide film, the inhibition of osteoclast proliferation and osteoblasts It stimulates differentiation and has the effect of reducing the healing time.

1 is a step diagram for explaining a method of manufacturing a biocompatibility-enhancing titanium-based alloy according to a first embodiment of the present invention.
2 is a step diagram for explaining a method of manufacturing a biocompatibility enhanced titanium-based alloy according to a second embodiment of the present invention.
3 is an XRF graph of the titanium-based alloy prepared in Comparative Example 3 and Examples 1 to 3 of the present invention, respectively.
4 is an optical microscope image of a titanium-based alloy prepared in Comparative Example 3, Examples 1 to 3, respectively, of the present invention, (a) is Comparative Example 3, (b) is Example 1, (c) is Example 2, (d) is Example 3.
5 is an XRD graph of each titanium-based alloy prepared in Comparative Example 1, Comparative Example 3, and Examples 1 to 3 of the present invention.
6 is an image of the indentation marks appearing on the surface of the titanium-based alloy prepared in Comparative Example 3 and Examples 1 to 3 of the present invention after nanoindentation measurement, (a) is Comparative Example 3, (b) ) is Example 1, (c) is Example 2, (d) is Example 3.
7 is a graph showing the nanoindentation results of the titanium-based alloy prepared in Comparative Examples 1 to 3 and Examples 1 to 3 of the present invention, respectively.
8 is a graph showing the elastic modulus and indentation hardness of the titanium-based alloy prepared in Comparative Examples 1 to 3 and Examples 1 to 3, respectively, of the present invention.
9 is an optical image observing the reaction occurring on the surface according to the plasma electrolytic oxidation treatment time when preparing Comparative Examples 4 and 4 to 6 of the present invention.
10 is an optical image observing the reaction occurring on the surface according to the plasma electrolytic oxidation treatment time when preparing Comparative Examples 5 and 7 to 9 of the present invention.
11 is an image showing the FE-SEM results of the titanium-based alloy prepared by the method for producing a biocompatibility-enhancing titanium-based alloy according to the present invention, (a), (b), (c), (d) is 10㎛ (a-1), (b-1), (c-1), and (d-1) are confirmed at a magnification of 2 μm, (a), (a-1) is a comparative example 4, (b), (b-1) is Example 4, (c), (c-1) is Example 5, (d), (d-1) is Example 6.
12 is an image showing the FE-SEM results of the titanium-based alloy prepared by the method for producing a biocompatibility-enhancing titanium-based alloy according to the present invention. (a), (b), (c), (d) is 10 μm; (a-1), (b-1), (c-1), and (d-1) are confirmed at a magnification of 2 μm, (a), (a-1) is a comparative example 5, (b), (b-1) is Example 7, (c), (c-1) is Example 8, (d), (d-1) is Example 9.
13 is a graph showing the porosity of each titanium-based alloy prepared in Comparative Example 4, Comparative Example 5, and Examples 4 to 9 of the present invention.
14 is a graph showing pore sizes in each of the titanium-based alloys prepared in Comparative Example 4, Comparative Example 5, and Examples 4 to 9 of the present invention.
15 is a graph showing the number of pores in each titanium-based alloy prepared in Comparative Example 4, Comparative Example 5, and Examples 4 to 9 of the present invention.
16 is a graph showing the ratio of large pores in the titanium-based alloy prepared in Comparative Example 4, Comparative Example 5, and Examples 4 to 9 of the present invention, respectively.
17 is an image showing a cross-section of a titanium-based alloy prepared in Comparative Example 4 and Examples 4 to 6 of the present invention, respectively, (a) is Comparative Example 4, (b) is Example 4, (c) is Examples 5 and (d) are Example 6.
18 is an image showing a cross section of a titanium-based alloy prepared in Comparative Example 5 and Examples 7 to 9 of the present invention, respectively, (a) is Comparative Example 5, (b) is Example 7, (c) is Example 8, (d) is Example 9.
19 is a graph of measuring the oxide film thickness of the titanium-based alloy prepared in Comparative Example 4, Comparative Example 5, and Examples 4 to 9 of the present invention, respectively.
20 is an image showing the EDS results of the titanium-based alloy prepared in Comparative Example 4, Examples 4 to 6, respectively, of the present invention, (a) is Comparative Example 4, (b) is Example 4, (c) ) is Example 5, (d) is Example 6.
21 is an image showing the ESD results of the titanium-based alloy prepared in Comparative Example 5 and Examples 7 to 9 of the present invention, respectively, (a) is Comparative Example 5, (b) is Example 7, (c) ) is Example 8, (d) is Example 9.
22 is a graph showing XRD results of titanium-based alloys prepared in Comparative Example 4 and Examples 4 to 6 of the present invention, respectively.
23 is a graph showing XRD results of titanium-based alloys prepared in Comparative Example 5 and Examples 7 to 9 of the present invention, respectively;
24 is a graph showing XRD results of titanium-based alloys prepared in Comparative Examples 4 and 5 of the present invention, respectively.
25 is a result of confirming the surface image according to the deposition time of the Sr coating layer forming step in the present invention by FE-SEM. (a), (b), (c), (d), (e) are surface images near the pores. and (a-1), (b-1), (c-1), (d-1), (e-1) are surface images not near the pore, (a), (a-1) ) is before deposition, (b), (b-1) is 3 min, (c), (c-1) is 5 min, (d), (d-1) is 10 min, (e), (e) -1) is the surface image at 20 minutes.
26 is an image showing the FE-SEM results of titanium-based alloys prepared in Comparative Example 6, Examples 10 to 12, respectively, of the present invention, (a), (b), (c) and (d) are 10 It was confirmed with a magnification of μm, (a-1), (b-1), (c-1) and (d-1) were confirmed with a magnification of 2 μm, and (a), (a-1) were compared Examples 6, (b) and (b-1) are Example 10, (c), (c-1) are Example 11, and (d), (d-1) is Example 12.
27 is an image showing the EDS results of the titanium-based alloy prepared in Comparative Example 6, Examples 10 to 12, respectively, of the present invention, (a) is Comparative Example 6, (b) is Example 10, (c) ) is Example 11 and (d) is Example 12.
28 is a graph showing XRD results of titanium-based alloys prepared in Comparative Example 6 and Examples 10 to 12 of the present invention, respectively.
29 is a graph showing XRD results of titanium-based alloys prepared in Comparative Examples 4 and 6 of the present invention, respectively.
30 is a graph showing the surface roughness through a surface roughness tester of the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12 of the present invention, respectively.
31 is a 2D image showing the AFM results of the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12 of the present invention, respectively, (a) is Comparative Example 4, (a-1) is Example 4, (a-2) is Example 5, (a-3) is Example 6, (b) is Comparative Example 5, (b-1) is Example 7, (b-2) is Example 8, (b-3) is Example 9, (c) is Comparative Example 6, (c-1) is Example 10, (c-2) is Example 11, (c-3) is Example 12 .
32 is a 3D image showing the AFM results of titanium-based alloys prepared in Comparative Examples 3 to 6 and Examples 1 to 12, respectively, of the present invention. (a) is Comparative Example 4, (a-1) is Example 4, (a-2) is Example 5, (a-3) is Example 6, (b) is Comparative Example 5, (b-1) is Example 7, (b-2) is Example 8, (b-3) is Example 9, (c) is Comparative Example 6, (c-1) is Example 10, (c-2) is Example 11, (c-3) is Example 12 .
33 is an image measuring the contact angle of the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12 of the present invention, respectively, (a) is Comparative Example 3, (b) is Example 1 , (c) is Example 2, (d) is Example 3, (a-1) is Comparative Example 4, (b-1) is Example 4, (c-1) is Example 5, (d- 1) is Example 6, (a-2) is Comparative Example 5, (b-2) is Example 7, (c-2) is Example 8, (d-2) is Example 9, (a- 3) is Comparative Example 6, (b-3) is Example 10, (c-3) is Example 11, (d-3) is Example 12.
34 is FE observation of the appearance of hydroxyapatite at a magnification of 100 μm after 1 day by immersing the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12, respectively, in an SBF solution of the present invention; -SEM image (a) is Comparative Example 3, (b) is Example 1, (c) is Example 2, (d) is Example 3, (a-1) is Comparative Example 4, (b-1) ) is Example 4, (c-1) is Example 5, (d-1) is Example 6, (a-2) is Comparative Example 5, (b-2) is Example 7, (c-2) ) is Example 8, (d-2) is Example 9, (a-3) is Comparative Example 6, (b-3) is Example 10, (c-3) is Example 11, (d-3) ) is Example 12.
35 is an FE-SEM image in which the titanium-based alloy prepared in Examples 7 and 10 of the present invention, respectively, was immersed in an SBF solution, and the appearance of hydroxyapatite was observed at a magnification of 2 μm after one day (a) is Example 7, (b) is Example 10.
36 is an FE-SEM image of observing the appearance of hydroxyapatite after 1 day after immersing the titanium-based alloy prepared in Examples 1, 4, 7 and 10 of the present invention in an SBF solution ( a), (b), (c) and (d) are confirmed at a magnification of 4 μm, and (a-1), (b-1), (c-1) and (d-1) are 400 nm It is confirmed by magnification, (a), (a-1) is Example 1, (b), (b-1) is Example 4, (c), (c-1) is Example 7, (d) , (d-1) is Example 10.
37 is a schematic diagram of the nucleation and growth process of hydroxyapatite of a titanium-based titanium-based alloy with increased biocompatibility according to the present invention.
38 is a FE showing the morphology of MC3T3-E1 osteoblasts at a magnification of 100 μm, which were cultured for 2 days in the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12, respectively, of the present invention. -SEM image (a) is Comparative Example 3, (b) is Example 1, (c) is Example 2, (d) is Example 3, (a-1) is Comparative Example 4, (b-1) ) is Example 4, (c-1) is Example 5, (d-1) is Example 6, (a-2) is Comparative Example 5, (b-2) is Example 7, (c-2) ) is Example 8, (d-2) is Example 9, (a-3) is Comparative Example 6, (b-3) is Example 10, (c-3) is Example 11, (d-3) ) is Example 12.
Figure 39 is an FE-SEM image showing cell growth according to the surface shape of the titanium-based alloy prepared in Comparative Example 3, Example 1, Example 4, Example 7 and Example 10 of the present invention, respectively (a), (b), (c), (d) are confirmed with a magnification of 10㎛, (a-1), (b-1), (c-1), (d-1) is confirmed with a magnification of 2㎛ (a), (a-1) is Comparative Example 3, (b), (b-1) is Example 1, (c), (c-1) is Example 4, (d), (d) -1) is Example 7, (e), (e-1) is Example 10.

