WO2018174475A1 - Electrolyte composition containing metals and silicon in plasma electrolytic oxidation process and method for manufacturing dental implants coated with hydroxyapatite and containing metal ions and silicon ions by using same composition - Google Patents

Abstract

The present invention relates to formation of a porous oxide film, by means of plasma electrolytic oxidation, on the surface of a titanium-based alloy which is a metallic material that is generally used by being inserted into bones in a human body. More specifically, the present invention relates to a method for manufacturing implants for improving bioactivity by forming, by means of plasma electrolytic oxidation, a surface of a porous oxide film containing metal ions, silicon ions, calcium and phosphorus on the surface of dental implants, by using an electrolyte solution containing, from among plenty of ions constituting a human body, metals (magnesium, zinc, strontium, manganese) and silicon that play an important role in the cell adhesion and bone formation. In addition, the present invention relates to an electrolyte composition containing metals and silicon in a plasma electrolytic oxidation process and a method for manufacturing dental implants coated with hydroxyapatite and containing metal ions and silicon ions by using the composition, wherein the plasma electrolytic oxidation process comprises: a titanium alloy preparation step of sequentially subjecting a dental titanium alloy to grinding, micro-grinding, and ultrasonic cleaning; an insertion step of installing the titanium alloy prepared in the preparation step on an anode of an electrolysis tank, installing platinum on a cathode thereof, and inserting 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, after the oxide film is formed on the titanium alloy in the plasma forming step, cleaning the same with ethanol and distilled water, and then drying the same. The electrolyte composition containing metals and silicon in the plasma electrolytic oxidation process and the method for manufacturing dental implants coated with hydroxyapatite and containing metal ions and silicon ions by using the composition have the effect of simplifying steps of a manufacturing process and reducing time for manufacturing implants and a therapeutic period by treating the surface of the dental implants by employing the plasma electrolytic oxidation process in a titanium-based bio-alloy. Also, a porous oxide film having biocompatibility has been generated through complex substitution of metal ions and silicon ions using plasma electrolytic oxidation, an oxide film that is thicker and denser than conventional metal oxide films is manufactured, and the biocompatibility is rapidly increased by containing bioactive materials of metal ions and silicon ions, thereby enhancing the initial fixing force of the dental implants and reducing the therapeutic period.

Description

In the plasma electrolytic oxidation process, an electrolyte composition containing metal and silicon and a method for manufacturing a dental implant coated with apatite hydroxide containing metal ions and silicon ions using the composition

The present invention is to form a porous oxide film by using plasma electrolytic oxidation (Plasma Electrolytic Oxidation) on the surface of titanium-based alloy, which is a metal material that is generally inserted into the bone in the human body, more specifically, Porous inclusions of metal ions, silicon ions, calcium and phosphorus on the surface of dental implants using electrolyte solutions containing metals (magnesium, zinc, strontium, manganese) and silicon, which play an important role in cell adhesion and bone formation among ions An implant manufacturing method for improving the bioactivity by forming the surface of the oxide film by plasma electrolytic oxidation method, the process is a titanium alloy preparation step of sequentially polishing, fine polishing and ultrasonic cleaning the dental titanium alloy, the titanium prepared in the preparation step The alloy is installed at the anode of the electrolytic bath, and the cathode is bag After the gold is installed, an electrolyte solution is added to the electrolyte solution, a plasma is generated by applying a constant voltage and current density to form an oxide film on the titanium alloy, and an oxide film is formed on the titanium alloy in the plasma forming step. The present invention relates to an electrolyte composition containing metals and silicon and a method for producing dental implants coated with apatite hydroxide containing metal ions and silicon ions using the composition in a plasma electrolytic oxidation process including drying after washing with distilled water. .

