KR20180106886A - An electrolyte composition containing manganese and silicon in a plasma electrolytic oxidation process and a method for manufacturing dental implants coated by hydroxyapatite containing manganese and silicon ions using the composition - Google Patents

Abstract

The present invention relates to an implant manufacturing method capable of improving bioactivity by forming the surface of a porous oxide film through plasma electrolytic oxidation. The method includes: a titanium alloy preparation step of sequentially polishing, fine-polishing, and cleaning a dental titanium alloy with ultrasonic waves; an injecting step of installing the prepared titanium alloy on the positive pole of an electrolysis chamber and installing platinum on the negative pole thereof, and then, injecting an electrolyte solution; a plasma forming step of forming an oxide film on the titanium alloy by generating plasma by applying constant voltage and current density; and a drying step of washing the oxide film, which has been formed on the titanium alloy through the plasma forming step, with ethanol and distilled water, and then, drying the same.

Description

TECHNICAL FIELD The present invention relates to an electrolytic composition containing manganese and silicon in a plasma electrolytic oxidation process, and a method for producing dental implants coated with apatite hydroxide containing manganese and silicon ions using the composition. oxidation process and a method for manufacturing dental implants containing hydroxyapatite containing manganese and silicon ions using the composition}

The present invention relates to a method for forming a porous surface containing calcium ions and phosphorus, which are components of bone, including manganese ions by using plasma oxidation method (Plasma Electrolytic Oxidation), which is anodic oxidation method, on a surface of a dental implant. More specifically, The surface of the porous oxide film containing manganese and silicon ions and calcium and phosphorus on the surface of the dental implants is removed by using an electrolytic solution containing manganese and silicon, The present invention relates to a method for manufacturing an implant that is formed by a plasma electrolytic oxidation method and improved in biological activity. The process comprises the steps of preparing a titanium alloy for sequentially polishing, fine polishing and ultrasonic cleaning the dental titanium alloy, And the anode is platinum, and then the cathode A plasma forming step of forming a plasma on the titanium alloy by applying a constant voltage and a current density to form an oxide film on the titanium alloy, and an oxidation film formed on the titanium alloy in the plasma forming step, followed by washing with ethanol and distilled water, The present invention relates to an electrolytic composition containing manganese and silicon, and a method for producing dental implants coated with apatite containing manganese and silicon ions by using the composition and a composition thereof in a plasma electrolytic oxidation process including a drying step.

The dental implants are subjected to various surface treatments to improve the bone conformity of the implants after mechanical machining of the titanium-based alloys. The surface treatment methods include a corrosion surface using an acid, a plasma sputtering method using titanium and hydroxyapatite, Porous sintering, and anodic oxidation. The anodic oxidation method is characterized in that osteoblast adhesion and osteogenesis are promoted. In the case of dental implants, surface treatment using anodic oxidation method is preferred.

In more detail, the majority of commercially available implants have high biocompatibility and are believed to have a surface suitable for healing, producing and maintaining bone, but still can not completely overcome the adverse bone condition. On the other hand, the titanium-based alloy used as the main material has been reported to be superior to the conventional bio-metals such as low elasticity and excellent biocompatibility and corrosion resistance. However, since it is in vivo inert, it does not directly induce bone formation, takes a long time for treatment to achieve bone connection, and the naturally formed oxide film has a thin thickness, which leads to rapid dissolution and does not lead to regeneration of adjacent bone tissue .

Therefore, in order to solve the above-mentioned problem that the implant can not directly bond with the bone, and to relax the shortening period to shorten the period of bone connection, bioactivity is given through the implant surface treatment. By physically and chemically surface-treating the surface of the titanium used as the main material of the implant, the bioactivity is further improved to shorten the period of healing after the implant is placed in the human body. Studies for more effective surface treatment are continuously carried out In fact. The chemical surface treatment during the titanium surface treatment includes anodizing, sol-gel, plasma spraying, chemical vapor deposition (CVD), and plasma-electrolytic oxidation (PEO-Plasma Electrolytic Oxidation) .

The anodizing method is a method of forming oxide and metal salts relatively thick on a metal surface using an external power source, and a metal to be an oxide layer is formed on the anode and another insoluble metal is brought into contact with the cathode to generate an electric current If an electric current is applied to anodize by flowing, the hydroxide of the metal forms a fine film at a very low voltage, and when a voltage of about 10 V is applied, a metal oxide layer is formed. However, once the oxide layer is formed, resistance is increased, internal stress is concentrated in the metal oxide layer, the oxide layer is destroyed at 70 V, and when the voltage is raised again, a second porous oxide layer is formed. The electric efficiency is poor due to the formation of the oxide layer by applying electricity, and the sparked localized portions are subject to thermal stress, which not only adversely affects the physical properties of titanium, but also adversely affect the final properties.