The terms used in the present invention used in the present invention have been selected as widely used general terms as possible, but in specific cases, there are also terms arbitrarily selected by the applicant. The meaning should be grasped in consideration of the meaning used.

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 biocompatibility-enhancing titanium-based alloy according to a first embodiment of the present invention.

Referring to Figure 1, the biocompatibility enhancement type titanium-based alloy manufacturing method according to the first embodiment of the present invention is to form a porous oxide film on the titanium-based alloy using a plasma electrolytic oxidation device to produce an alloy for implants. A method of manufacturing a biocompatibility-enhancing titanium-based alloy.

First, a titanium-based alloy manufacturing step (S100) of manufacturing a titanium-based alloy is performed.

In the titanium-based alloy, Ti metal, Nb metal, and Ta metal are put into a vacuum arc melting furnace, heat-treated for 1 hour at a temperature of 1000° C. to 1100° C. under an argon (Ar) gas atmosphere, and then cooled with water at 0° C. It can be made of Nb-Ta alloy.

Here, the titanium-based alloy is Ti-35Nb-xTa, and x is preferably 3 to 15.

The reason is that when the Ta content is less than 3% by weight, the stress shielding phenomenon occurs due to the difference in the elastic modulus with the cortical bone, and when the Ta content exceeds 35% by weight, cell growth is reduced. This is because the healing time is increased.

In addition, the titanium-based alloy manufacturing step (S100) may include a first polishing step and a second polishing step.

Here, in the first polishing step, the prepared titanium-based alloy is polished to 100, 600, 1000 and 2000 grit using a carbide abrasive, and in the second polishing step, the polished titanium-based alloy is 0.3 μm alumina Fine grinding using powder (Al ₂ O ₃ ).

Next, a porous oxide film forming step (S200) of forming a porous oxide film on the surface of the Ti-Nb-Ta alloy using a plasma electrolytic oxidation (PEO) is performed.

In the porous oxide film forming step (S200), the prepared Ti-Nb-Ta alloy is immersed in an electrolyte solution, and a pulse current is applied to a plasma electrolytic oxidation device to form a porous oxide film.

At this time, the pulse current may be applied at a voltage of 250 to 280V for 2 minutes and 30 seconds to 3 minutes and 30 seconds.

Here, the electrolyte solution comprises Ca ions, P ions and Sr ions.

More specifically, the electrolyte solution contains calcium acetate monohydrate [Ca(CH ₃ COO) ₂ ·H ₂ O] containing Ca ions, calcium glycerophosphate containing P ions [C ₃ H ₇ CaO ₆ P] and Contains strontium acetate [Sr(CH ₃ COO) ₂ ·0.5H ₂ O] containing Sr ions.

Here, Ca and P ions contained in the electrolyte solution may form an oxide layer including a HA (hydroxyapatite) structure that is stable, has a high density, and has a high chemical and structural similarity to a mineral component of bone.

