KR102462380B1 - Manufacturing method of HA-coated dental implant using titanium-based alloy And dental implant - Google Patents

Abstract

The present invention relates to a method for manufacturing an HA-coated dental implant using a titanium-based alloy, and more specifically, a Ti-Nb-Hf alloy is prepared and then anodized to form a nanotube array layer, and an HA coating layer By forming , it is possible to reduce the stress shielding phenomenon with the bone by lowering the elastic modulus, and relates to a method for manufacturing an HA-coated dental implant using a titanium-based alloy that can improve the induction of bone fusion and a dental implant.

Description

Manufacturing method of HA-coated dental implant using titanium-based alloy and dental implant {Manufacturing method of HA-coated dental implant using titanium-based alloy And dental implant}

The present invention relates to a method for manufacturing an HA-coated dental implant using a titanium-based alloy, and more specifically, a Ti-Nb-Hf alloy is prepared and then anodized to form a nanotube array layer, and an HA coating layer By forming , it is possible to reduce the stress shielding phenomenon with the bone by lowering the elastic modulus, and relates to a method for manufacturing an HA-coated dental implant using a titanium-based alloy that can improve the induction of bone fusion and a dental implant.

In general, dental implants are mechanically processed titanium or titanium alloy, and then various surface treatment processes are performed to improve the intraosseous compatibility of the implant.

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 when 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 vapor 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, or 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 the biocompatibility is poor, resulting in implant failure.

Accordingly, the present inventors 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. 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 in that biocompatibility is greatly reduced or clinical failure occurs.

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

The present invention has been devised to solve this problem, and an object of the present invention is to use a Ti-Nb-Hf alloy, thereby lowering the elastic modulus to reduce the stress shielding phenomenon with bone. To provide a method and a dental implant.

Another object of the present invention is to prepare a Ti-Nb-Hf alloy, then anodize to form a nanotube array layer, and form an HA coating layer, thereby improving biocompatibility of an HA-coated dental implant. To provide a manufacturing method 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; a nanotube array layer forming step of anodizing the prepared titanium-based alloy to form a nanotube array layer; HA coating layer forming step of forming an HA (hydroxyapatite) coating layer on the surface of the titanium-based alloy on which the nanotube array layer is formed provides

In a preferred embodiment, the titanium-based alloy is Ti-Nb-Hf.

In a preferred embodiment, the titanium-based alloy is Ti-40Nb-xHf, where x is 3 to 15.

In a preferred embodiment, in the step of forming the nanotube array layer, the titanium-based alloy is used as a working electrode, the platinum electrode is used as an auxiliary electrode, and an electrolyte solution containing H ₃ PO ₄ and NaF is used to form nanotubes. An oxide film layer having a tube structure is formed.

In a preferred embodiment, the electrolyte solution comprises 1M H ₃ PO ₄ and 0.8 wt % NaF.

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

In a preferred embodiment, in the HA coating layer forming step, an HA/Zn composite layer including HA and Zn ions is formed by RF-magnetron sputtering and DC-magnetron sputtering.

In a preferred embodiment, after the nanotube array layer forming step, the titanium-based alloy on which the nanotube array layer is formed is washed with ethanol and distilled water and then dried; a drying step is performed, and the HA coating layer forming step is performed .

In addition, the present invention further provides a dental implant, characterized in that manufactured by the manufacturing method of the HA-coated dental implant using the titanium-based alloy.

In a preferred embodiment, a nanotube array layer is formed on the surface of the dental implant.

In a preferred embodiment, the HA coating layer is formed on the surface of the nanotube array layer.

In a preferred embodiment, an HA/Zn composite layer including HA and Zn ions is formed on the surface of the nanotube array layer.

The present invention has the following excellent effects.

According to the manufacturing method of the HA-coated dental implant and the dental implant of the present invention, by using the Ti-Nb-Hf alloy, there is an effect that can reduce the stress shielding phenomenon with bone by lowering the elastic modulus.

In addition, according to the method for manufacturing an HA-coated dental implant and dental implant of the present invention, an anodization treatment is performed to form a nanotube array layer on the surface of the titanium-based alloy, and then, HA and By allowing the HA/Zn composite layer including Zn ions to be formed, corrosion resistance is increased and biocompatibility can be improved.