The sol-gel method is a method of preparing a solution which becomes a gel by hydrolysis and polymerization reaction with alcohol, water and acid in order to prepare a coating film, and a homogeneous solution is prepared in a relatively low viscosity state The wet coating method, such as dip-coating, which applies the sol-gel method by coating on the substrate by gelling on the substrate, is a low-temperature process and can be coated regardless of the area, and the thickness and microstructure of the film can be controlled However, there is a disadvantage in that a post heat treatment process for crystallization is added, formation of a flat plate coating is restricted, and an adhesive for strengthening the adhesion strength is inserted into the intermediate layer so that the coating has a sufficient bonding force with the base material.

Plasma spraying refers to a process in which a material having a high melting point, such as a metal and a non-metallic ceramic material, is deposited on a substrate in a molten state or a semi-molten state. There is no restriction on the material and the size of the base material, it is possible to construct on the spot without causing deformation of the base material, it is possible to form a thick film, easy to control the thickness of the coating, and various kinds of coating materials. Is 0.6 to 15%. It is not a metallic bond, but it has a disadvantage that it is weak against impact when titanium is coated with a ceramic by a mechanical bond, and it is difficult to apply an implant because its bonding with a base material is weak.

The chemical vapor deposition (CVD) method is a method of treating a surface by exposing a gas mixture to a sample at a high temperature, so that various reactions occur to deposit one or more components of the gas mixture in the base material, Method. Is a method commonly used in the field of biomaterials for depositing pyrolytic carbon coatings on substrates such as tantalum, molybdenum, rhenium or graphite.

Plasma electrolytic oxidation is principally the same as anodizing. The anodic oxidation is performed by using a metal (e.g., a sintered steel or a platinum alloy) having a relatively high electrochemical stability with respect to the cathode, The metal to be oxidized, such as magnesium, is placed in the anode. In the plasma electrolytic oxidation process, when a voltage higher than a dielectric breakdown voltage is applied to the pre-formed anodic oxide layer (or dielectric film), a strong current field formed locally in the reacted gas (hydrogen or oxygen gas) An arc (or spark or plasma) is generated. These plasma energy plays a role of fusing momentarily formed oxides, and the surface of the metal located on the anode is formed by a very dense and hard oxide which is completely different from the oxide formed by the anodic oxide film. It is a surface treatment technology applied to a wide range of fields ranging from marine and petrochemical industries. It forms CaO and PO ₄ ions in the electrolyte to form an oxide film that induces the bonding of bone to the metal surface inserted into the bone in the human body By improving the bioactivity, the biocompatibility is improved while being economical. However, problems such as shortening of treatment time due to problems such as failure to bring about regeneration of adjacent bone tissue and disadvantages such as rapid disappearance of oxide film, which are possessed in the prior art, have been partially improved, and still have problems.

Prior art for surface treatment of implants by plasma electrolytic oxidation process is disclosed in Korean Patent No. 10-1314073 (Oct. 31, 2013). A method for manufacturing a titanium implant coated with an oxide film containing calcium triphosphate and a titanium implant A method for manufacturing a titanium implant for bone implant coated with an oxide film containing calcium phosphate, which is a biocompatible material, comprises the steps of: preparing an electrolyte solution containing phosphate ions; Dispersing the hydroxyapatite particles in the electrolytic solution; And performing a plasma electrolytic oxidation coating on the electrolyte in which the hydroxyapatite particles are dispersed with a titanium implant as an anode. In the course of performing the plasma electrolytic oxidation coating, the phosphoric acid ions of the electrolyte react with hydroxyapatite The method for forming a coating by plasma electrolytic oxidation is a method in which calcium triethoxide formed is contained in an oxide film and a titanium implant is provided. Korean Patent No. 10-1419276 (Apr. 14, 2014) A voltage higher than a voltage applied during a subsequent process is applied at an initial stage of the plasma electrolysis oxidation process and a positive voltage pulse is applied at a voltage applied to the positive electrode and the negative electrode in the plasma electrolytic oxidation chamber, And the ratio of the number of times between the negative voltage pulse The present invention provides a method for forming a coating by plasma electrolytic oxidation applied at a rate of 1: 1 to 2: 1 initially in a zmaic electrolytic oxidation process and at a rate of 30: 1 to 50: 1 after the middle of the process, (A) an electrolytic bath containing phosphoric acid dihydrate potassium (KH ₂ PO ₄ ) and calcium chloride (CaCl ₂ ); and Forming an electrolyte with a mixed aqueous solution; (b) impregnating the electrolytic bath with titanium or titanium for an anode and a metal for a cathode having a reduction potential higher than that of the titanium metal; (c) applying a constant current and voltage to the titanium metal and the cathode metal to generate an arc discharge on the titanium metal to generate a plasma; (d) forming hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ) on the surface of the titanium metal with ionic materials within the electrolytic cell using the plasma; (e) placing zirconium chloride (ZrCl ₄ ) and titanium metal coated with hydroxyapatite on its surface through the step (d); And (f) heating the inside of the reaction vessel to vaporize the zirconium chloride in a constant gas atmosphere to form a hydroxyapatite / zirconium oxide composite on the surface of the titanium metal.