In addition, Sr ions contained in the electrolyte solution can improve osteocompatibility by inhibiting osteoclast proliferation and promoting osteoblast differentiation.

In addition, the present invention further provides a biocompatibility-enhancing titanium-based alloy manufactured by the method for manufacturing a biocompatibility-enhancing titanium-based alloy according to the first embodiment.

The biocompatible titanium-based alloy comprises a titanium-based alloy and a porous oxide film.

Here, the titanium-based alloy is a Ti-Nb-Ta alloy, and Ta and Nb are β-stabilizing elements of Ti, which are less toxic than Ti-6Al-4V alloys, and are very stable in a wide range of pH, so it is advantageous for biocompatibility And, it contributes to lowering the modulus of elasticity of the Ti alloy, thereby reducing the stress shielding phenomenon and improving bone compatibility.

In addition, the titanium-based alloy is Ti-35Nb-xTa, where x is preferably 3 to 15.

In addition, the porous oxide film is formed on the surface of the titanium-based alloy, and includes Ca, P and Sr ions.

Here, the porous oxide film containing Ca, P, and Sr ions forms an HA structure and chemically and structurally has a high similarity with the mineral component of bone to increase biocompatibility, and Sr contained in the porous oxide film Ions play a role in improving osteocompatibility by inhibiting osteoclast proliferation and promoting osteoblast differentiation.

In addition, the present invention further provides a dental implant made of the biocompatible titanium-based alloy.

The dental implant provided in the present invention is biocompatible and has the advantage of reducing the healing period.

2 is a step diagram for explaining a method of manufacturing a biocompatibility enhanced titanium-based alloy according to a second embodiment of the present invention.

Referring to FIG. 2 , in the method of manufacturing a biocompatibility-enhancing titanium-based alloy according to a second embodiment of the present invention, a titanium-based alloy is prepared, and then Ca ions and P After forming a porous oxide film containing ions, it is a biocompatibility enhancement type titanium-based alloy manufacturing method in which an Sr coating layer is formed using an RF-magnetron sputtering device.

That is, the manufacturing method of the biocompatibility-enhancing titanium-based alloy according to the second embodiment of the present invention is compared with the manufacturing method of the biocompatibility-enhancing titanium-based alloy according to the first embodiment of the present invention described above, porous oxidation In the film forming step (S200), an electrolyte solution containing Ca and P ions rather than Ca, P, and Sr ions is used, and the Sr coating layer forming step (S300) is further performed after the porous oxide film forming step (S200).

Hereinafter, a method of manufacturing a biocompatibility-enhancing titanium-based alloy according to a second embodiment of the present invention will be described in more detail.

In the method of manufacturing a biocompatibility-enhancing titanium-based alloy according to a second embodiment of the present invention, first, a titanium-based alloy manufacturing step (S100) of manufacturing a titanium-based alloy is performed.

Here, since the titanium-based alloy manufacturing step (S100) has substantially the same configuration as the titanium-based alloy manufacturing step (S100) of the first embodiment of the present invention, the overlapping description will be omitted.

Next, a porous oxide film forming step (S200) of forming a porous oxide film on the surface of the prepared Ti-Nb-Ta alloy is performed.

In the porous oxide film formation step (S200), the prepared Ti-Nb-Ta alloy is immersed in an electrolyte solution containing Ca ions and P ions, and a pulse current is applied to the plasma electrolytic oxidation device to generate Ca and P ions. A porous oxide film containing

More specifically, the electrolyte solution used in the second embodiment of the present invention contains calcium acetate monohydrate [Ca(CH ₃ COO) ₂ ·H ₂ O] containing Ca ions and glycerophosphoric acid containing P ions. calcium [C ₃ H ₇ CaO ₆ P].

This is because the porous oxide film does not contain Sr ions, but contains Ca and P ions, so that the HA (hydroxyapatite) structure has a higher chemical and structural similarity than the mineral component of bone than the porous oxide film of the first embodiment. to form an oxide layer containing

That is, the step of forming the porous oxide film of the second embodiment according to the present invention is compared with the step of forming the porous oxide film of the first embodiment of the present invention, except that Ca and P ions are included in the electrolyte solution, and the remaining components are each other same.

Next, an Sr coating layer forming step (S300) of forming an Sr coating layer on the surface of the titanium-based alloy on which the porous oxide film is formed by using an RF-magnetron sputtering device is performed.

The Sr coating layer forming step (S300) is to further form a uniform Sr coating layer on the surface of the porous oxide layer including Ca and P ions formed through the porous oxide layer forming step (S200).

In addition, the RF-power of the magnetron sputtering device is preferably applied to 40W to 60W.

Accordingly, the manufacturing method of the biocompatibility-enhancing titanium-based alloy according to the second embodiment of the present invention is chemically and structurally compared to the manufacturing method of the biocompatibility-enhancing titanium-based alloy according to the first embodiment of the present invention. It is possible to form a porous oxide film containing an HA structure very similar to the mineral component of bone, and since an Sr coating layer is further deposited on the surface of the porous oxide film, the content of Sr compared to the content of Sr contained in the porous oxide film can be further increased, and bone fitness can be further increased.

In addition, the present invention further provides a biocompatibility-enhancing titanium-based alloy manufactured by the method for manufacturing a biocompatibility-enhancing titanium-based alloy according to the second embodiment.

The biocompatibility-enhancing titanium-based alloy is composed of a titanium-based alloy, a porous oxide film, and an Sr coating layer coated on the porous oxide film, and the titanium-based alloy is the same as in the first embodiment of the present invention.

In addition, the porous oxide film is formed on the surface of the titanium-based alloy, and includes Ca and P ions.

Here, the porous oxide film containing Ca and P ions forms an HA structure, chemically and structurally, as compared to the porous oxide film containing Ca, P and Sr ions of the first embodiment of the present invention. It may have a higher similarity to that and may play a role in enhancing biocompatibility.

In addition, by further forming an Sr coating layer on the porous oxide film containing Ca and P ions, an Sr coating having a higher composition than the Sr composition of the first embodiment of the present invention is possible, and forming the Sr coating layer through this It can play a role in further improving osseointegration.

In addition, the present invention further provides a dental implant made of the biocompatibility enhancement type titanium-based alloy.

The dental implant is more suitable for a living body and has the advantage of further reducing the healing period compared to the dental implant according to the first embodiment of the present invention.

Example 1 (Ti-35Nb-3Ta alloy)

In a vacuum arc furnace-melting furnace under a high-purity argon atmosphere, pure titanium is melted 5 to 10 times to remove trace oxygen.

Next, Ti, Nb and Ta in the form of pellets are melted 10 times in a button shape and 10 times in an ingot shape, respectively, to increase the homogeneity of each alloy.

Then, the manufactured ingot-shaped alloy was cut to a thickness of 3 mm using a diamond cutting machine operating at a speed of 2000 rpm.