In recent years, the biggest concern in the implant field is the shortening of the treatment period, and the most important factor in shortening the treatment period is the early development and maintenance of bone adhesion. Most of the recently commercialized implants are believed to have high biocompatibility and have a surface suitable for healing, producing and maintaining bone, but still cannot fully overcome adverse bone conditions. Meanwhile, titanium-based alloys used as main materials have been reported to be superior to conventional biometals, such as low elastic modulus and corrosion resistance with excellent biocompatibility. However, because it is bioinert, it does not directly induce bone formation, and it takes a long time for treatment to achieve bone bonding, and the naturally formed oxide film is thin so that its disappearance proceeds quickly and does not lead to regeneration of adjacent bone tissue. Have problems.

Therefore, in order to solve the above problem that the implant does not directly bond with the bone, and to solve the disadvantage of relaxing to shorten the bone bonding period is given bioactivity through the surface treatment of the implant. By treating the surface of titanium used as the main material of implants physically and chemically to improve the bioactivity, the healing period is shortened after the implant is placed in the human body, and research for more effective surface treatment is continuously conducted. There is a situation. Chemical surface treatment of the titanium surface treatment is anodizing, sol-gel, plasma spraying, chemical vapor deposition (CVD) and plasma electrolytic oxidation (PEO-Plasma Electrolytic Oxidation). .

The anodizing is a method of forming an oxide layer and a metal salt on a metal surface by using an external power source so that an oxide layer is formed on the anode, and the other insoluble metal is brought into contact with the cathode to generate a current in the electrolyte. When an electric current is applied to anodize the metal hydroxide, a metal hydroxide forms a fine film at a very low voltage, and when a voltage of about 10V is applied, a metal oxide layer is formed. However, once the oxide layer is formed, the resistance is increased to concentrate internal stress in the metal oxide layer, the oxide layer is destroyed at 70V, and when the voltage is increased again, a second porous oxide layer is formed, and sparks occur during this process. Since the oxidation layer is formed by applying electricity, the electrical efficiency is poor, and the sparked localized parts are not only adversely affecting titanium properties due to thermal stress, but also have a problem in that the adhesion is reduced and the final properties are degraded.

The sol-gel method is to prepare a solution which becomes a gel by hydrolysis and polymerization reaction by alcohol, water, acid, etc. in order to prepare a coating film. A wet coating method such as dip-coating, which is applied to a substrate, gelled on a substrate, and applied to a sol-gel method is a low temperature process, and can be coated regardless of area, and can control the thickness and microstructure of the film. There is an advantage, but the post-heat treatment process for crystallization is added, the plate-like coating is limited, and the adhesive has to be inserted into the intermediate layer to strengthen the adhesive force in order to have a sufficient bonding force with the base material.

Plasma spraying is a field of thermal spraying, in which a high melting point material such as a ceramic, which is a metal and a nonmetallic material, is deposited on a substrate in a molten or semi-melted state. There are no limitations on the material and size of the base material, and it can be installed on site without causing deformation to the base material, thick film coating, easy to control coating thickness, and various kinds of coating materials. It shows up to 0.6 ~ 15%, and it is weak to impact when ceramic coating of titanium due to mechanical bonding rather than metallic bonding, and it is difficult to apply implant because of weak bonding with the base metal.

Chemical Vapor Deposition (CVD) is a method of treating a surface by exposing a gas mixture to a sample at a high temperature, where a variety of reactions occur to decompose one or more components of the gas mixture, resulting in deposition on the substrate. Way. It is generally used to deposit pyrolytic carbon coatings on substrates such as tantalum, molybdenum, rhenium or graphite in the application of biomaterials.