Surface treatments of commercially available dental implants are commercially available in which micro roughness is imparted to the surface using alumina powder or hydroxyapatite powder and micro roughness is imparted by pretreatment with hydrochloric acid and sulfuric acid solution. The above prior art and commercially available products are characterized in that an oxide film is formed on the surface of a titanium alloy and potassium triphosphate, potassium phosphate (KH ₂ PO ₄ ) and calcium chloride (CaCl ₂ ) are added to the electrolyte solution used in the plasma electrolytic oxidation process. And changes the voltage and current density. Thus, a porous surface on which an oxide film is formed on the surface of an implant made of a titanium-based alloy is formed to improve bioactivity, thereby inducing bone cell adhesion and bone- And it is a fact that the elements included in the electrolytic solution and the prior art are lacking in biocompatibility.

Korean Patent No. 10-1314073 (Oct. Korean Patent No. 10-1419276 (Jul. 15, 2014) Korean Patent No. 10-1081687 (2011.11.09.)

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method and apparatus for etching an implant using an acid, which has a possibility of causing an inflammation reaction and corrosion of an implant surface due to an acid remaining on the surface, It is a commonly used method for coating bioceramics commercially on the implant. However, it has a disadvantage that the amount of osseointegration is small, and these problems appear to be a bad result of future implantation failure. Therefore, in the plasma electrolytic oxidation process aiming at increasing the initial fixation and reducing the failure rate in the clinic through the provision of the oxide film by using the ions favorable to bone formation in the titanium based bio-alloy used as the implant material, the electrolyte composition containing manganese and silicon And a method for producing dental implants coated with hydroxyapatite containing manganese and silicon ions using the composition.

In order to solve the above-mentioned problems and to achieve the object, in the plasma electrolytic oxidation process according to an embodiment of the present invention, the electrolyte composition containing manganese and silicon contains calcium acetate monohydrate, calcium glycerophosphate ), Manganese acetate, sodium metasilicate nonahydrate, and distilled water to form an electrolyte solution.

The electrolytic solution was prepared by dissolving 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerophosphate, 0.02 mol L ^{-1 of} manganese ion, 20 mol% of calcium ion, and 5 mol% TKO provides needs 0.03mol L ^-1 and sodium metasilicate 0.001mol L ^-1 plasma electrolytic damaged and needs containing silicon oxide in the process electrolyte composition comprising a.

 Also, a method for preparing dental implants coated with apatite hydroxide containing manganese and silicon ions using the electrolyte composition comprises: a) a titanium alloy preparation step (S10) of sequentially polishing, fine polishing and ultrasonic washing the dental titanium alloy; ); b) an inputting step (S20) of installing the titanium alloy prepared in the preparation step on the anode of the electrolysis bath, placing the anode on the platinum, and then injecting the electrolytic solution containing manganese and silicon; c) forming a plasma by applying a constant voltage and current density to form an oxide film on the titanium alloy; And d) a drying step (S40) in which an oxide film is formed on the titanium alloy in the plasma forming step, followed by washing with ethanol and distilled water, followed by drying.

The polishing is carried out with a silicon carbide abrasive paper, and is polished stepwise with an abrasive paper having 100, 600, 800, 1200, 2000 grit.

The fine grinding is performed using 0.3 mu m alumina powder, and the alumina powder is removed in the ultrasonic cleaning.

The electrolyte solution is prepared by mixing calcium acetate monohydrate, calcium glycerophosphate, manganese acetate, and sodium metasilicate nonahydrate in distilled water.

0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerophosphate, and 0.02 mol L ^{-1 of} manganese ion in the electrolyte solution so that the concentration of manganese ion is 20 mol% relative to calcium ion and 5 mol% 0.03 mol L ^{-1 of} manganese and 0.001 mol L ^-1 of sodium metasilicate.

The voltage, the current density and the usable time are 250 to 280 V, 50 to 100 mA / cm & lt ^; " ² & gt ^; for 3 minutes, and coated with apatite containing manganese and silicon ions.

As described above, in the plasma electrolytic oxidation process according to the present invention, an electrolytic composition containing manganese and silicon and a method for producing dental implants coated with apatite containing manganese and silicon ions using the composition and the composition thereof, It has the same effect.

(1) According to the present invention, the surface of a dental implant is treated with a titanium-based bio-alloy using a plasma electrolytic oxidation process, thereby simplifying the manufacturing process and reducing the manufacturing time and the duration of the implant.

(2) According to the present invention, a biocompatible porous oxide film is formed by a complex substitution of manganese and silicon ions by a plasma electrolytic oxidation method, and an oxide film thicker and denser than conventional metal oxide films is produced.