Subsequently, the cut alloy is subjected to heat treatment at 1000° C. to 1100° C. for 1 hour under a high-purity argon atmosphere, followed by water cooling to 0° C. to homogenize.

Thereafter, the homogenized Ti-Nb-Ta alloy is polished to 100, 600, 1000 and 2000 grit using a carbide abrasive, and finely polished using 0.3 μm alumina powder (Al ₂ O ₃ ) to Ti -35Nb-3Ta alloy was obtained.

Example 2 (Ti-35Nb-7Ta alloy)

A Ti-35Nb-7Ta alloy prepared under the same conditions as in Example 1 was obtained, except that the Ta content was 7% by weight.

Example 3 (Ti-35Nb-15Ta alloy)

A Ti-35Nb-15Ta alloy prepared under the same conditions as in Example 1 was obtained, except that the Ta content was 15% by weight.

Example 4 (Ti-35Nb-3Ta alloy + PEO (Ca, P) treatment)

In order to perform plasma electrolytic oxidation treatment on the surface of the Ti-35Nb-3Ta alloy of Example 1, a sample was prepared by polishing up to 2000 grit using a carbide abrasive and then washing with ethyl-alcohol and distilled water.

Then, the sample washed using DC power was used as an anode, and a carbon rod was installed as a cathode, and then a voltage of 280V was applied for 3 minutes.

The coated sample was washed with ethyl-alcohol and distilled water and dried in air to obtain a Ti-35Nb-3Ta alloy with a porous oxide film.

Here, the electrolyte solution was a mixed solution of calcium acetate monohydrate [Ca(CH ₃ COO) ₂ ·H ₂ O] 0.015M and calcium glycerophosphate [C ₃ H ₇ CaO ₆ P] 0.02M.

Example 5 (Ti-35Nb-7Ta alloy + PEO (Ca, P) treatment)

A Ti-35Nb-7Ta alloy in which a porous oxide film containing Ca ions and P ions was formed was obtained by performing plasma electrolytic oxidation under the same conditions as in Example 4, except that Example 2 was used.

Example 6 (Ti-35Nb-15Ta alloy + PEO (Ca, P) treatment)

A Ti-35Nb-15Ta alloy having a porous oxide film including Ca ions and P ions was obtained by performing plasma electrolytic oxidation under the same conditions as in Example 4, except that Example 3 was used.

Example 7 (Ti-35Nb-3Ta alloy + PEO (Ca, P, Sr) treatment)

Example 1 (Ti-35Nb-3Ta) was used, and in comparison with Example 4, the electrolyte solution was prepared in the same manner as in Example 4 except that Ca ions, P ions and Sr ions were used. A Ti-35Nb-3Ta alloy in which a porous oxide film containing ions and Sr ions was formed was obtained.

Here, the electrolyte solution is calcium acetate monohydrate [Ca(CH ₃ COO) ₂ ·H ₂ O] 0.015M, calcium glycerophosphate [C ₃ H ₇ CaO ₆ P] 0.02M and strontium acetate [Sr(CH ₃ COO) ) ₂ ·0.5H ₂ O] 0.0075M.

Example 8 (Ti-35Nb-7Ta alloy + PEO (Ca, P, Sr) treatment)

A Ti-35Nb-7Ta alloy having a porous oxide film including Ca ions, P ions and Sr ions was obtained under the same conditions as in Example 7, except that Example 2 was used.

Example 9 (Ti-35Nb-15Ta alloy + PEO (Ca, P, Sr) treatment)

A Ti-35Nb-15Ta alloy having a porous oxide film including Ca ions, P ions and Sr ions was obtained under the same conditions as in Example 7 except that Example 3 was used.

Example 10 (Ti-35Nb-3Ta alloy + PEO (Ca, P) treatment + Sr sputtering)

An Sr coating layer was further formed on the surface of Example 4. For this purpose, an RF-magnetron sputtering device equipped with an Sr (99.5%) target was used.

The diameter of the Sr target was 63.5 mm, and the distance between the substrate and the target was 50 mm. To form the plasma, the initial vacuum degree was reduced to ^10-3 Torr with a rotary pump, and then the vacuum degree was reduced to ^10-6 Torr using an oil diffusion pump.

Next, a high purity Ar gas of 40 sccm was injected using a mass flow meter and a vacuum degree of 1.1 mTorr was maintained. Next, pre-sputtering was performed for 20 minutes at a power of 50 W for washing. Thereafter, an Sr coating layer was further formed for 3 minutes using an RF-magnetron sputtering device. Detailed conditions of RF-sputtering using the Sr target are shown in Table 1 below.

sputtering configuration Sputtering Configuration Conditions target Sr (99.99%) base pressure 10 ^-3 Torr performing pressure 110 mTorr input gas Ar (40 sccm) run temperature 25℃ pre-sputtering time 20 minutes run time 3 minutes carry current 50W

Example 11 (Ti-35Nb-7Ta alloy + PEO (Ca, P) treatment + Sr sputtering)

Except for using Example 5, RF-magnetron sputtering was performed under the same conditions as in Example 10 to obtain a Ti-35Nb-7Ta alloy in which an Sr coating layer was formed.

Example 12 (Ti-35Nb-15Ta alloy + PEO (Ca, P) treatment + Sr sputtering)

Except for using Example 6, RF-magnetron sputtering was performed under the same conditions as in Example 10 to obtain a Ti-35Nb-15Ta alloy in which an Sr coating layer was formed.

Comparative Example 1 (Ti-6Al-4V alloy)

In comparison with Example 1, a Ti-6Al-4V alloy was prepared in the same manner as in Example 1, except that Ti metal, Al metal, and V metal were used as element materials.

Comparative Example 2 (Cp-Ti)

Pure titanium was used.

Comparative Example 3 (Ti-35Nb)

Compared with Example 1, a Ti-35Nb alloy was prepared in the same manner except that Ti metal and Nb metal were used as element materials.

Comparative Example 4 (Ti-35Nb + PEO (Ca, P) treatment)

A Ti-35Nb alloy in which a porous oxide film containing Ca ions and P ions was formed was obtained by performing plasma electrolytic oxidation under the same conditions as in Example 4, except that Comparative Example 3 was used.

Comparative Example 5 (Ti-35Nb + PEO (Ca, P, Sr) treatment)

A Ti-35Nb alloy having a porous oxide film including Ca ions, P ions and Sr ions was obtained by performing plasma electrolytic oxidation under the same conditions as in Example 4, except that Comparative Example 3 was used.

Comparative Example 6 (Ti-35Nb + PEO (Ca, P) treatment + Sr sputtering)

Except for using Comparative Example 4, RF-magnetron sputtering was performed under the same conditions as in Example 10 to obtain a Ti-35Nb alloy in which an Sr coating layer was formed.