Plasma Electrolytic Oxidation is in principle the same as anodizing, but anodic oxidation is a metal having high electrochemical stability relative to a cathode (Skinny's steel or platinum alloy, etc.), On the anode is placed a metal to be oxidized, such as magnesium. In the case of the plasma electrooxidation process, when a voltage equal to or higher than a dielectric breakdown voltage is applied to the previously formed anodization layer (or dielectric layer), a strong current field locally formed in the gas (hydrogen or oxygen gas) reacted inside the oxide layer is applied. Arc (or spark or plasma) is generated by. These plasma energies serve to fuse the oxides formed at the moment, so that the surface of the metal located at the anode is formed with a very dense and hard oxide which is completely different from the oxide formed by the anodization film. It is a surface treatment technology applied to a wide range of fields from marine and petrochemical industries. By adding Ca and PO ₄ ions in the electrolyte, it forms an oxide film that induces bonding with bone on the metal surface inserted into bone in the human body. Increasing bioactivity improves economical and biocompatibility. However, some problems such as shortening of treatment time due to problems such as failure of regenerating adjacent bone tissues and rapid loss of oxide film, which have been improved in some prior arts, still have conventional problems.

Prior art for surface treatment of implants by plasma electrolytic oxidation process is a method for preparing a titanium implant coated with an oxide film containing beta tricalcium phosphate, and a titanium implant prepared accordingly. Preparing an electrolyte solution containing phosphate ions as a method of preparing a titanium implant for bone implants coated with an oxide film containing beta tricalcium phosphate as a biocompatible material; Dispersing hydroxyapatite particles in the electrolyte solution; And performing a plasma electrolytic oxidation coating using titanium implant as an anode in the electrolyte in which the hydroxyapatite particles are dispersed. In the process of performing the plasma electrolytic oxidation coating, the phosphate ions of the electrolyte and the hydroxyapatite react. It provides a manufacturing method and titanium implant formed beta calcium phosphate formed in the oxide film, the Korean Patent Registration No. 10-1419276 (2014.07.15.) Coating formation method by plasma electrolytic oxidation 50mA / at a voltage range of 350V to 600V A current having a current density in the range of from 100 mA / range is applied, but a voltage greater than the voltage applied during the subsequent process is applied at the beginning of the plasma electrolytic oxidation process. The ratio of the number of times between and the negative voltage pulse Zma electrolytic oxidation is initially applied in a ratio of 1: 1 to 2: 1, and after the middle of the process to provide a coating forming method by plasma electrolytic oxidation is applied in a ratio of 30: 1 to 50: 1, Korea Patent Registration No. 10-1081687 (2011.11.09.) The biomaterial manufacturing method relates to the material for implants and artificial bone material, (a) potassium dihydrogen phosphate (KH ₂ PO ₄ ) and calcium chloride (CaCl ₂ ) in the electrolytic bath Forming an electrolyte with the mixed aqueous solution; (b) immersing an anode titanium or titanium alloy and a cathode metal having a higher reduction potential than the titanium metal in the electrolytic cell; (c) generating plasma by applying arc current to the titanium metal by applying a constant current and voltage to the titanium metal and the cathode metal; (d) forming hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ) on the surface of the titanium metal with ionic materials in the electrolytic cell using the plasma; (e) placing zirconium chloride (ZrCl ₄ ) and titanium metal coated with hydroxyapatite on the surface through step (d) in the reaction vessel; 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 complex on the surface of the titanium metal.

Looking at the prior art to form an oxide film on the surface of the titanium alloy, but the beta tricalcium phosphate (KH ₂ PO ₄ ) and calcium chloride (CaCl ₂ ) and the like in the electrolyte solution used in the plasma electrolytic oxidation process, voltage and It is composed of a structure that changes the current density, etc. It forms a porous surface where an oxide film is formed on the implant surface made of conventional titanium-based alloys, thereby improving bioactivity, thereby inducing bone cell adhesion and bone growth. Metabolic processes and elements included in the electrolyte solution as bone constituent elements are a reality that lacks biocompatibility.

The technical problem to be achieved by the present invention is to increase the initial fixation in the clinical, to reduce the failure rate by providing an oxide film using ions that are beneficial to bone formation in commercially available titanium-based bioalloy, and to achieve the object Plasma electrolytic oxidation is used as a means, but calcium and phosphorus include magnesium and silicon ions which induce bone and binding by the addition of calcium and phosphorus ions in the electrolyte, and induce bone cell adhesion and bone growth among bioactive substance ions. The electrolyte composition containing magnesium and silicon and the apatite containing magnesium and silicon ions were coated in the plasma electrolytic oxidation process in addition to the prepared electrolyte solution to provide complex titanium alloy surface treatment by the plasma oxidation process. Providing a method for manufacturing dental implants The.