1 is a step diagram for explaining a method of manufacturing an HA-coated dental implant using a titanium-based alloy according to an embodiment of the present invention.
2 is an image showing the chemical composition of the Ti-40Nb-xHf alloy according to an embodiment of the present invention using XRF.
3 is a photograph of observing the microstructure using an optical microscope after homogenizing the Ti-40Nb-xHf alloy according to an embodiment of the present invention at 1050° C. for 1 hour.
Figure 4 shows the X-ray diffraction peak (XRD) after homogenizing the Ti-40Nb-xHf alloy according to an embodiment of the present invention at 1050 ℃ for 1 hour.
5 is a graph showing the average value of Vickers hardness of Ti-40Nb-xHf alloy according to an embodiment of the present invention.
6 is a graph of a nano-indentation test in which the modulus of elasticity of a Ti-40Nb-xHf alloy according to an embodiment of the present invention is measured.
7 is a result of observing the surface of a specimen in which nanotubes are formed in a Ti-40Nb-xHf alloy according to an embodiment of the present invention by FE-SEM.
8 is a graph showing changes in the thickness and size of nanotubes as the Hf content increases.
9 is an image of observing a bamboo knob on the surface of a column of a nanotube when the cross-section of the nanotube is observed.
10 is an X-ray diffraction peak image of nanotubes formed on the surface of a Ti-40Nb-xHf alloy.
11 is an image showing a process of coating HA and Zn on a specimen using RF and DC sputter.
12 is an image of observing the surface with a scanning electron microscope after HA coating using RF-sputter on the surface after formation of nanotubes.
13 is an image confirming the distribution of Ca and P elements through EDS-mapping of the surface portion of the HA-coated specimen using RF-sputter.
14 is an image confirming the distribution of Ca and P elements through EDS-mapping of the cross-section of the HA-coated specimen using RF-sputter.
15 is an image of observation of the surface with a scanning electron microscope after HA/Zn composite coating was applied to the surface after formation of nanotubes using RF and DC-sputter.
16 is an image confirming the distribution of Ca, P and Zn elements through EDS-mapping of the surface portion of the specimen coated with HA and Zn using RF and DC-sputter.
17 is an image confirming the distribution of Ca, P, and Zn elements through EDS-mapping of a cross-section of a specimen coated with HA and Zn using RF and DC-sputter.
18 is an X-ray diffraction peak image of a specimen coated with HA and HA/Zn using RF-sputter, RF, and DC-sputter on a Ti-40Nb-xHf alloy surface formed with nanotubes.
19 is a result of X-ray diffraction analysis after heat-treating a specimen coated with HA and HA/Zn at 500° C. for one hour using RF-sputter and DC-sputter.
20 shows the wettability test results of a specimen coated with HA and Zn using magnetron sputtering after forming nanotubes on the alloy surface.
21 is a potentiodynamic polarization test (potentiodynamic) in 0.9% NaCl solution at 25±1° C. to investigate the electrochemical properties according to the Hf content after preparing a Ti-40Nb-xHf alloy and quenching it in water at 0° C. after homogenization treatment. ) is a graph of the results.
22 is a graph showing the result of performing a potentiometric polarization test in 0.9% NaCl electrolyte at 25±1° C. in order to investigate the electrochemical properties after the formation of nanotubes in Ti-40Nb-xHf alloy.
23 is a graph showing the result of performing a potentiometric polarization test in 0.9% NaCl electrolyte at 25±1° C. in order to investigate the electrochemical properties of the HA-coated specimen using RF-sputter after the formation of nanotubes on the surface.
24 is a graph showing the result of performing a potentiometric polarization test in 0.9% NaCl electrolyte to investigate the electrochemical properties of HA and Zn-coated specimens using RF-sputter and DC-sputter after formation of nanotubes on the surface.

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 must 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 an HA-coated dental implant using a titanium-based alloy according to an embodiment of the present invention.

Referring to FIG. 1 , in the method for manufacturing an HA-coated dental implant using a titanium-based alloy according to an embodiment of the present invention, a Ti-Nb-Hf alloy is prepared and then anodized to form a nanotube array layer. A titanium-based alloy is first prepared as a method of manufacturing a dental implant that can improve corrosion resistance and biocompatibility while reducing stress shielding with bone by forming an HA coating layer with a similar elastic modulus to bone. (S100).

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

In this case, the Ti-Nb-Hf alloy may be expressed as Ti-40Nb-xHf, where x is preferably 3 to 15.

Next, a nanotube array layer forming step (S200) of forming a nanotube array layer by anodizing the surface of the Ti-Nb-Hf alloy is performed.

In the nanotube array layer forming step (S200), the produced Ti-Nb-Hf alloy is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and an electrolyte solution containing H ₃ PO ₄ and NaF is used. Thus, an oxide film layer having a nanotube structure is formed.

Here, the electrolyte solution is preferably a solution containing 1M H ₃ PO ₄ and 0.8% by weight of NaF.

That is, through the nanotube array layer forming step (S200), an electrochemical oxidation treatment is performed, and a nanotube structure Tano tube array layer in which a plurality of grooves are formed in an array type on the surface of the Ti-Nb-Hf alloy will be formed

Next, a drying step (S300) of washing the titanium-based alloy on which the nanotube array layer is formed with ethanol and distilled water and then drying may be performed.

Next, an HA coating layer forming step (S400) of forming an HA (hydroxyapatite) coating layer on the surface of the titanium-based alloy on which the nanotube array layer is formed is performed.

For example, in the HA coating layer forming step ( S400 ), an HA (hydroxyapatite) coating layer may be formed by RF-magnetron sputtering using a single HA (hydroxyapatite) target.