(3) The present invention rapidly increases biocompatibility including manganese and silicon ion bioactive materials, thereby increasing the initial fixing power of dental implants and reducing the treatment period.

(4) The present invention remarkably reduces manufacturing time and manufacturing cost by reducing the manufacturing process and the treatment period.

1 is a flowchart of a method of manufacturing a dental implant coated with apatite hydroxide containing manganese and silicon ions by a plasma electrolytic oxidation process according to a preferred embodiment of the present invention.
FIG. 2 is a basic reaction diagram of a plasma electrolytic oxidation surface treatment according to a preferred embodiment of the present invention.
3 is a photograph of a titanium alloy surface treated by plasma electrolytic oxidation in a solution containing manganese and silicon ions according to a preferred embodiment of the present invention.
FIG. 4 is a graph of an EDS (Energy Dispersive X-ray Spectroscopy) result of a titanium alloy subjected to plasma electrolytic oxidation according to a preferred embodiment of the present invention.
FIG. 5 is an actual EDS mapping view of a titanium alloy subjected to plasma electrolytic oxidation according to a preferred embodiment of the present invention.
FIG. 6 is a biostability test result for evaluating the degree of elution of metal ions by plasma electrolytic oxidation according to a preferred embodiment of the present invention.
FIG. 7 is an apatite real image generated on the surface of a titanium alloy subjected to plasma electrolytic oxidation according to a preferred embodiment of the present invention after immersing the titanium alloy in a bio-similar solution for 12 hours.

The name of the present invention is an electrolytic composition containing manganese and silicon in a plasma electrolytic oxidation process and a method for producing a dental implant coated with apatite containing manganese and silicon ions using the composition and a conventional technique For the sake of easy understanding, the specific contents are described, and the detailed description which can sufficiently be deduced is omitted, and the examples and drawings are described, if necessary. In addition, terms defined in the present specification and claims are not to be interpreted as limiting, and may be changed according to the intention or custom of the operator, and should be construed in a meaning and a concept consistent with the technical idea of the present invention.

In one aspect of the present invention,

FIG. 1 is a flow chart of a method of manufacturing a dental implant in which apatite hydroxide coated with manganese and silicon ions is coated by a plasma electrolytic oxidation process according to a preferred embodiment of the present invention. FIG. 2 is a cross- , Which is a basic reaction diagram of the plasma electrolytic oxidation surface treatment according to the present invention, and will be described in more detail below with reference to FIG. 1 to FIG.

In the electrolytic composition of the plasma electrolytic oxidation process,

The electrolyte composition comprises

The electrolytic solution is made up of calcium acetate monohydrate, calcium glycerophosphate, manganese acetate, sodium metasilicate nonahydrate and distilled water.

The electrolytic solution was prepared by dissolving 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerophosphate, 0.02 mol L ^{-1 of} manganese ion, 20 mol% of calcium ion, and 5 mol% 0.03 mol L ^{-1 of} manganese and 0.001 mol L ^-1 of sodium metasilicate.

A method of manufacturing a dental implant comprising a titanium alloy,

The dental implant manufacturing method includes:

a) preparing a titanium alloy (S10) for sequentially polishing, fine polishing and ultrasonic cleaning the dental titanium alloy;

b) an inputting step (S20) of installing the titanium alloy prepared in the preparation step on the anode of the electrolysis bath, placing the anode on the platinum, and then injecting the electrolytic solution containing manganese and silicon;

c) forming a plasma by applying a constant voltage and current density to form an oxide film on the titanium alloy; And

d) forming an oxide film on the titanium alloy in the plasma forming step, followed by washing with ethanol and distilled water, followed by drying (S40).

Ti-6Al-4V and Ti-6Al-4V extra low interstitial (ELI) are widely used as the commonly used titanium, and titanium is an element constituting the crust and oxygen, silicon, aluminum, , Is the ninth most abundant element following sodium, potassium, and magnesium. Its density is 4.5 g / ㎤ which is 40% lighter than stainless steel (7.95 g / ㎤) and relatively low specific gravity. And the microstructure is composed of only HCP (alpha phase). The diameter of the crystal grains becomes 10 ~ 150 mu m according to the effect of cold working, and the material is strengthened by forming an interstitial solid solution.

The Ti-6Al-4V alloy is mixed with HCP (alpha phase) and BCC (beta phase), and the microstructure is largely affected by the heat effect and is also affected by the processing process. When the temperature is maintained at the above temperature, the α phase of the needle and plate is precipitated in a specific direction in the crystal of β, and this is called "Widmanstten" structure. When the β phase is quenched, martensite is formed. The ordinary Ti-6Al-4V is processed by heating at a temperature of about 882 ° C, which is the transformation temperature of the β phase. Annealing is performed to precipitate β-phase grains on a fine α phase matrix and grain boundaries. And low thermal conductivity and electrical conductivity, and α-Ti is transformed into β-Ti at a temperature of 882 ° C. However, high-temperature β-Ti can not bring the β-phase to room temperature by quenching, and it becomes an acicular α-Ti structure.