In order to solve the above problems and achieve the object, the electrolyte composition containing metal and silicon in the plasma electrolytic oxidation process according to an embodiment of the present invention is calcium acetate monohydrate, calcium glycerophosphate (Calcium glycerophosphate) Electrolyte solution, including sodium metasilicate nonahydrate and distilled water and one selected from magnesium acetate tetrahydrate, zinc acetate, strontium acetate, and manganese acetate. Is done.

The electrolyte solution is 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerate and metasilicate so that the metal ion is 20 mol% relative to the calcium ion and the silicon ion is 5 mol% relative to the phosphorus ion. Provided is an electrolyte composition containing metal and silicon in a plasma electrolytic oxidation process comprising 0.001 mol L ^{-1 of} sodium and 0.03 mol L ^-1 of a metal ion selected from magnesium acetate, zinc aspartate, strontium acetate and manganese acetate.

A method for preparing a dental implant coated with a hydroxide of apatite containing metal ions and silicon ions comprises the steps of: a) preparing a titanium alloy for sequentially polishing, micropolishing and ultrasonic cleaning the dental titanium alloy; b) a titanium alloy prepared in the preparation step is installed in the electrolytic bath positive electrode, the negative electrode is platinum, and then the step of inputting an electrolyte solution containing metal 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 drying after washing with ethanol and distilled water.

The polishing is carried out with a silicon carbide abrasive paper, containing metal ions and silicon ions, characterized in that the polishing step by step with a polishing paper consisting of 100, 600, 800, 1200, 2000 grit.

The micropolishing is performed using 0.3 μm alumina powder, and is removed so that the alumina powder does not remain during ultrasonic cleaning.

The electrolyte solution is selected from magnesium acetate tetrahydrate, zinc acetate, zinc acetate, strontium acetate and manganese acetate, and calcium acetate monohydrate and calcium glycerate. Calcium glycerophosphate) and sodium metasilicate nonahydrate are prepared by mixing in distilled water.

The electrolyte solution is 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerate and metasilicate so that the metal ion is 20 mol% relative to the calcium ion and the silicon ion is 5 mol% relative to the phosphorus ion. Sodium 0.001 mol L ^-1 and the metal ion 0.03 mol L ^-1 selected from magnesium acetate, zinc acetate, strontium acetate and manganese acetate.

The voltage and current density and the available time is 250 ~ 280V, 50 ~ 100 mA / cm ^-2 and provides a method for producing a dental implant coated with hydroxide containing a metal ions and silicon ions carried out for 3 minutes.

As described above, in the plasma electrolytic oxidation process according to the present invention, an electrolyte composition containing metal and silicon and a method for preparing dental implants coated with apatite hydroxide containing metal ions and silicon ions using the composition are as follows. It works.

(1) The present invention has a dental implant surface treatment to the titanium-based bioalloy using a plasma electrolytic oxidation process to simplify the manufacturing process process, it is effective in reducing the implant manufacturing time and treatment period.

(2) The present invention produces a porous oxide film having biocompatibility through complex substitution of metal ions and silicon ions by plasma electrolytic oxidation, and a thicker and denser oxide film than a conventional metal oxide film is produced.

(3) The present invention includes a bioactive material of metal ions and silicon ions to quickly increase the biocompatibility, thereby increasing the initial fixation force of the dental implant to reduce the treatment period.