As another example, in the HA coating layer forming step (S400), an HA/Zn composite layer containing HA and Zn ions is formed by RF-magnetron sputtering and DC-magnetron sputtering using an HA (hydroxyapatite) target and a Zn target. can be formed.

That is, in the method for manufacturing an HA-coated dental implant using a titanium-based alloy according to the present invention, a Ti-Nb-Hf alloy is prepared and then anodized to form a nanotube array layer (oxide layer) having a nanotube structure. This is a technique of forming an HA (hydroxyapatite) coating layer or an HA/Zn composite layer on the surface of the nanotube array layer by magnetron sputtering.

This is because by using a Ti-Nb-Hf alloy prepared in an optimal weight ratio, the elastic modulus is lowered compared to the conventional Ti-6Al-4V alloy and has an elastic modulus similar to that of the bone, thereby reducing the stress shielding phenomenon with the bone. In addition, by forming an HA coating layer or an HA/Zn composite layer on the surface of the nanotube array layer (oxide layer), it is possible to increase corrosion resistance and improve biocompatibility and blood compatibility.

In addition, the present invention further provides a dental implant manufactured by the method for manufacturing an HA-coated dental implant using a titanium-based alloy according to the present invention.

A nanotube array layer is formed on the surface of the dental implant, and an HA coating layer or an HA/Zn composite layer including HA and Zn ions is formed on the surface of the nanotube array layer.

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

Cp-Ti (G & S Titanium, Grade 4, 99.95%, USA) in pellet form, Nb and Hf (Kurt J. Lesker Company, 99.95% pure, USA) was used.

Ti-40Nb-xHf alloy fixed the content of Nb to 40 wt.%, Hf was changed to 0, 3, 7, and 15 wt.% and weighed, Ti was quantified with a balance, and then quantified by arc melting in a vacuum atmosphere. (Arc skull melting system, Acevacuum, Korea) was charged into a copper (Cu) frame through which cooling water flows. After filling the chamber with high-purity argon gas under a vacuum atmosphere maintained at 10 ^-3 torr, the alloy is oxidized by first dissolving pure titanium for the purpose of removing trace amounts of oxygen before manufacturing the alloy. minimized.

The prepared sample was melted while turning over the alloy 10 times repeatedly using a tungsten (W) electrode in a button-shaped mold, and then transferred to an ingot mold and dissolved homogeneously by repeating 10 times. For homogeneous treatment, the above dissolution was repeated a total of two times to prepare an alloy.

The prepared specimen was cut to a diameter of 10 mm and a thickness of 3 mm through laser cutting, and then homogenized using an electric furnace (Model KDF-S270. Denken, Japan). The homogenization treatment was maintained for 1 hour at 1050°C in an Ar atmosphere electric furnace with reference to the Ti-Nb binary alloy phase diagram, and then rapidly cooled in ice water at 0°C.

Example 2 (Nanotube Array Layer Formation)

1M H ₃ PO ₄ (phosphoric acid) + 0.8 wt.% NaF (sodium fluoride) + 1000 ml H ₂ O was mixed to form an oxide layer having a nanotube structure on the surface of the Ti-40Nb-xHf alloy. A solution was prepared, and a DC power supply (6812B, Keysight Co., USA) was used as a voltage application device, and the experiment was carried out by maintaining it for 2 hours under a voltage of 30V. In addition, an oxide film layer having a nanotube structure was formed on the surface of the specimen using a specimen (Ti-40Nb-xHf alloys) as a working electrode and a platinum rod as an auxiliary electrode, respectively. After each washing process, it was dried naturally at room temperature.

Example 3 (HA coating layer formation)

The targets used in the experiment were HA (tooth ash powder 99.99%) and Zn (A-Tech system Co., Korea). For HA and Zn coatings, RF and DC-Magnetron sputtering systems were used.

Ultra-high purity Ar was used to form a coating film on the Ti-40Nb-xHf alloy in which the nanotubes were formed, and the initial vacuum was lowered to 10 ^-3 torr using a rotary pump. Then, the vacuum degree was dropped to 10 ^-6 torr using an oil diffusion pump. In order to form the HA/Zn composite layer, first, HA was deposited for 1 hour after maintaining the amount of Ar mixed gas at 40 sccm with a power of 50 W using an RF-magnetron sputter. Then, in order to form the HA/Zn composite layer, when the HA RF-magnetron sputtering time was 40 minutes, Zn was deposited for 20 minutes at 100W power using a DC-magnetron sputter. During deposition, the temperature of the chamber substrate was maintained at 150°C.

In the present invention, the enrichment conditions for obtaining the HA/Zn coating layer are shown in Table 1 below. To evaluate the thin film coating layer, it was divided into HA-deposited specimens and HA/Zn composite-deposited specimens to confirm the phase of the thin film formed by XRD. The surface shape of the thin film was observed by FE-SEM.