Titanium is currently the most widely used implant material because of its excellent mechanical properties and biocompatibility. Titanium is highly reactive and oxidizes when contacted with air or body fluids. This oxidation reaction increases the resistance of the corrosion reaction in the body, And it is preferable to use Ti-6Al-4V as the material of the titanium alloy of the present invention.

In the plasma electrolytic anodization process according to the present invention, a dense oxide film is initially formed on the surface of the metal, and a barrier layer is formed over time, and the porous surface layer is generated in proportion to the applied voltage and continues to grow. When the generation and destruction of the oxide film are repeatedly performed by the plasma discharge after the formation, localized high temperature heat is generated to cause a dissolving action on the surface. Such repetition of the reaction is stopped when the applied voltage stops and the surface roughness is increased, And the main reaction occurring in the anode during the plasma electrolytic oxidation process is as follows.

First, the reaction at the Ti / Ti oxide interface

Ti - > Ti < ^{2 +} & ^{gt ;} + 4e ^-

Second, it can be divided into two reactions at the Ti oxide / electrolyte interface. Oxygen ions react with Ti to form oxides, and an oxygen gas reaction formed on the electrode surface appears.

2H ₂ O → 2O ^{2 -} + 4H ⁺

2H ₂ O? O ₂ (gas) + 4H ⁺ + 4e ^-

Third, the final reaction

Ti ^{2 +} + 2O ^{2 -} > TiO ₂ + 2e ^-

When a voltage is applied to an aqueous solution containing an electrolyte in an electrolytic bath, oxygen gas is generated at the surface of the anode, oxidation reaction of the metal occurs, hydrogen gas is generated at the cathode, or reduction reaction occurs.

The manganese (Mn) is an indispensable element in animals and plants as an essential trace element of human. In manganese deficiency in green plants, the production of chlorophyll decreases and coexists with iron in animal tissues, Liver, pancreas and hair. When manganese is deficient, the amount of acidic mucopolysaccharide of cartilage is significantly lowered in guinea pig, and the egg hatching rate of chicken and the like is lowered, and the skeletal development is remarkably lowered in chick. It also participates in radical elimination by elements essential for normal skeletal growth and development and enzymes such as superoxide dismutase in the body. Thus, manganese ions are less toxic than aluminum and vanadium, and when doped into alloys, they increase the corrosion resistance and mechanical properties of biomaterials. Manganese is added to the tricalcium phosphate bioceramics to exhibit sufficient cell compatibility, and manganese is added to the titanium alloy to improve cell attachment properties.

The polishing is carried out with a silicon carbide abrasive paper, and is polished stepwise with an abrasive paper having 100, 600, 800, 1200, 2000 grit.

The fine polishing is performed using 0.3 mu m alumina powder. Ultrasonic cleaning is performed in ethyl alcohol for 10 minutes to remove the alumina powder. In this step, the electrolyte solution is applied before the positive electrode is installed, It is preferable to stir the mixture at 200 rpm and to dispose the anode and the cathode at a distance of 20 to 40 mm.

The electrolyte solution is prepared by mixing calcium acetate monohydrate, calcium glycerophosphate, manganese acetate, and sodium metasilicate nonahydrate in distilled water.

0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerophosphate, and 0.02 mol L ^{-1 of} manganese ion in the electrolyte solution so that the concentration of manganese ion is 20 mol% relative to calcium ion and 5 mol% 0.03 mol L ^{-1 of} manganese and 0.001 mol L ^-1 of sodium metasilicate.

The voltage, the current density and the usable time were 250 to 280 V, 50 to 100 mA / cm ^-2 and 3 minutes, and a separate cooling system was installed to maintain the internal temperature of the electrolytic bath at 25 ° C. It is preferable to dry it after forming an oxide film and then using warm air.

Example  : plasma  Manufacture of dental implants coated with hydroxyapatite containing manganese and silicon ions by an electrolytic oxidation process

Ti-6Al-4V disc (grade 5, Timet Co., Ltd., japan diameter: 10 mm, thickness: 3 mm) was used as the abrasive for silicon carbide abrasive paper and graded to 100, 600, 800, Polishing and micronizing with aluminum oxide (Al ₂ O ₃ ) having a particle size of 0.3 탆, ultrasonic cleaning was carried out, and manganese ions in the electrolytic solution were adjusted to 0, 5, 10 and 20 mol% relative to calcium ion, Ions such as calcium acetate monohydrate, calcium glycerophosphate, manganese acetate, and sodium metasilicate were prepared in the same manner as in the design shown in Table 1, metasilicate nonahydrate) was weighed and placed in a sterilized sterilized beaker at the third distilled water of the ultrapure water production apparatus. The above reagent was put in a distilled water and stirred at 200 rpm for 30 minutes using a magnetic bar in a stirrer to obtain a homogeneous solution It was prepared. The electrolytic solution is manufactured and filled in the electrolyzer, the installation of the specimens finished the ultrasonic cleaning of the anode, cathode electrolytic plasma after installing platinum by applying 280V, 70mA / ㎝ ^-2 3 minutes and subjected to oxidation treatment Respectively.