The above-described comparative examples and examples may be divided into Table 2 below.

Comparative Example 1 Ti-6Al-4V alloy Comparative Example 2 Cp-Ti Comparative Example 3 Ti-35Nb Comparative Example 4 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb alloy with porous oxide film Comparative Example 5 Through the PEO process using an electrolyte solution containing Ca, P and Sr ions
Ti-35Nb alloy with porous oxide film Comparative Example 6 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb alloy with porous oxide film
Ti-35Nb alloy with Sr coating layer formed using RF-magnetron sputtering Example 1 Ti-35Nb-3Ta alloy Example 2 Ti-35Nb-7Ta alloy Example 3 Ti-35Nb-15Ta alloy Example 4 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb-3Ta alloy with porous oxide film Example 5 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb-7Ta alloy with porous oxide film Example 6 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb-15Ta alloy with porous oxide film Example 7 Through the PEO process using an electrolyte solution containing Ca, P and Sr ions
Ti-35Nb-3Ta alloy with porous oxide film Example 8 Through the PEO process using an electrolyte solution containing Ca, P and Sr ions
Ti-35Nb-7Ta alloy with porous oxide film Example 9 Through the PEO process using an electrolyte solution containing Ca, P and Sr ions
Ti-35Nb-15Ta alloy with porous oxide film Example 10 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb-3Ta alloy with porous oxide film
Ti-35Nb-3Ta alloy with Sr coating layer formed using RF-magnetron sputtering Example 11 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb-7Ta alloy with porous oxide film
Ti-35Nb-7Ta alloy with Sr coating layer formed using RF-magnetron sputtering Example 12 Through the PEO process using an electrolyte solution containing Ca and P ions
Ti-35Nb-15Ta alloy with porous oxide film
Ti-35Nb-15Ta alloy with Sr coating layer formed using RF-magnetron sputtering

Experimental Example 1 (Comparative Examples 1 to 3 and Examples 1 to 3 microstructure, crystal phase, elastic modulus, hardness analysis)

3 is an XRF graph of the titanium-based alloy prepared in Comparative Examples, 3, and Examples 1 to 3 of the present invention, respectively.

Referring to FIG. 3 , the peak of Ta could not be confirmed in Comparative Example 3, but as the content of Ta increased, it could be confirmed that the peak increased in Examples 1, 2 and 3, and the analyzed The composition of the alloy is shown in Table 3.

Furtherance Comparative Example 3 Example 1 Example 2 Example 3 Ti 64.50 ± 0.96 61.06 ± 0.67 57.43 ±0.84 49.87 ± 0.78 Nb 35.50 ± 0.96 35.99 ± 0.62 35.53 ±0.70 35.39 ± 0.55 Ta 0 2.95 ± 00.17 7.03 ± 0.30 14.74 ± 0.36

4 is an optical microscope image of a titanium-based alloy prepared in Comparative Example 3 and Examples 1 to 3, respectively.

Referring to FIG. 4 , martensite (α,α˝) structures were observed in (a) and (b), and only equiaxed structures (β) were observed in (c) and (d). (a), (b) and (c) show that the martensitic structure decreases as the Ta content increases.

5 is an XRD graph of the titanium-based alloy prepared in Comparative Example 1, Comparative Example 3, and Examples 1 to 3, respectively.

Referring to FIG. 5, in Comparative Example 1 with a small content of β-stabilizing element, low β-phase and α-phase were observed, and in Example 3 with more β-stabilizing element than Comparative Example 1, it was divided into α˝ phase and β phase. lost. Also, as the content of Ta was increased, the α˝ phase disappeared, and the β phase peak narrowed and sharpened, and it was clearly visible. Therefore, it can be seen that Nb and Ta act as β-stabilizing elements to leave the β phase at room temperature, and it is consistent with the decrease in the martensite (α, α˝) structure according to the increase in the Ta content in FIG. 4 . Able to know.

6 is an image of the indentation marks on the surface of the titanium-based alloy prepared in Comparative Example 3 and Examples 1 to 3, respectively, after nanoindentation measurement.

Referring to FIG. 6 , (a), (b), (c) and (d) all appeared similarly difficult to distinguish. However, in (a) and (b), the boundary of the indentation mark was sharply divided where the martensitic structure was visible, but in the region showing the beta phase of (c) and (d), the boundary where ductile deformation could be seen represents

7 is a graph showing the nanoindentation results of the titanium-based alloy prepared in Comparative Examples 1 to 3 and Examples 1 to 3, respectively.

Referring to FIG. 7 , it can be seen that all metals are divided into an elastic region and a plastic region, and it can be seen that Examples 1, 2, and 3 increase the amount of plastic deformation significantly, and the nanoindentation hardness It shows that the curve shifts to the right as α is lowered. In addition, as the modulus of elasticity increases, the slope at the time of removal of the load appears sharply.

8 is a graph showing the elastic modulus and indentation hardness of the titanium-based alloy prepared in Comparative Examples 1 to 3 and Examples 1 to 3, respectively.

Referring to FIG. 8 , the modulus of elasticity of Comparative Examples 3, 1, 2 and 3 was lower than that of Comparative Examples 1 and 2, and Comparative Example 3 having a low modulus of elasticity. , Examples 1, 2, and 3 can reduce the stress shielding phenomenon due to the difference in elastic modulus between the bone and the implant. In addition, the elastic modulus and indentation hardness of FIG. 8 are shown in Table 4 below.

specimen Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 indentation hardness 5.34±0.14 3.17±0.12 2.61±0.05 2.30±0.11 2.23±0.11 2.30±0.12 modulus of elasticity 135.01±0.36 124.01±1.17 84.57±0.76 81.58±1.45 71.80±3.29 63.41±1.21

Experimental Example 2 (Surface structure, cross-section and surface characteristic analysis of Comparative Example 4, Comparative Example 5 and Examples 4 to 9)

9 is an optical image observing the reaction occurring on the surface according to the plasma electrolytic oxidation treatment time when preparing Comparative Examples 4 and 4 to 6, and FIG. 10 is Comparative Example 5, Examples 7 to 6 It is an optical image observing the reaction occurring on the surface according to the plasma electrolytic oxidation treatment time when manufacturing 9.

9 and 10, for all alloys, an oxide film is instantaneously generated in 0.02 seconds after voltage is applied to the plasma electrolytic oxidation device, and then gas bubbles and sparks are generated, and the Reduced sparks and gas bubbles. In addition, regardless of the presence or absence of Sr used as the electrolyte solution, sparks occurred up to 20 seconds only in Examples 6 and 9 in which the composition of Ta was 15 wt%, and the spark generation decreased after 20 seconds. This means that the higher the composition of Ta, the more the reaction occurs.