[Table 1]

Experimental Example 1 (Microstructure and phase analysis of Ti-Nb-Hf alloy)

The heat-treated specimen was subjected to wet polishing step by step up to 100-2000 grit SiC (silicon carbide) polishing for microstructure observation, and finally, 0.3㎛ alumina powder (Al ₂ O ₃ ) was used until a mirror surface appeared. After finishing by polishing, ultrasonic cleaning was performed for 10 minutes with acetone and distilled water so that no residue remained on the surface.

The prepared specimen was acid etched with Keller's solution of 2㎖ HF + 3㎖ HCl + 5㎖ NHO ₃ + 190㎖ H ₂ O, and then the alloy structure was used using an optical microscope (OM: optical microscopy, Olympus BM60M, Japan). was observed.

For the crystal structure of the specimen, an X-ray diffraction analyzer (XRD: X-ray diffraction) was used, and a 2θ section of 10° to 90° was analyzed. In addition, X-ray fluorescence (XRF: Analyzer Mode-Alloy, Analyzer Serial number-581331, Olympus, Japan) was analyzed to confirm the content of the component composition of each specimen.

2 is an image confirming the chemical composition using XRF in order to find out the composition of the Ti-40Nb-xHf alloy manufactured using arc melting.

In addition, Table 2 below shows the results of the chemical composition of the homogenized alloy, and the chemical composition of each alloy showed a value almost close to that of the designed alloy, confirming that the alloy was well manufactured.

[Table 2]

3 is a photograph of the microstructure observed using an optical microscope after homogenizing the Ti-40Nb-xHf alloy manufactured by arc melting at 1050° C. for 1 hour. In the case of (a), it is a Ti-40Nb alloy to which Hf is not added, (b) Ti-40Nb-3Hf, (c) Ti-40Nb-7Hf, and (d) Ti-40Nb-15Hf. As a result of microstructure observation, it shows an equiaxed structure.

When Hf is added to Ti-40Nb alloy, the β phase is mainly exhibited as Hf increases. There was no significant difference in the microstructure change, only the equiaxed structure appeared, and it was observed that the grain boundary size increased.

4 shows the X-ray diffraction peak (XRD) of the Ti-40Nb-xHf alloy homogenized at 1050° C. for 1 hour, and the β-phase peak was detected in the entire alloy. In case of (a), α" and β phases were detected at 35° and 53° with Ti-40Nb alloy without Hf added, (200) plane at 55.68° orientation, (211) plane at 70.09° orientation, 83.03° It was confirmed that the (220) plane Nb ₂ O ₅ peak was detected in the orientation, (bd) is an alloy containing 3, 7, and 15 wt% of Hf, respectively, and the β phase was mainly detected, and as the Hf content increased, β The peak of the phase increased but the α″ phase decreased. As the Hf content increased, it was confirmed that the α″ phase was transformed into the β phase.

Experimental Example 2 (Mechanical properties of Ti-Nb-Hf alloy)

Table 3 below shows the measured values of Vickers hardness of Ti-40Nb-xHf alloy. After measuring the Vickers hardness 10 times for each specimen, the average value is shown as a chart in FIG. 5 .

[Table 3]

Ti-40Nb-0Hf specimen showed 686.697 Hv, Ti-40Nb-3Hf specimen showed 427.493Hv, Ti-40Nb-7Hf specimen showed 413.164Hv and Ti-40Nb-15Hf specimen showed 268.946Hv.

As a result of measuring the hardness, it was confirmed that the Vickers hardness value decreased when the Hf content was increased. This is considered to be because the β phase increased and the α″ phase decreased as the Hf content increased.

6 shows a graph of the nano-indentation test in which the modulus of elasticity is measured. Ti-40Nb-15Hf alloy with the highest Hf content showed the lowest modulus of elasticity of 78.185 GPa.

Table 3 shows the results of the measurement of the elastic modulus of the alloys, and it was shown that the value of the elastic modulus decreased with the increase of the β phase as the Hf content increased. If the modulus of elasticity is high, a stress shielding effect may occur, which may cause osteoporosis or fracture, so an alloy with a low modulus of elasticity similar to bone needs to be developed. In the present invention, a low modulus of elasticity was obtained by adding Hf to the Ti-40Nb alloy.

Experimental Example 3 (Ti-Nb-Hf alloy nanotube formation)

7 shows the results of observing the surface of a specimen in which nanotubes are formed on a Ti-40Nb-xHf alloy by FE-SEM. 7 (a-d) is a nanotube surface of Ti-40Nb-xHf alloy, FIGS. 7 (a-1 to d-1) are the bottom of the nanotube after removing the formed nanotube, FIG. 7 (a-2 to) d-2) shows the alloy surface of the portion from which the nanotubes are removed, and FIGS. 7 (a-3 to d-3) show cross-sectional photographs of the nanotubes, respectively.

