KR100953126B1 - Method of coating of hydroxyapatite on titanium implant surface - Google Patents

Abstract

The present invention relates to a method for coating apatite hydroxide on a titanium implant surface, which comprises dry dipping the titanium implant onto apatite hydroxide powder and thermally sintering the same in an electric furnace. Unlike the conventional method, by coating apatite hydroxide on the surface of the titanium implant using a dry dipping (DRY-Dipping) coating technology, the manufacturing process is simple and the manufacturing cost is reduced and mass production is possible.

Titanium, Implants, Apatite Hydroxide, Coating, Dry Dipping, Sintered

Description

Method of coating of hydroxyapatite on titanium implant surface

The present invention is dry-dipping a titanium implant on the apatite hydroxide powder to perform a surface treatment, so that the coating layer maintains sufficient strength without changing the components of the apatite hydroxide, and has excellent biocompatibility and bone adhesion. Relates to a method for coating apatite hydroxide on a titanium implant surface

In general, titanium and titanium alloy materials are transition metal materials widely used in dentistry and orthopedics, and do not have excellent characteristics of biocompatibility and chemical compatibility. Inserted into the bones of the human body maintains only mechanical coupling has a disadvantage that the bone and bone fusion of the human body is not made.

Therefore, research is being actively conducted on a technique of coating a surface of a titanium implant with a biocompatible apatite (HAp, Hydroxyapatite) in order to improve the titanium implant tissue in contact with the bone of the human body.

Apatite hydroxide (HAp, Hydroxyapatite) is a compound having excellent biocompatibility and bone adhesion properties, and is widely used in orthopedic, dental, and pharmaceutical fields. However, in the case of apatite hydroxide, there is a problem in that it has a limitation in use due to low mechanical strength. Recently, related research institutes and industries have developed a bio-ceramic apatite (HAp), which has sufficient mechanical strength and torque. Is being applied.

Plasma spraying is most commonly used as a method of coating apatite hydroxide on an implant. However, conventional implants coated with hydroxide apatite have a problem of coating layer falling off during the procedure due to weak uniformity and adhesion of the coating layer, and there is a problem of high price and mass production of implant due to expensive equipment and complex coating process. .

In order to solve the above problems, the present invention provides a dry implant of a titanium implant treated with a resolbable blast media (RBM) to apatite hydroxide powder having a particle size of 45 μm or less, followed by dry sintering in an electric furnace to make titanium. By coating apatite hydroxide on the surface of the implant, it is possible to provide a method of coating apatite hydroxide on the surface of titanium implant, characterized in that it does not change the apatite hydroxide component of the coating layer so that the biocompatibility is excellent and sufficient mechanical strength can be maintained. There is this.

Conventionally, the coating of apatite hydroxide on the surface of the titanium implant is mainly performed by plasma spraying, so that the apatite phase is easily decomposed to obtain a pure and uniform composition layer, the peeling occurs easily on the surface of the titanium implant, and the surface roughness There are reports that there are problems that are too large to reduce bone adhesion.

In the present invention for solving the above problems in the method of coating apatite hydroxide on the surface of the titanium implant,
The titanium implant is dry dipped in apatite hydroxide powder having a particle size of 45 μm or less and then sintered by heating at an electric temperature of 900 ± 10 ° C. for 10 to 50 minutes,
The surface of the titanium implant is a surface treatment by the RBM (Resolbable Blast Media) method using a media of calcium phosphate particles (Abpatite) coating method of hydroxide apatite, characterized in that the problem solution.

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The present invention, unlike the conventional method through expensive equipment and complex process, by coating the surface of the titanium implant with apatite hydroxide using a simple dry DRY-Dipping coating technology, manufacturing process is simple The advantage is that it can be reduced and mass produced.

The present invention for achieving the above-mentioned effect is characterized in that the titanium implant is dry-dipping (dry-dipping) to the apatite hydroxide powder and heat-sintered in an electric furnace to coat the apatite hydroxide on the surface of the titanium implant.

Hereinafter, a method of coating the hydroxide apatite on the titanium implant surface according to the present invention will be described in detail with reference to the accompanying drawings.

1 is a view showing a manufacturing process for coating apatite hydroxide on the surface of the titanium implant in accordance with the present invention.

The present invention dry dipping the titanium implant (B) to the apatite hydroxide powder (A) (Dry-Dipping) (100) and then heat sintered (200) inside the electric furnace finished product coated with the hydroxide apatite on the surface of the titanium implant ( C) is prepared.

A feature of the present invention is the dry dipping (100) of titanium implant (B) on the apatite hydroxide powder (A) and then heat sintering (200) inside the electric furnace.