Furthermore, the dental implants made of the same material of titanium alloy were subjected to the oxidation treatment under the same conditions as those of the specimens subjected to the plasma electrolytic oxidation in the above example.

Test Example  1: Ca (Mg) / P ( Si ) Mol%  Surface porosity of specimen according to the ratio

The surface of the specimens and dental implants subjected to plasma electrolytic oxidation in the above example were measured by electron microscope, and the manganese ions were 5 mol%, 10 mol%, 20 mol%, and 5 mol%, respectively, We examined the pore state of the treated surface.

FIG. 3 is a detailed view of the surface of the titanium alloy subjected to the plasma electrolytic oxidation treatment in a solution containing manganese and silicon ions according to a preferred embodiment of the present invention, with reference to FIG. 3. FIG.

3 is a graph showing the results of plasma electrolytic oxidation in a solution containing manganese and silicon ions. The surface of a specimen was observed at an electron microscope image of 5,000 times. On the oxide film surface of manganese and silicon ions, , And showed smaller pore morphology with increasing concentration of manganese. Therefore, it was found that as the concentration of manganese ions (20Mg / 5Si) was increased, a lot of small pores were formed, and accordingly, it was found that a favorable condition for bone joining was obtained.

Test Example  2: plasma  EDS and EDS mapping of electrolytically oxidized titanium alloy specimens

Energy Dispersive X-ray Spectroscopy (EDS) is used as an additional equipment to the scanning electron microscope equipment. It collects the specific X-rays of the sample generated by the electron beam of the scanning electron microscope and analyzes the components. More specifically, when an electron beam is applied to a sample (a titanium-based alloy specimen subjected to a plasma electrolytic oxidation treatment in the embodiment), electrons in the atom absorb energy to become excited, and the excited electrons are stabilized again, Since the emitted X-rays have a unique energy value for each substance, X-rays are collected using a detector, and the collected X-rays are classified according to intensity to perform qualitative analysis on the samples.

 FIG. 4 is a graph of an EDS (Energy Dispersive X-ray Spectroscopy) of a titanium alloy subjected to a plasma electrolytic oxidation treatment according to a preferred embodiment of the present invention, and FIG. 5 is a graph showing the results of a plasma- Titanium alloy EDS mapping actual view, which will be described in more detail below with reference to Figs. 4 to 5.

FIG. 4 shows that the components used in the electrolytic solution are uniformly distributed as a result of the EDS analysis of the components of calcium, manganese, phosphorus and silicon ions on the surface of the titanium alloy oxide film, and FIG. As a result of observing the distribution of calcium, manganese, phosphorus and silicon ions on the surface of the specimen, it was confirmed that EDS mapping was also uniformly distributed throughout the surface of the titanium alloy through the plasma electrolytic process.

Test Example  3: plasma  the year before By oxidation  Biosafety due to the degree of elution of metal ions

FIG. 6 is a more detailed diagram illustrating the result of a biostabilization test for evaluating the degree of elution of metal ions by plasma electrolytic oxidation according to a preferred embodiment of the present invention.

The corrosion behavior of each specimen was evaluated by using potentiostat (Mdel PARSTAT 2273, EG & G, USA) at 36.5 ± 1 ° C, similar to the oral environment Of 0.9% NaCl. More specifically, the electrochemical corrosion behavior was examined by the prepared potentiodynamic method. The applied electric potential was applied at a scanning speed of 1.67 mV / min from -1500 mV to 2000 mV, and a body-like solution, 36.5 The test was performed in 0.9% NaCl solution at ± 1 ° C. From the polarization curves, the dissolution behavior of metal was investigated by the corrosion potential, the corrosion current density and the current density in the passivation region.

The values for surface coating were 0, 5, 10 and 20 mol% respectively (-470 ± 3.0) mV (-650 ± 5.0) mV, (-820 ± 4.0) mV and (-690 ± 2.0) , And the Ecorr value observed at a concentration of 10 mol% of manganese added to the oxide film was lowered, indicating that the corrosion potential was decreased with increasing manganese ion after the plasma electrolytic oxidation treatment.