11 is an image showing FE-SEM results of titanium-based alloys prepared in Comparative Example 4 and Examples 4 to 6, respectively, and FIG. 12 is titanium prepared in Comparative Example 5 and Examples 7 to 9, respectively. It is an image showing the FE-SEM result of the alloy based alloy.

All of the titanium-based alloys of FIGS. 11 and 12 were porous, and irregularly shaped pores were observed, and as the content of Ta increased, the size of the pores increased and the surface was flattened, and in FIGS. 11 (d) and 12 In (d), both surrounding pores were connected to form groove-shaped pores, and pores with a size of 1 μm or less were not observed.

13 as a graph showing the porosity of the titanium-based alloy prepared in Comparative Example 4, Comparative Example 5, and Examples 4 to 9, respectively, FIG. 14 as a graph showing a large pore size, and a graph showing the number of pores FIG. 15 , is a graph showing the ratio of large pores in FIG. 16 .

13, 14, 15 and 16, the porosity, the size of large pores, and the ratio of large pores increased as the content of Ta increased regardless of the presence or absence of Sr ions included in the electrolyte. number decreased. The results of FIGS. 13, 14, 15 and 16 and the size values of small pores of 1 μm or less are shown in Table 5 below.

specimen Comparative Example 4 Example 4 Example 5 Example 6 porosity 7.25±0.16 10.39±0.04 12.01±0.91 25.65±1.16 large pore size 1.86±0.40 1.90±0.62 2.24±0.65 2.83±1.15 small pore size 0.48±0.13 0.63±0.17 0.77±0.14 - number of pores 66.80±5.53 55.00±4.34 40.40±5.31 12.00±1.90 ratio of large pores 27.32±6.11 48.40±3.31 61.14±3.87 90.00±8.43 Comparative Example 5 Example 7 Example 8 Example 9 porosity 7.91±0.02 10.27±0.47 11.81±0.72 26.23±1.10 large pore size 1.81±0.44 1.87±0.46 2.15±0.53 2.81±1.09 small pore size 0.46±0.13 0.58±0.15 0.64±0.20 - number of pores 69.20±8.08 58.20±3.49 40.40±5.24 12.20±2.79 ratio of large pores 29.28±3.57 47.11±2.42 65.51±4.29 87.24±6.91

17 is an image showing a cross section of a titanium-based alloy prepared in Comparative Example 4, Examples 4 to 6, respectively.

Referring to FIG. 17 , the oxide film is composed of a dense oxide film and an oxide film having many pores, and pores inside the oxide film are composed of connected pores and closed pores.

18 is an image showing a cross-section of a titanium-based alloy prepared in Comparative Example 5 and Examples 7 to 9, respectively, and the structure of the cross-section is not different from that of FIG. 17 .

19 is a graph confirming the oxide film thickness of each titanium-based alloy prepared in Comparative Example 4, Comparative Example 5 and Examples 4 to 9 using an image analysis program (Image J, Wayne Rasband, USA).

Referring to FIG. 19 , as the content of Ta increases, the thickness of the oxide film increases. In addition, the thickness of the oxide film measured through image J is shown in Table 6 below.

thickness of oxide film thickness of oxide film Comparative Example 4 3.084 ± 0.570 Comparative Example 5 3.200 ± 0.382 Example 4 3.926 ± 0.476 Example 7 3.889 ± 0.319 Example 5 4.613 ± 0.368 Example 8 4.789 ± 0.258 Example 6 5.850 ± 0.497 Example 9 6.106 ± 0.538

20 is an image showing the EDS results of the titanium-based alloy prepared in Comparative Example 4, Examples 4 to 6, respectively.

Referring to FIG. 20 , the Ca/P ratio was 1.66 in (a), 1.60 in (b), 1.70 in (c), and 1.70 wt% in (d). Hydroxyapatite has a stoichiometric Ca/P ratio of 1.67 wt%, similar to (a), (b), (c) and (d). This chemical and structural similarity to the bones of the living body helps in the nucleation and growth of bones in the human body.

21 is an image showing the ESD results of the titanium-based alloy prepared in Comparative Example 5, Examples 7 to 9, respectively.

Referring to FIG. 21, (Ca+Sr)/P ratio is 1.67 for (a), 1.98 for (b), 1.89 for (c), and 2.26 wt.% for (d) of the titanium-based alloy in FIG. It showed a value higher than the Ca/P ratio. As a reason, Sr ions may be substituted with Ca ions in the HA crystal structure to exist as Sr-HA, and when substituted, the ionic radius of Sr is larger than that of Ca, so the crystal structure of Sr atoms becomes unstable.

22 is a graph showing XRD results of titanium-based alloys prepared in Comparative Example 4 and Examples 4 to 6, respectively.

Referring to FIG. 22 , anatase, HA, Nb ₂ O ₅ , and TiO ₂ crystal phases were confirmed in all titanium-based alloys. In addition, as the content of Ta increases, the generation of Ta ₂ O ₅ is higher than that of the TiO ₂ oxide layer, and the peaks of the anatase phase, TiO ₂ phase, and HA crystal phase, which are Ti oxide crystal phases, are lowered. Here, representative crystal phases of Ti oxide are anatase, rutile, and brookite. It is more favorable for the formation of hydroxyapatite than the crystal structure.

In addition, Ta and Nb elements may be substituted for Ti in the crystal structure of Ti. Therefore, when the content of Ta and Nb elements in the Ti alloy is small, a TiO ₂ oxide film is mainly formed, and Nb and Ta occupy the position of the Ti element in the crystal structure of TiO ₂ . However, when the content of Nb and Ta elements increases, the formation of Nb ₂ O ₅ and Ta ₂ O ₅ increases, and the Ti element replaces these positions. Therefore, when the content of Nb and Ta elements in the Ti alloy is increased, the generation of anatase phase, TiO ₂ phase, and HA crystal phase is reduced, and thus the peak is reduced.

23 is a schematic diagram of the XRD patterns of Comparative Examples 5, 7, 8 and 9.

Referring to FIG. 23 , as in FIG. 22 , when the content of the TA element in the Ti alloy is increased, the generation of the anatase phase, the TiO ₂ phase, and the HA crystal phase is reduced, so that the peak decreases.

24 is a graph showing XRD results of titanium-based alloys prepared in Comparative Examples 4 and 5, respectively.

Referring to FIG. 24 , the peak of Comparative Example 5 appeared to the left of the peak of Comparative Example 4. This is because the Sr ion radius of Sr-HA produced in Comparative Example 5 is larger than the Ca ion radius of Ca-HA.

Experimental Example 3 (Comparative Example 6, Comparative Example 10 to Comparative Example 12 surface property analysis)

25 is a result of confirming the surface image according to the deposition time of the Sr coating layer forming step in the present invention by FE-SEM. (a), (b), (c), (d), (e) are surface images near the pores. and (a-1), (b-1), (c-1), (d-1), (e-1) are surface images not near the pore, (a), (a-1) ) is before deposition, (b), (b-1) is 3 min, (c), (c-1) is 5 min, (d), (d-1) is 10 min, (e), (e) -1) is the surface image at 20 minutes.