It can be seen that nanotube growth can be affected by adding alloying elements to titanium. Titanium oxide mainly grows as long nanotubes, whereas niobium oxide nanotubes and hafnium nanotubes have an irregular double structure due to the difference in dissolution rate in a fluorine-containing solution. Confirmation of the double structure of the nanotube can be confirmed from the bottom of the nanotube surface and after the nanotube is removed.

Table 4 shows the size of the nanotubes, the distance between the nanotubes, and the length of the nanotubes, respectively.

[Table 4]

7 (a-1) and (a-2) show that when the bottom of the nanotubes formed in the Ti-40Nb-0Hf alloy and the surface of the alloy from which the nanotubes are removed are observed, the arrangement of the nanotubes is not aligned. , it was confirmed that large nanotubes and small nanotubes were formed. 7 (b-1 to d-1) and (b-2 to d-2) show that the bottom of the nanotubes and the nanotubes formed in the alloy in which the Hf content is increased to 3, 7, and 15 wt%, respectively, are removed. When the surface of the alloy was observed, it was found that the size of the large nanotubes became smaller and the arrangement of the nanotubes was aligned. As the nanotubes were aligned, the distance between the nanotubes became closer.

8 is a graph showing changes in the thickness and size of nanotubes as the Hf content increases. Figure 8 (a) shows the distance between the nanotubes, (b) shows the size change of the nanotubes. The thickness of the Ti-40Nb alloy nanotube without Hf is 2.24 ± 0.17 μm, the specimen with 3Hf is 2.80 ± 0.09 μm, the sample with 7Hf is 3.00 ± 0.07 μm, and the specimen with 15Hf is 3.19 ± 0.11 μm was measured. As the Hf content was increased, it was confirmed that the thickness of the nanotube increased, affecting the growth.

9 is a photograph of observing a bamboo knob on the surface of a column of a nanotube when the cross-section of the nanotube is observed.

As listed in Table 5 below, it was found that the number and size of bamboo knobs were affected by Hf.

[Table 5]

According to the previous report, nanotube formation depends on the oxide film, but the elution rate is different in the oxide film composed of TiO ₂ and the film composed of Ta ₂ O ₅ , ZrO ₂ , Nb ₂ O ₅ and HfO ₂ is believed to have influenced

10 is an X-ray diffraction peak image of the nanotubes formed on the alloy surface. To analyze the coated phase, it was analyzed (PCPDFWIN, ICDD) in the range of 10° to 90°, and peaks of TiO ₂ (200) plane and Nb ₂ O ₅ (110) plane were detected at 38.63° orientation, and at 55.92° orientation. In the TiO ₂ (221) plane, Nb ₂ O ₅ (200) plane _, HfO ₂ (200) plane peaks were detected, and it was found that the TiO ₂ (123) plane peak was detected in the 69.70 ° orientation. When the Hf content was increased, the peaks of TiO _{2 ,} Nb ₂ O ₅ and HfO ₂ at 38°, 55°, and 69° were observed to increase.

As reported in the previous study, elements such as Nb and Hf contribute to the formation of the oxide film, and when the oxide film is eluted by fluoride ions, it is believed that it contributed to influencing the size of the nanotube layer by varying the elution rate.

Experimental Example 4 (HA and HA/Zn coating using sputtering after nanotube formation of Ti-Nb-Hf alloy)

11 is a photograph showing a process of coating HA and Zn on a specimen using RF and DC sputter, showing plasma light sources of (a) RF-sputter HA, and (b) RF and DC-sputter HA/Zn. have. The HA plasma light source showed white light, and the Zn plasma light source showed blue light. From this photograph, it was found that the plasma light was stably formed and the coating was well performed.

12 is an observation of the surface with a scanning electron microscope after HA coating using RF-sputter on the surface after formation of nanotubes. 12 (a, a-1, a-2) is Ti-40Nb-0Hf, (b, b-1, b-2) is Ti-40Nb-3Hf, (c, c-1, c-2) is Ti-40Nb-7Hf, and (d, d-1, d-2) are Ti-40Nb-15Hf. The HA coating was applied to the surface of the alloy using an RF-sputter at 50W voltage for 1 hour. As a result of observing the surface of the nanotube with a scanning electron microscope, it was confirmed that HA was accumulated on the surface of the nanotube and between the nanotubes. When the Hf content increases, the nanotubes are aligned, the pores of the nanotubes are reduced, and HA is easily nucleated and grown on the surface of the nanotubes, and the coating materials are agglomerated and coated on the surface.

13 and 14, the distribution of Ca and P elements was confirmed through EDS-mapping of the surface and cross-section of the HA-coated specimen using RF-sputter. 13 and 14, (a) is Ti-40Nb-0Hf, (b) is Ti-40Nb-3Hf, (c) is Ti-40Nb-7Hf, and (d) is Ti-40Nb-15Hf. Ca and P were mainly detected on the surface, and it was found that Ca and P elements were also distributed in the cross section.

Table 6 below shows Ca and P components by EDS analysis of the HA-coated alloy surface.