It was also confirmed that the active sites of the voids contained chlorine ions from the solution and thus exhibited a low corrosion potential on the voided surfaces

Test Example  4: plasma  Electrolytically oxidized titanium alloy was added to the bio-similar solution Immersed  Apatite generated on the posterior surface

FIG. 7 is a graph showing the relationship between the thickness of a titanium alloy sample and the thickness of a simulated body (hereinafter abbreviated as " SBF ") of the titanium alloy sample prepared in Example 1, after immersing the titanium alloy subjected to the plasma electrolytic oxidation treatment according to a preferred embodiment of the present invention in a bio- fluid was prepared by immersing in apatite.

The biocompatible solution contained Na ⁺ (142.0 mM), K ⁺ (5.0 mM), Ca ²⁺ (2.5 mM), Cl ^- (103.0 mM), HCO ^{3 -} (10.0 mM), HPO ^{4 -} (1.0 mM) and SO ₄ ^2- (0.5 mM) were prepared and placed in a beaker in 200 ml increments. The samples were maintained at 36.5 ° C ± 1 ° C, pH 7.4, similar to the oral environment in an incubator, And observed after immersion.

As shown in FIG. 7, after observation for 12 hours, it was found that apatite was formed on the surface of manganese and silicon ions of the oxide film formed on the surface of the titanium alloy within a short time.

In a further aspect,

Silver nanoparticles may be added to the electrolyte solution to add silver ions to impart antimicrobial properties to the oxide film. The implant implants may have bacterial infections, which may result in periarticular inflammation in the implanted tissue, which is characterized by osseointegration loss at the site of osseointegration in the implanted implant and is known to be caused by excessive occlusal force or infection have. Implants can be divided into peri-implant mucositis and peri-implantitis, and peri-implantitis is characterized by edema, redness, and hemorrhage. peri-implntitis has a wider range of inflammatory symptoms, with loss of crater-like bone along with pyrogen.

On the other hand, if we look at the antimicrobial mechanism of silver ions due to the addition of silver nanoparticles, the cell membrane is composed of a bilayer of phospholipids. Since oxygen bonded to the phospholipids contains anions, the cell membrane has a characteristic of negative charge as a whole, The silver ions reach the cell membrane by diffusion, adsorbing to the cell membrane and destroying the cell structure. Silver ions adsorbed to proteins such as cell membranes and enzymes bind to the sulfhydryl group (-SH) of cysteine, a protein-forming amino acid, to convert it to sulfide and cause energy metabolism disorders by modification of protein enzymes. In addition, silver ions are directly ingested in microorganisms, and they bind with DNA, RNA, celluara protein, and resporatory enzyme to interfere with movement, growth and division, or cause metabolic disturbances in the cytoplasm of bacteria and inactivate them. It destroys cell walls or adsorbs silver ions on the cell membrane, causing the phospholipids of the cytoplasmic anions to migrate to one side, resulting in inactivation of microorganisms by loss of DNA replication ability.

0.03 mol L ^-1 of silver nanoparticles is further added to the electrolyte solution to plasma-electrolytically oxidize the titanium-based alloy to have antimicrobial activity on the surface, thereby enhancing the effect of osseointegration by manganese and silicon ions.

Further, in the present invention, the plasma electrolytic oxidation process is performed using the positive electrode or the three electrode using the DC voltage, but an AC voltage may be used. In this case, the AC voltage may use an asymmetrically pulsed voltage, Applying an asymmetric pulsed voltage can cause the positive portion of the pulse to form the converted surface and the oxide layer is formed and the surface converted at the initial stage of the layer growth process has a dense structure and the thickness of the oxide layer coating The thickness of the oxide film can be increased by performing the plasma oxidation process multiple times by changing the ratio of the current density given to the anode and the cathode, and increasing the porosity of the coating by increasing the porosity of the coating.

In addition, the attachment of osteoblasts to the implants depends on the surface characteristics of the implants. Chemical composition, surface energy, and surface morphology have an important influence on maturation as well as osteoblast attachment, The increase promotes early cell adhesion and expansion, thereby inducing a wider range of bone formation. In general, differences in surface chemical composition and surface energy may be due to differences in hydrophilicity, which acts as a moderate factor for early osteoblast attachment and differentiation. Accordingly, in order to increase the biocompatibility of the surface of the implant, ultraviolet rays, UV-ozone may be treated on the surface of the titanium alloy of the present invention which has been subjected to the plasma electrolytic oxidation treatment, or a step of irradiating a laser to add hydrophilicity to the surface of the implant have.

In order to treat ultraviolet rays and ultraviolet ray-ozone, an oxide film is formed after the plasma electrolytic oxidation process in the present invention, and ultraviolet rays or ultraviolet ray-ozone is applied to the surface of the titanium alloy after the drying step is finished, and the surface is treated for 5 minutes to hydrophilize the surface of the titanium alloy Or Er-Cr.YSGG laser, which is widely used recently, is used to increase the biocompatibility by using CO ₂ laser or Er-Cr.YSGG laser after completion of the drying step as above, It is preferable to set the energy to 100 to 120 mJ and the 20 Hz frequency for 2 minutes at the distance.