Referring to FIG. 25 , it can be seen that a circular columnar structure is formed on the surface of the oxide film in the Sr coating layer forming step, and the columnar structure grows as the deposition time increases. As the deposition time increased to 0, 3, 5, 10 and 20 minutes, it increased to 0, 1.59, 2.75, 5.78 and 8.13 wt%, respectively. EDS results according to the deposition time of the Sr coating layer forming step are shown in Table 7 below.

Here, referring to FIG. 21 , it can be seen that the content most similar to the Sr ion content of 1.0 to 2.0 wt% is when the deposition is carried out for 3 minutes.

Time (minutes) ＼ composition Example 4 O K P K Ca K Ti K Sr L Nb L Ta M Totals 0 37.20 5.11 8.19 32.42 - 16.21 0.87 100 3 37.65 5.05 7.61 29.67 1.59 15.90 2.53 100 5 38.39 5.35 8.05 29.32 2.75 14.34 1.79 100 10 38.30 4.72 8.38 28.23 5.78 13.24 1.34 100 20 36.50 4.62 7.63 27.23 8.13 12.86 3.04 100

26 is an image showing the FE-SEM results of the titanium-based alloy prepared in Comparative Example 6, Examples 10 to 12, respectively.

Referring to FIGS. 26 and 11 , there is no significant difference between the surface shapes of FIGS. 11 and 26 . This means that the thickness of the thin film deposited during the sputtering process is very thin and does not affect the porous oxide film formed after plasma electrolytic oxidation.

27 is an image showing the EDS results of the titanium-based alloy prepared in Comparative Example 6, Examples 10 to 12, respectively.

Referring to FIG. 27 , it was shown that Sr ions were coated on the porous surface in a composition of 1.0 to 2.0% by weight, and the composition of Sr ions of Comparative Examples 5, 7, 8 and 9 of FIG. 21 is similar. .

28 is a graph showing XRD results of titanium-based alloys prepared in Comparative Example 6 and Examples 10 to 12, respectively.

Referring to FIG. 28 , as the XRD patterns of Comparative Examples 6, 10, 11 and 12, the intensity of the XRD peak was lowered overall due to the effect of sputtering, and crystalline phases of anatase, HA, Nb2O5, Ta2O5 and TiO2 was observed, and the peaks of the crystal phase of Sr are low and broad, and peaks of the crystal phase of Sr exist at 23.39°, 34.91°, 46.19° and 62.63°. In addition, the shape of the low, broad peak of the Sr crystal phase in the XRD analysis indicates that the coating deposited through sputtering has amorphous or low crystalline quality.

29 is a graph showing XRD results of titanium-based alloys prepared in Comparative Examples 4 and 6, respectively.

In FIG. 29, as the XRD patterns of Comparative Examples 4 and 6, the HA peak shifted from 25.125° of the HA peak of Comparative Example 4 to 25.11° of the HA peak of Comparative Example 6, similar to FIG. It means that HA is generated.

Experimental Example 4 (Surface roughness, wettability, hydroxyapatite formation and growth, cell proliferation and growth analysis of Comparative Examples 3 to 6 and Examples 1 to 12)

30 is a graph showing the surface roughness through a surface roughness tester of the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12, respectively.

Referring to FIG. 30 , there is no difference in surface roughness depending on the electrolyte, meaning that the surface roughness is changed according to the content of Ta. The surface roughness decreased as the content of Ta increased. When the composition of Ta was 15, the surface roughness increased again. Comparing FIGS. 11, 12, and 26, when the Ta composition is 15, the shape of the pores appears as a groove shape. This means that the increase in surface roughness increases due to the groove shape. The results of surface roughness analysis are shown in Table 8 below.

In addition, in this surface roughness, a rough surface promotes the adhesion of proteins necessary for bone cell adhesion and cell adhesion rather than a smooth surface, and considering that the roughness range of 50 nm to 1.2 μm affects the initial adhesion of osteo cells, the groove This means that the biocompatibility is improved when the shape appears.

Surface roughness (㎛) Surface roughness (㎛) Surface roughness (㎛) Comparative Example 4 0.388 ± 0.035 Comparative Example 5 0.374 ± 0.039 Comparative Example 6 0.383 ± 0.033 Example 4 0.355 ± 0.029 Example 7 0.353 ± 0.029 Example 10 0.353 ± 0.033 Example 5 0.320 ± 0.028 Example 8 0.310 ± 0.041 Example 11 0.319 ± 0.016 Example 6 0.530 ± 0.044 Example 9 0.450 ± 0.034 Example 12 0.536 ± 0.074

31 is a 2D image showing AFM results of titanium-based alloys prepared in Comparative Examples 3 to 6 and Examples 1 to 12, respectively, at a magnification of 5 μm, and FIG. 32 is an AFM result at a magnification of 5 μm. 3D image shown.

Referring to FIGS. 31 and 32 , in the same manner as the pore shape observed in the FE-SEM image after surface treatment in each of the conditions of FIGS. 11, 12, and 26 , as the content of Ta increased, the surface became flat. , when the Ta content was 15, groove-shaped pores were formed and the surface roughness was increased.

33 is an image of measuring the contact angle of the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12, respectively.

Referring to Figure 33, (a) to (d) the wettability decreased as the content of Ta increased, (a-1) to (d-1), (a-2) to (d-2), (a-3) to (d-3) means that the wettability increases as the content of Ta increases. The results of wettability are shown in Table 9 below. Here, an increase in wettability equals a decrease in the contact angle.

In addition, the wettability of the biomaterial affects the adsorption and activation of proteins, platelet adhesion, and bone cell adhesion in a physiological environment. It helps in early bone formation and improves biocompatibility.

contact angle contact angle contact angle contact angle Comparative Example 3 54.67±2.25 Comparative Example 4 43.47±0.93 Comparative Example 5 42.78±2.81 Comparative Example 6 42.06±1.22 Example 1 59.29±0.84 Example 4 38.75±0.88 Example 7 38.61±1.55 Example 10 36.56±0.65 Example 2 67.42±1.11 Example 5 31.58±1.95 Example 8 32.07±0.42 Example 11 31.26±0.79 Example 3 72.57±1.86 Example 6 20.23±1.93 Example 9 19.56±0.97 Example 12 18.70±0.90

34 is an FE-SEM image in which the titanium-based alloy prepared in Comparative Examples 3 to 6 and Examples 1 to 12, respectively, was immersed in an SBF solution, and the appearance of hydroxyapatite after one day was observed at a magnification of 100 μm. to be.