1 is a flowchart of a method for manufacturing a dental implant coated with apatite hydroxide containing metal ions and silicon ions by a plasma electrolytic oxidation process according to an embodiment of the present invention;

2 is a basic reaction diagram of the plasma electrolytic oxidation surface treatment according to an embodiment of the present invention,

3 is a realistic view of the surface of the titanium alloy treated with plasma electrolytic oxidation in a solution containing metal ions and silicon ions according to an embodiment of the present invention,

4 is a realistic view of the dental implant surface treated with plasma electrolytic oxidation in a solution containing magnesium and silicon ions according to an embodiment of the present invention,

FIG. 5 is a graph showing results of Energy Dispersive X-ray Spectroscopy (EDS) of a plasma electrolytic oxidation-treated titanium alloy using an electrolyte solution containing magnesium, zinc, and strontium according to an embodiment of the present invention;

6 is an EDS mapping photogram of a titanium alloy treated with plasma electrolytic oxidation using an electrolyte solution containing magnesium, strontium, and manganese according to an embodiment of the present invention;

7 is a graph showing an XRD (X-ray Diffractometer) result of a titanium electrolytically treated titanium alloy using an electrolyte solution containing magnesium, zinc, and strontium according to an embodiment of the present invention;

8 is an apatite photogram produced on a surface after immersing a plasma electrolytic oxidation-treated titanium alloy in a bio-like solution for 12 hours according to a preferred embodiment of the present invention,

9 is a photogram showing the degree of cell adhesion on the surface of the plasma implanted dental implant alloy using an electrolyte solution containing magnesium, zinc and strontium according to an embodiment of the present invention,

10 is a graph showing an XRD (X-ray Diffractometer) result of a plasma electrolytic oxidation-treated titanium alloy surface apatite using zinc-containing electrolyte solution according to an exemplary embodiment of the present invention.

11 is a table showing the ion distribution in the surface and the surface of the specimen of the plasma electrolytic oxidation-treated titanium alloy using the strontium-containing electrolyte solution according to an embodiment of the present invention,

12 is a biostabilization test result for evaluating the degree of metal ions eluted by plasma electrolytic oxidation using an electrolyte solution containing manganese according to an exemplary embodiment of the present invention.

Hereinafter, with reference to the drawings in the plasma electrolytic oxidation process according to an embodiment of the present invention using a metal and silicon-containing electrolyte composition and the composition to prepare a dental implant coated with a hydroxide containing metal ions and silicon ions The method is described in detail.

In the electrolyte composition of the plasma electrolytic oxidation step,

The electrolyte composition is

Calcium acetate monohydrate, Calcium glycerophosphate, Sodium metasilicate nonahydrate and distilled water, Magnesium acetate tetrahydrate, Zinc acetate, Strontium acetate and One selected from Manganese acetate forms an electrolyte solution.

The electrolyte solution is 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerate and metasilicate so that the metal ion is 20 mol% relative to the calcium ion and the silicon ion is 5 mol% relative to the phosphorus ion. Sodium 0.001 mol L ⁻¹ and the metal ion 0.03 mol L ⁻¹ selected from magnesium acetate, zinc asthite, strontium acetate and manganese acetate.

In the dental implant manufacturing method consisting of a titanium alloy,

The dental implant manufacturing method,

a) titanium alloy preparation step of sequentially polishing, fine polishing and ultrasonic cleaning the dental titanium alloy;

b) a titanium alloy prepared in the preparation step is installed in the electrolytic bath positive electrode, the negative electrode is platinum, and then the step of inputting an electrolyte solution containing metal and silicon;

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

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

Commonly used titanium (Pure-titanium) is divided into Ti-6Al-4V and Ti-6Al-4V extra low interstitial (ELI) .Titanium is an element that forms the earth's crust. Oxygen, silicon, aluminum, iron, calcium , The ninth most abundant element after sodium, potassium, and magnesium, with a relatively low specific gravity and a density of 4.5 g / cm 3, 40% lighter than stainless steel (7.95 g / cm 3), and pure titanium is currently an implant material for dental applications. It is widely used as, and the microstructure is composed only of HCP (α phase), the diameter of the crystal grain becomes 10 ~ 150㎛ according to the cold working effect, to form an interstitial solid solution to strengthen the material.