[Table 6]

As a result, it was found that Ca and P elements were uniformly coated on the surface of the nanotube using RF-sputter. The HA coating promotes biobonding on the surface and is expected to promote bone formation on the implant surface.

15 is a HA/Zn composite coating on the surface after formation of nanotubes using RF and DC-sputter, and then the surface was observed with a scanning electron microscope. 15 (a, a-1, a-2) is Ti-40Nb-0Hf, (b, b-1, b-2) is Ti-40Nb-3Hf, (c, c-1, c-2) is Ti-40Nb-7Hf, and (d, d-1, d-2) are Ti-40Nb-15Hf.

HA coating was coated on the surface of the alloy at 50W voltage for 1 hour using RF-sputter, and Zn coating was coated on the alloy surface at 100W voltage for 20 minutes using DC-sputter. As a result of observing the surface of the coated nanotubes with a scanning electron microscope, when compared to the surface of the HA-coated specimen, the coating pattern was higher in the case of coating Zn and HA than in the case of coating only HA. It shows that the material is formed on the surface. Also, when the cross-section was observed, it was found that a large amount of HA and Zn coating materials were distributed on the surface of the small nanotube in the coating layer structure of the nanotube. This is because when the content of Hf increases, the distance of the nanotube is narrowed and the size of the pores is reduced, so that HA and Zn cover the surface and grow by nucleation on the surface, and the grown coating material aggregates with each other and spreads over the entire surface. It is believed that the coating was made.

16 and 17 show the distribution of Ca, P and Zn elements through EDS-mapping of the surface and cross-section of the specimen coated with HA and Zn using RF and DC-sputter. 16 and 17, (a) is Ti-40Nb-0Hf, (b) is Ti-40Nb-3Hf, (c) is Ti-40Nb-7Hf, and (d) is Ti-40Nb-15Hf.

It was found that mainly Ca, P and Zn were distributed on the surface and cross-section.

Table 7 below shows the results of confirming Ca, P, and Zn ion components through EDS analysis of the HA/Zn-coated alloy surface.

[Table 7]

As a result, it was found that Ca, P, and Zn ions were uniformly coated on the alloy using RF and DC-sputter. It is believed that HA and Zn coated on the surface and cross section of the nanotube stimulate osteoblasts to promote bone growth, thereby affecting osseointegration.

18 is an X-ray diffraction peak image of a specimen coated with HA and HA/Zn using RF-sputter, RF, and DC-sputter on a Ti-40Nb-xHf alloy surface formed with nanotubes. 18 (A) is the HA-coated specimen, (B) is the peak of the HA/Zn-coated specimen, (a) Ti-40Nb-0Hf, (b) Ti-40Nb-3Hf, (c) Ti-40Nb- 7Hf, (d) Ti-40Nb-15Hf.

The phase of the sputter-coated specimen was analyzed in the range of 10° to 90°, TiO ₂ peak was detected at 38.54° orientation, TiO ₂ (221) plane, Nb ₂ O ₅ (200) plane _, HfO ₂ at 55.64° orientation A peak was detected on the (200) plane, and it was confirmed that the TiO ₂ peak was detected in the 70.24° orientation.

19 shows X-rays after heat treatment of a specimen coated with HA and HA/Zn with RF-sputter and DC-sputter for one hour at 500° C. because no HA peak was detected in the thin film of the specimen analyzed in FIG. Diffraction analysis was performed. After heat treatment, HA phases were grown on the (201) plane at 24.91° orientation, (132) plane at 47.23° orientation, and (502) plane at 62.06° orientation on the surface of the specimen after heat treatment. After heat treatment, the HA peak phase increased. This is because the amorphous HA coating layer exhibits a high dissolution rate when in contact with body fluids, and post heat treatment can provide energy to form the crystalline HA layer. The crystallization of the HA surface will release Ca and P from the coated surface and will affect the bioactivity between the bone and dental implant interface for clinical use.

Experimental Example 5 (Wettability test result of Ti-Nb-Hf alloy according to Pyoman treatment)

20 shows the wettability test results of a specimen coated with HA and Zn using magnetron sputtering after forming nanotubes on the alloy surface. 20 (a-d) is a specimen etched after micro-polishing, FIG. 20 (a-1 to d-1) is a specimen in which nanotubes are formed in Ti-40Nb-xHf alloy, FIG. 20 (a-2 to d-2) is a specimen coated with HA after formation of nanotubes, and FIG. 20 (a-3 to d-4) shows the droplet contact angle values of specimens coated with HA and Zn after formation of nanotubes, respectively.

As shown in Table 8 below, the contact angle increased as the Hf content increased.