Referring to FIG. 34 , nuclei are generated on the entire surface of hydroxyapatite, and in the case of an untreated alloy, growth is active in a high surface roughness area, and in the case of an alloy having a surface treatment, growth is active around the pores. In addition, the growth of hydroxyapatite was most active in (a-2), (b-2), (c-2), and (d-2), where a porous oxide film containing Ca ions, P ions and Sr ions was formed. This means that the addition of Sr ions to the pores and oxide film generated during the plasma electrolytic oxidation treatment promotes the nucleation and growth of hydroxyapatite.

35 is an FE-SEM image of the titanium-based alloy prepared in Examples 7 and 10, respectively, in an SBF solution, and the appearance of hydroxyapatite after 1 day was observed at a magnification of 2 μm.

It can be seen from the mapping result of FIG. 35 that the precipitated hydroxyapatite contains Sr ions. Therefore, it can be confirmed that the Sr ions contained in the oxide film affect the precipitation of hydroxyapatite.

FIG. 36 is an FE-SEM image showing the appearance of hydroxyapatite after 1 day by immersing the titanium-based alloy prepared in Examples 1, 4, 7 and 10, respectively, in an SBF solution.

Referring to FIG. 36, (b), (c), (d) contains an anthase phase and an HA phase in the oxide film, so nucleation occurred more actively on the surface than (a) without surface treatment, and sputtering In the case of (d) on which an Sr coating film was formed as a result, nucleation was reduced due to a thin coating deposited on the surface of the oxide film.

37 is a schematic diagram of a process of nucleation and growth of hydroxyapatite in an oxide film of a titanium-based alloy having a porous oxide film formed thereon.

Referring to FIG. 37 , hydroxyapatite formation is nucleated over the entire surface, and grows mainly in places with pores or high roughness.

38 is an FE-SEM image showing the morphology of MC3T3-E1 osteoblasts cultured for 2 days in each of the titanium alloys prepared in Comparative Examples 3 to 6 and Examples 1 to 12 at a magnification of 100 μm. to be.

Referring to FIG. 38 , it can be seen that cell adhesion and proliferation are active as the content of Ta increases in all alloys. In addition, in the surface-treated titanium-based alloy, cells are well attached as a whole and proliferation is active, and when Sr ions are contained, cell proliferation is more active.

39 is an FE-SEM image showing cell growth according to the surface shape of the titanium-based alloy prepared in Comparative Example 3, Example 1, Example 4, Example 7, and Example 10, respectively.

Referring to FIG. 39, in the case of (b), (c), (d), and (e) having micropores on the surface, it can be seen that lamellipodia have grown long, and the lamellipodia cover the micropores and spread widely in all directions. while growing up In addition, filopodia do not grow on the surface, but grow into the pores inside or around the pores. This means that osteoblasts grow through rough surfaces and nanoparticles or pores. In addition, osteoblasts grow actively in the pore size of 1.2 to 3 μm. Referring to the pore sizes in Table 5, considering that the small pore sizes of Comparative Examples 4, 4, 5, 5, 7, and 8 are 0.48 to 2.24 μm, osteoblasts It can be seen that the growth of In the case of Examples 6 and 9, it can be seen that the filopodia grow toward the shorter distance between the pores.

As described above, according to the method for manufacturing a biocompatibility-enhancing titanium-based alloy according to the present invention, as compared to a conventional Ti-6Al-4V titanium-based alloy, vanadium and aluminum are not used, and thus, while having non-toxicity, cortical bone It has an elastic modulus similar to that of , and has the effect of preventing stress shielding.

In addition, the method for manufacturing a sanitary compatibility-enhancing titanium-based alloy according to the present invention forms a porous oxide film containing Ca ions and P ions on the surface of the Ti-Nb-Ta alloy, so that it is chemically and structurally similar to the bone of a living body. It has the effect of improving osseointegration and increasing the surface roughness to promote the adsorption of proteins required for bone cell adhesion or cell adhesion.

In addition, the method for manufacturing a biocompatibility-enhancing titanium-based alloy according to the present invention forms an Sr coating layer on a porous oxide film layer containing Ca and P, thereby inhibiting osteoclast proliferation and stimulating osteoblast differentiation, thereby reducing the healing period. have

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 (12)

Titanium-based alloy manufacturing step of producing a titanium-based alloy;
a porous 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 Sr coating layer forming step of forming an Sr coating layer using an RF-magnetron sputtering device on the surface of the titanium-based alloy on which the porous oxide film is formed,
The titanium-based alloy is made of Ti-35Nb-xTa, where x is a method for producing a biocompatibility enhancement-type titanium-based alloy, characterized in that 3 to 15wt%.
The method of claim 1,
The electrolyte solution is a method for producing a biocompatibility-enhanced titanium-based alloy, characterized in that it contains Ca and P ions.
3. The method of claim 2,
The electrolyte solution is a biocompatibility enhancement type titanium alloy comprising calcium acetate monohydrate [Ca(CH ₃ COO) ₂ ·H ₂ O] and calcium glycerophosphate [C ₃ H ₇ CaO ₆ P] manufacturing method.
The method of claim 1,
In the step of forming the porous oxide film, a voltage of 250V to 280V is applied for 2 minutes and 30 seconds to 3 minutes and 30 seconds.
The method of claim 1,
In the step of forming the Sr coating layer, the RF-power of the magnetron sputtering device is applied in a range of 40W to 60W.
The method of claim 1,
The titanium-based alloy manufacturing step,
a first polishing step of polishing the titanium-based alloy to 100, 600, 1000 and 2000 grit using a silicon carbide abrasive; and a second polishing step of micro-polishing the polished titanium-based alloy with alumina powder (Al ₂ O ₃ ).
Claims 1 to 6, wherein any one of the biocompatibility enhancement-type titanium-based alloy produced by the method for manufacturing the titanium-based alloy.
8. The method of claim 7,
The biocompatibility-enhancing titanium-based alloy is
titanium-based alloys;
a porous oxide film formed on the surface of the titanium-based alloy and containing Ca ions and P ions;
Including; Sr coating layer formed on the porous oxide film,
The titanium-based alloy is made of Ti-35Nb-xTa, wherein x is biocompatibility enhanced titanium-based alloy, characterized in that 3 to 15wt%.
Dental implant comprising the biocompatibility enhancement type titanium-based alloy of claim 8.
The method of claim 1,
The electrolyte solution is a method for producing a biocompatibility-enhanced titanium-based alloy, characterized in that it contains Ca, P and Sr ions.
11. The method of claim 10,
The electrolyte solution is calcium acetate monohydrate [Ca(CH ₃ COO) ₂ ·H ₂ O], calcium glycerophosphate [C ₃ H ₇ CaO ₆ P] and strontium acetate [Sr(CH ₃ COO) ₂ ·0.5H ₂ O], characterized in that it comprises a biocompatibility enhancement-type titanium-based alloy manufacturing method.
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