In the titanium implant used in the present invention, it is preferable to surface-treat the surface by RBM (Resolbable Blast Media) to increase the bonding strength with the apatite hydroxide.

The media particles by the RBM method are preferably calcium phosphate particles which are compounds which are completely dissolved in the body.

And the size of the apatite hydroxide powder particles used in the present invention is preferably 45㎛ or less.

When the size of the apatite hydroxide powder particles exceeds 45㎛, it is difficult to obtain a film of a uniform apatite hydroxide composition on the surface of the titanium implant, there is a concern that the surface roughness of the coating layer is too large, rather it may cause a problem of reducing the bone adhesion.

Dry dipping (100) of the titanium implant having the above conditions in the attaphite hydroxide powder is preferably sintered (200) by heating for 10 to 50 minutes at 900 ± 10 ℃ in an electric furnace.

Dry-dipping the titanium implant into the crucible containing the apatite hydroxide powder (100) and then heated at 900 ± 10 ° C. in an electric furnace for 10 to 50 minutes, while the titanium of the implant is melted on the surface of the titanium implant. Apatite hydroxide powder will be coated.

When the heating conditions are below the range of the above-defined conditions, there is a risk that the atta hydroxide is not sufficiently sintered, thereby forming a coating layer in which the atta hydroxide is incomplete on the surface of the titanium implant, and the heating conditions are limited above. In the case of exceeding a range of conditions, the thickness of the attaphite hydroxide coating layer is too thick on the surface of the implant, so the roughness of the surface of the coating layer is too large and may cause a problem of reducing bone adhesion.

Then, the finished product (C) coated with apatite hydroxide is prepared on the surface of the titanium implant of the type as shown in the photo of FIG.

Hereinafter, the configuration of the present invention will be described in more detail based on the following examples, but the present invention is not necessarily limited only to the following examples.

1. Preparation of Titanium Implants with Athapatite Coating Layer

(Example 1)

Titanium implant surface-treated with calcium phosphate particles by the Resolbable Blast Media (RBM) method in a crucible containing a powder of atta hydroxide (98% purity or more, particle size 125 ~ 300㎛) of 45 µm or less Sintering the attaphite hydroxide powder while heating it at 900 ± 2 ℃ for 10 minutes in the electric furnace in the DRY-Dipping state to form a coating layer on the surface of the titanium implant, and then finishing the mounting process to finish the attaphite coating layer. The formed titanium implant was prepared.

(Example 2)

A titanium implant was prepared by sintering at 900 ± 2 ° C. for 20 minutes in the same manner as in Example 1 to form a hydroxyapatite coating layer.

(Example 3)

A titanium implant was prepared by sintering at 900 ± 2 ° C. for 30 minutes in the same manner as in Example 1 to form a hydroxyapatite coating layer.

(Example 4)

A titanium implant was prepared by sintering at 900 ± 2 ° C. for 40 minutes in the same manner as in Example 1 to form a hydroxyapatite coating layer.

(Example 5)

A titanium implant was prepared by sintering at 900 ± 2 ° C. for 50 minutes in the same manner as in Example 1 to form a hydroxyapatite coating layer.

2. X-ray Diffraction Analysis (XRD) for Apatite Hydroxide

X-ray diffraction analysis (XRD) of the apatite hydroxides used in Examples 1 to 5 of the present invention showed that the XRD of the apatite hydroxide coincided with the theoretical peak of the apatite hydroxide as shown in FIG. have. 3B shows the crystal phase of apatite hydroxide photographed by scanning electron microscopy (SAM), and was analyzed to be 1.668 which is close to 1.67 which is the Ca / P molar ratio of apatite hydroxide.

3. Inductively Coupled Plasma Emission Analysis for Apatite Hydroxide (ICP-OES)

Example 1, an inductively coupled plasma emission analysis (ICP-OES) to the hydroxide apatite used in to 5 results of the invention [Table 1] the same as information, the main component of CaO and P ₂ O ₅ of hydroxide apatite 98 It turns out that it is more than weight%.

(Unit: weight%) Analyte Analysis SiO ₂ 0.13 Al ₂ O ₃ 0.10 CaO 57.00 MgO 0.02 Fe ₂ O ₃ 0.01 Na ₃ O 0.14 TiO ₂ 0.10 SrO 0.02 P ₂ O ₅ 41.40 Combustion loss 1.05

4. Scanning Electron Microscopy (SEM) Analysis of Apatite Hydroxide-coated Titanium Implants

The photograph of the titanium implant coated with the hydroxide of apatite of Examples 1 to 5 using a scanning electron microscope (SEM) is shown in FIG. 4. Example 1 sample (FIG. 4A) having a sintering time of 10 minutes has a thickness of 12 μm, and Example 2 sample (FIG. 4B) having a sintering time of 20 minutes has a thickness of 14 μm and a sintering time of 30 minutes. Sample 4 (FIG. 4C) has a coating layer thickness of 22 µm and sintering time of 40 minutes. Example 4 Sample (FIG. 4D) has a coating layer thickness of 24 µm and a sintering time of 50 minutes. It can be seen that the thickness of the coating layer is 32 μm.