The Ti-6Al-4V alloy is a mixture of HCP (α phase) and BCC (β phase), the microstructure is largely dependent on the thermal effect and is affected by the processing process, 1000 ℃ that β phase is formed into a homogeneous phase In the above-described case, when cooling slowly, the needle and plate-like α phases are precipitated in a specific direction in the crystal of β, and this is called a “Widmanstten” structure. When rapidly cooled on β, martensite is formed. Normal Ti-6Al-4V is processed by heating near 882 ℃, which is β phase transformation temperature, and annealed to precipitate β phase particles in fine α phase matrix and grain boundary, and titanium has high melting point. Due to its low thermal conductivity and low electrical conductivity, phase transformation of α-Ti to β-Ti occurs at a temperature of 882 ° C. However, high temperature β-Ti does not bring β phase to room temperature by quenching, but becomes a needle-like α-Ti structure.

Therefore, titanium is the most widely used implant material at present because of its excellent mechanical properties and biocompatibility. Titanium is highly reactive and oxidizes in contact with air or body fluids. It is preferable as a material, and it is preferable to use Ti-6Al-4V as a material of the titanium alloy of this 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 as time passes, a barrier layer is formed and the porous surface layer is continuously generated in proportion to the applied voltage. When the oxide film is repeatedly formed and destroyed by plasma discharge after formation, heat is generated locally at high temperature to dissolve the surface. Such a repetition of the reaction is stopped when the applied voltage is stopped, thereby increasing the surface roughness. It has a porous surface, and the main reaction occurring at the anode during the plasma electrolytic oxidation process is as follows.

First, the reaction at the Ti / Ti oxide interface

Ti → Ti ²⁺ + 4e ^-

Second, it can be divided into two reactions at the Ti Oxide / electrolyte interface. Oxygen ions react with Ti to form an oxide, 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, final reaction

_{^{Ti 2+ + 2O 2- → TiO 2}} + 2e -

When voltage is applied to the aqueous solution containing the electrolyte in the electrolysis tank, oxygen gas is generated on the surface of the positive electrode or an oxidation reaction of the metal occurs, and hydrogen gas is generated or a reduction reaction occurs at the negative electrode.

Recently, as an element that affects bone regeneration by metal ions such as magnesium, zinc, strontium, and manganese, research is being actively conducted in the related fields, and more detailed descriptions regarding magnesium, zinc, strontium, and manganese are given below. do.

Magnesium is the fourth most abundant cation in the extracellular matrix of bone because it is contained in enamel, dentin, and bone as one of calcium and major substitution factors. Magnesium deficiency affects bone metabolism and bone cell growth, affecting bone density and bone ductility, and more specifically, the ionic strontium (Sr-strontium) and magnesium (Mg-magnesium) , Zinc (Zn-zinc), sodium (Na-sodium), silicon (Si-silicon), silver (Ag-silver) and yttrium (Y-yttrium) play an important role in bone formation because it affects bone density. Known. In particular, the preparation of magnesium-substituted apatite phase and crystal formation and growth in HA have been studied, and magnesium is known as a calcium substitute because HA has a structure in which the cationic lattice structure can be easily substituted with various elements. Ca ₁₀ - _x Mg _x (PO ₄ ) ₆ (OH) _{2 It} can be represented by the chemical formula. In this case, influence the particle shape, cell size, degree of crystallization, the thermodynamic properties of the powder and, by such a factor is substituted cations ^{(Mg 2+, Zn 2+, Sr} 2+) and negative ions ^{_{(SiO 4 4-, F -,}} CO ₃ ^2- ) are mainly used. In addition, magnesium is one of the major substitution factors of calcium and enamel, dentin and bone are 0.2 wt.%, 1.1 wt.% And 0.6 wt.%, Respectively. It is the fourth most abundant cation in. Magnesium deficiency reduces bone renal metabolism and bone growth and activity of osteoblasts, affecting bone mineral density and bone ductility, increasing the likelihood of fracture. Therefore, calcium deficiency HA [d-HA, Ca _10-x (HPO) ₄ ) _x (PO ₄ ) _6-x (OH) _2-x ; 0 = x = 1] Substitution of magnesium in the lattice provides excellent biocompatibility of Mg-HA and comparable to hard tissue. Therefore, magnesium is a product of solubility, crystallinity, particle shape, and nanoparticle synthesis by controlling physicochemical properties, controlling biocompatibility and biological activity, and showing good effect as a bioactive material.Silicone is also involved in new metabolism and bone formation. It is closely related to, and has the same effect as a bioactive substance as magnesium.