[Table 8]

As can be seen from FIG. 7, the pore size of the nanotubes decreased as the Hf content was increased to 3, 7, and 15 wt%, respectively, and as the nanotubes were aligned, the distance between the nanotubes became closer, which affected the wettability. is presumed to be

In addition, the coated specimen after the formation of the nanotubes showed a higher contact angle than the specimen in which only the nanotubes were formed. It is thought that increasing the Hf content decreases the pore size of the nanotubes, causing the HA and Zn coatings to aggregate between the nanotube surface and the nanotube, resulting in a higher contact angle of the water droplet. The contact angle is important for predicting cell proliferation and biocompatibility. Specimens in which nanotubes were formed showed lower contact angles than specimens without nanotubes. This contact angle can predict good biocompatibility as it shows much higher wetting compared to the polished titanium alloy surface.

Experimental Example 6 (electrochemical corrosion test of Ti-Nb-Hf alloy)

In order to quantitatively evaluate the corrosion properties of the test alloy through an electrochemical method, a potential test was conducted. The specimen was wet-polished to 100-2000 grit using SiC abrasive paper, and then finely polished to 1.0 μm using Al ₂ O ₃ powder. To confirm the polarization behavior, an isotonic polarization test was performed in 0.9% NaCl electrolyte at 25°C±1 at a scanning rate of 1.67 mV/sec, and PARSTAT MC (Youngin AT, Korea) equipment was used.

Before analysis, the surface of each specimen was washed with ethanol and distilled water to remove contaminants. Using three electrodes, the working electrode is the specimen, the auxiliary electrode is a high-density carbon electrode, and the reference electrode is a saturated calomel electrode. , SCE) were used. The dynamic potential test was conducted in the range of -1500mV to 2000mV.

21 is a potentiodynamic polarization test (potentiodynamic) in 0.9% NaCl solution at 25±1° C. to investigate the electrochemical properties according to the Hf content after preparing a Ti-40Nb-xHf alloy and quenching it in water at 0° C. after homogenization treatment. ) is the result of

As a result of the graph observation, it was found that all specimens formed a stable passivation film. Table 9 below shows the values of corrosion potential (E _corr ), corrosion current density (I _corr ), and current density (I _{300 mV} ) at 300 mV.

[Table 9]

The E _corr value of Ti-40Nb-0Hf was -468.458 mV, and the I _corr value was 25.09×10 ^-9 A/cm 2 . Among the specimens to which the Hf element was added, the Ti-40Nb-7Hf alloy had an E _corr of -229.478 mV, and an I _corr value of 68.93×10 ^-9 A/cm 2 . In general, the lower the E _corr value, the greater the oxidation tendency and the _faster the corrosion occurs. That is, the higher the E _corr value and the lower the I _corr value, the better the corrosion resistance.

The specimen to which Hf was added showed a higher overall corrosion potential (E _corr ) than the binary alloy Ti-40Nb, and the corrosion current density (I _corr ) value was lower in the alloy to which Hf was added.

E _corr and I _corr values were changed according to the Hf content in Ti-40Nb-xHf alloy, and corrosion resistance showed a tendency to increase. This increased the influence of the oxide film formed on the surface, and it is thought to be due to the formation of the Hf oxide film as Hf increases in particular.

That is, it can be confirmed from the result that the polarization curve shifted to the left as the Hf content increased. Therefore, the Hf content increased the corrosion resistance, and this surface is considered to be helpful in improving osseointegration.

22 is a co-potential polarization test was performed in 0.9% NaCl electrolyte at 25±1° C. to investigate the electrochemical properties after the formation of nanotubes in Ti-40Nb-xHf alloy. A passivation film was formed in all specimens to show a passivation region, and the E _corr value of Ti-40Nb-0Hf shown in Table 9 was -891.912 mV, and the I _corr value was 4.107×10 ^-6 A/cm 2 , and Ti- The E _corr value of 40Nb-7Hf was -650.448 mV, and the I _corr value was 786.535×10 ^-9 A/cm 2 .

In the case of the polarization curve of the surface on which the nanotubes were formed, it was found that the film was no longer destroyed by maintaining a constant current density with the formation of a passivation film from -500 mV to 1500 mV. The surface on which the nanotubes were formed showed a lower corrosion potential compared to the surface of the bulk. It is considered that the corrosion potential is lowered by the pores generated on the surface on which the nanotubes are formed. In the process of nanotube formation, nanotubes are formed on oxide films such as TiO ₂ , Nb ₂ O ₅ , and HfO ₂ , and it is thought that these oxide films affect the corrosion behavior.

Also, due to the formation of nanotubes, it is considered that the corrosion resistance is further increased as it has a lower current density than that of the bulk surface.

23 shows a co-potential polarization test in 0.9% NaCl electrolyte at 25±1° C. in order to investigate the electrochemical properties of the HA-coated specimens using RF-sputter after the formation of nanotubes on the surface.

As for the corrosion potential and current density of the HA-coated specimen, the E _corr value of Ti-40Nb-0Hf was -678.544 mV, and the I _corr value was 77.304×10 ^-6 A/cm 2 . Among the specimens to which the Hf element was added, the Ti-40Nb-7Hf alloy had an E _corr of -456.943 mV, and an I _corr value of 11.065×10 ^-6 A/cm 2 .