As shown in the photographs of FIGS. 4A to 4E, it can be seen that as the sintering time increases, the thickness of the apatite hydroxide coating layer increases.

5. Energy Dispersion X-RAY (EDS) Analysis of Apatite Hydroxide Coating Layer

Scanning electron microscopy (SEM) of the sample of Example 1, and analyzed using the energy dispersive X-RAY (EDS) as shown in Figure 5, the Ca / P molar ratio of the apatite hydroxide coating layer was analyzed as 1.574, It can be seen that this is close to the theoretical molar ratio of the apatite hydroxide.

6. X-ray Diffraction (XRD) of Apatite Hydroxide-Coated Titanium Implants

As a result of X-ray diffraction analysis (XRD) of the samples of Examples 1 to 5, it was confirmed through JCPDS card number 9-432 that the crystal phase of apatite hydroxide was irrespective of the sintering time as shown in FIG. 6.

7. X-RAY Electron Spectroscopy (XPS) Analysis of Titanium Implants with Apatite Hydroxide

As a result of X-ray electron spectroscopy (XPS) analysis of the sample of Example 1, elements of Ca, P, Ti, and O were detected in the titanium implant and the apatite hydroxide coating site. Therefore, the analysis of such components shows that apatite hydroxide is coated on the surface of titanium.

8. Micro Vickers Hardness Analysis of Titanium Implants with Apatite Hydroxide

As a result of measuring the hardness of the apatite hydroxide coating layer using the micro-Vickers hardness tester for the samples of Examples 1 to 5, it can be seen that the Vickers hardness also increases as the sintering time increases as shown in the graph shown in FIG. 8.

In addition, the strength of the razor was investigated and the strength of the apatite-coated titanium implant using the conventional plasma spray method was found to be firm.As a result of the adhesion test, the conventional problem of the coating layer dropping during the procedure of the implant could be solved. there was.

In addition, as shown in FIG. 9, the titanium implant coated with apatite hydroxide was immersed in a biosimilar body fluid (SBF) for 4 weeks and then photographed with a scanning electron microscope (SEM). It can be seen that over time it is activated.

Therefore, according to the apatite hydroxide coating method of the present invention, it could be confirmed through the above examples that the titanium implant coated with apatite hydroxide can be manufactured by a dry dipping coating method.

As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated.

1 is a view showing a manufacturing process for coating apatite hydroxide on the surface of a titanium implant in accordance with the present invention;

Figure 2 is a photograph of a titanium implant coated with a hydroxide hydroxide in accordance with the present invention;

3 is an X-ray diffraction analysis (XRD) graph (A) and a scanning electron microscope (SEM) photograph (B) of apatite hydroxide according to the present invention;

FIG. 4 is a scanning electron microscope (SEM) analysis photograph of an apatite hydroxide coated titanium implant according to the present invention; FIG.

5 is a scanning electron microscope (SEM) analysis photograph and energy dispersive X-ray (EDS) analysis data of apatite hydroxide coated titanium implants according to the present invention;

6 is X-ray diffraction analysis (XRD) data of titanium hydroxide coated titanium implant according to the present invention;

Figure 7 is an X-RAY electron spectroscopy (XPS) analysis of the titanium hydroxide coated titanium hydroxide in accordance with the present invention;

8 is an analysis graph of the micro-Vickers hardness of titanium hydroxide coated titanium implant according to the present invention;

Figure 9 relates to a photograph taken with a scanning electron microscope (SEM) after immersion in aqua-body-like body fluid (SBF) for four weeks the titanium implant coated with hydroxide in accordance with the present invention.

Claims (5)

In the method of coating apatite hydroxide on the surface of the titanium implant, The titanium implant is dry dipped in apatite hydroxide powder having a particle size of 45 μm or less and then sintered by heating at an electric temperature of 900 ± 10 ° C. for 10 to 50 minutes, The surface of the titanium implant is a surface treatment of the surface of the titanium implant, characterized in that the surface treatment by RBM (Resolbable Blast Media) method using a medium of calcium phosphate particles. delete delete delete delete

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