As described above, an oxide film containing manganese and silicon ions is formed on the surface of a titanium alloy dental implant by plasma electrolytic oxidation, and nanostructured porosity is imparted to provide a nanostructure with a large surface area, thereby being more advantageously applied to osseointegration The porous space formed on the surface is used as a pathway for transferring various chemical substances, drugs, and biomolecules that reach the protein level, and acts only in a specific region. Therefore, the porous space exhibits a large effect as a small-capacity drug, Systemic side effects can be reduced.

In addition, the surface of the dental implant is treated with a titanium-based bio-alloy by a plasma electrolytic oxidation process, thereby simplifying the manufacturing process and reducing the implant preparation time and treatment period. The plasma electrolytic oxidation method is effective for reducing manganese and silicon ions Biocompatible porous oxide films were produced by complex substitution. The oxide films were thicker and denser than conventional metal coral membranes, and biocompatibility including manganese and silicon ion bioactive materials was rapidly increased. Thus, the initial dental implants By increasing the fixing force, the treatment period is reduced, and the manufacturing process is simplified and the treatment period is shortened, thereby remarkably reducing the manufacturing time and the manufacturing cost.

The present invention relates to an electrolytic composition containing manganese and silicon in a plasma electrolytic oxidation process filed on March 21, 2017, and a method for manufacturing dental implants coated with apatite containing manganese and silicon ions (Korean Patent Application No. 10-2017-0035347), and filed a patent as a domestic priority claim of the present invention. The present invention improves on the technique of the invention by applying the electrolytic oxidation process by adding sodium metasilicate nonahydrate to the electrolyte composition in the cited patent application No. 10-2017-0035347.

While the present invention has been described in connection with certain exemplary embodiments and drawings, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible.

Claims (8)

In the electrolytic composition of the plasma electrolytic oxidation process,
The electrolyte composition comprises
Wherein the electrolytic solution includes an electrolyte solution including calcium acetate monohydrate, calcium glycerophosphate, manganese acetate, sodium metasilicate nonahydrate, and distilled water. Wherein the electrolyte composition comprises manganese and silicon. The method according to claim 1,
The electrolytic solution was prepared by dissolving 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerophosphate, 0.02 mol L ^{-1 of} manganese ion, 20 mol% of calcium ion, and 5 mol% 0.03 mol L ^{-1 of} manganese, and 0.001 mol L ^-1 of sodium metasilicate. 2. The electrolyte composition according to claim ¹ , wherein the manganese and silicon are contained in the electrolyte solution. A method of manufacturing a dental implant comprising a titanium alloy,
The dental implant manufacturing method includes:
a) a titanium alloy preparation step in which a dental titanium alloy is sequentially polished, micro-polished and ultrasonically cleaned;
b) an injecting step of placing the titanium alloy prepared in the preparation step on an electrolytic bath anode, placing a platinum on the anode, and injecting an electrolyte solution containing manganese and silicon;
c) forming a plasma by applying a constant voltage and current density to form an oxide film on the titanium alloy; And
d) forming an oxidized coating on the titanium alloy in the plasma forming step, and then washing the coated surface with ethanol and distilled water, followed by drying; and d) applying the apatite hydroxide coated with manganese and silicon ions. The method of claim 3,
Wherein the polishing is performed with a silicon carbide abrasive paper and polished stepwise with an abrasive paper having 100, 600, 800, 1200, and 2000 grit, wherein the apatite is coated with manganese and silicon ions. The method of claim 3,
Wherein the fine polishing is performed using 0.3 mu m alumina powder and the alumina powder is removed so as not to be left in the ultrasonic cleaning, wherein the apatite hydroxide coated apatite containing manganese and silicon ions is coated. The method of claim 3,
Wherein the electrolytic solution is prepared by mixing calcium acetate monohydrate, calcium glycerophosphate, manganese acetate, and sodium metasilicate nonahydrate in distilled water. The electrolytic solution is prepared by mixing calcium carbonate monohydrate, calcium glycerophosphate, And hydroxyapatite containing silicon ions are coated on the surface of the dental implant. The method according to claim 6,
0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerophosphate, and 0.02 mol L ^{-1 of} manganese ion in the electrolyte solution so that the concentration of manganese ion is 20 mol% relative to calcium ion and 5 mol% 0.03 mol L ^{-1 of} manganese, and 0.001 mol L ^-1 of sodium metasilicate. 2. The method according to claim ¹ , wherein the manganese and silicon ions are coated with apatite. The method of claim 3,
Wherein the voltage and current density are 250 to 280 V, 50 to 100 mA / cm <" ² & gt ^; , and the dissolution time is 3 minutes, wherein the apatite hydroxide-coated dental implant is coated with manganese and silicon ions.

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