It was found that the corrosion potential value was higher than that of the specimen in which the nanotubes were formed on the surface. When the Hf content is increased, the pore size of the nanotubes is reduced, and the HA coating material is accumulated on the surface, and the HA layer acts as a barrier to the transfer of electrons and ions between the substrate and the electrolyte, thereby reducing the electrochemical reaction rate. However, when the potential increases, the corrosion resistance is greatly reduced, which is thought to be due to the elution of the coating film formed on the surface, resulting in a significant increase in the current density in the passivation film region. That is, RF-sputter coated HA is piled up on the surface of the nanotube, and it is thought that the HA coating material is dissolved before the nanotube.

24 is a co-potential polarization test in 0.9% NaCl electrolyte to investigate the electrochemical properties of HA and Zn-coated specimens using RF-sputter and DC-sputter after formation of nanotubes on the surface.

As for the corrosion potential and current density of the HA/Zn coated specimen, the E _corr value of Ti-40Nb-0Hf was -551.596 mV, and the I _corr value was 161.772×10 ^-6 A/cm 2 . Among the specimens to which the Hf element was added, the Ti-40Nb-7Hf alloy had an E _corr value of -320.769 mV and an I _corr value of 6.439×10 ^-6 A/cm 2 . It was found that the corrosion potential value was higher than that of the specimen in which the nanotubes were formed on the alloy surface.

This is thought to be because the site where the electrochemical reaction can occur is removed by the coating material reducing the pores formed in the nanotubes. The same trend was shown in Fig. 23, which is that when the HA and HA/Zn materials sputter-coated on the nanotube surface are attacked by the HA layer from chloride ions in the electrolyte, the dissolution of HA and Zn from the metal substrate increases in the passivation film region. It is considered that the current density increased significantly. If HA and Zn coating are applied to the implant surface using sputter, the coating material is formed on the surface of the nanotube, which is thought to induce bone bonding with the bone.

As described above, according to the manufacturing method and dental implant of the HA coating type dental implant using the titanium-based alloy according to the present invention, since the Ti-Nb-Hf alloy is used, the conventional Ti-6Al-4V alloy is used. In comparison, it has the effect of lowering the modulus of elasticity 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 elemental calcium and elemental phosphorus on the surface of the titanium-based alloy, thereby inducing bonding with bone, and adhesion of bone cells and bone bonding. It has the advantage of promoting growth and improving biocompatibility.

In addition, an anodic oxidation treatment was performed to form a nanotube array layer on the surface of the titanium-based alloy, and then, an HA/Zn composite layer containing HA and Zn ions was formed on the surface of the nanotube array layer using RF-magnetron sputtering. By forming it, it has the advantage of increasing corrosion resistance and improving biocompatibility.

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)

A titanium-based alloy preparation step of preparing a titanium-based alloy;
a nanotube array layer forming step of anodizing the prepared titanium-based alloy to form a nanotube array layer;
HA coating layer forming step of forming an HA (hydroxyapatite) coating layer on the surface of the titanium-based alloy on which the nanotube array layer is formed;
The titanium-based alloy is a method of manufacturing an HA-coated dental implant using a titanium-based alloy, characterized in that Ti-40Nb-15Hf.
delete delete The method of claim 1,
In the nanotube array layer forming step,
The titanium-based alloy is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and an oxide film layer having a nanotube structure is formed using an electrolyte solution containing H ₃ PO ₄ and NaF. A method of manufacturing an HA-coated dental implant using an alloy.
5. The method of claim 4,
The electrolyte solution is 1M H ₃ PO ₄ A method of manufacturing an HA-coated dental implant using a titanium-based alloy, characterized in that it contains NaF of 0.8 wt %.
The method of claim 1,
The HA coating layer forming step is
A method of manufacturing an HA-coated dental implant using a titanium-based alloy, characterized in that the HA coating layer is formed by RF-magnetron sputtering.
The method of claim 1,
The HA coating layer forming step is
A method of manufacturing an HA-coated dental implant using a titanium-based alloy, characterized in that a HA/Zn composite layer containing HA and Zn ions is formed by RF-magnetron sputtering and DC-magnetron sputtering.
The method of claim 1,
After the nanotube array layer forming step,
A drying step of washing the titanium-based alloy with the nanotube array layer formed thereon with ethanol and distilled water and then drying; is performed, and the HA coating layer forming step is performed. manufacturing method.
A dental implant, characterized in that it is manufactured by the method for manufacturing an HA-coated dental implant using the titanium-based alloy according to any one of claims 1 to 8.
10. The method of claim 9,
Dental implant, characterized in that the nanotube array layer is formed on the surface of the dental implant.
11. The method of claim 10,
Dental implant, characterized in that the HA coating layer is formed on the surface of the nanotube array layer.
11. The method of claim 10,
Dental implant, characterized in that the HA / Zn composite layer comprising HA and Zn ions is formed on the surface of the nanotube array layer.

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