Zinc ions have an effect on nucleic acid metabolism, protein synthesis, and bone formation in vitro and in vivo, and accordingly, research is being conducted to add zinc to hydroxyapatite (HA) thin films to obtain improved active substances.

In addition, zinc is an essential trace element of almost all living organisms, and the human body contains the most amount of transition metal after iron, and in adults, about 2g of zinc is contained in the brain, liver, muscle, bone, kidney, liver, prostate, etc. In particular, in high concentrations in the prostate, Zn2 + is present in almost all types of enzymes. Recently, the most noticed enzyme is carbonic anhydrase, an enzyme that rapidly converts carbon dioxide into water and converts it to carbonic acid. And catboxypeptidase, an enzyme involved in the hydrolysis of C-terminal peptide bonds during protein digestion. In addition to these enzymes, zinc is a component of enzymes involved in the synthesis and degradation of carbohydrates, fats, and nucleic acids, and contributes to the stabilization of antioxidant enzymes (SOD). Zinc is also bound to proteins that recognize DNA sequences and regulate the transfer of genetic information during DNA replication, are involved in the metabolism and signaling of RNA and DNA, and regulate apoptosis, It is also involved in immune function. In addition, zinc affects insulin action, and is reported to be associated with activities such as growth hormone, sex hormone, thyroid hormone, and prolactin hormone.Silicone is also involved in renal metabolism and is closely related to bone formation. This has the same effect as a bioactive material as zinc.

In addition, zinc deficiency can lead to a variety of symptoms, including malnutrition, chronic liver disease, chronic kidney disease, decreased immune function, delayed growth, diarrhea, hypogonadism, delayed maturation, and skin changes, especially in children. The fetus can be born with mental and physical problems.

Strontium (Strontium) is present in the 15th lot in the crust, and the human body contains a significant amount of calcium in the bones and teeth, strontium promotes bone growth and increases bone density, so strontium compounds are used as food supplements and osteoporosis drugs Strontium compounds have been used to purify sugar from sugar beets. Recently, it is added to the front glass of color TVs or computer monitors to prevent X-ray emission, and is a component of magnets, and is also used to emit dark red fireworks from fireworks, flares, and flares.

Looking at the biological action and use of strontium, it is similar in size and size to the calcium and electron placement directly above the same family in the periodic table, so that organisms are less able to distinguish strontium from calcium and absorb strontium. Animals replace some of the calcium that makes up bones and teeth. The body contains about 320 mg of strontium (70 kg body weight), and bones contain 36 to 140 ppm. Most strontium compounds are harmless to organisms, but SrCl ₂ and Srl ₂ are considered to be slightly toxic, and since the 1950s, strontium has been studied for human health, and lanthanum strontium promotes bone formation. It is used as a therapeutic agent for osteoporosis because it increases bone density and reduces fractures. The trade name is Protelos or Protos. In addition, the radiopharmaceutical metastron (Metastron) is a ⁸⁹ Sr chloride ( ⁸⁹ SrCl ₂ ) is used in the treatment of pain and metastatic cancer caused by bone metastasis of cancer, Silicon is also involved in kidney metabolism and is closely related to bone formation, and thus has the same effect as a bioactive material as the strontium.

Manganese (Mn) is an indispensable element in plants and animals as an essential trace element of humans, and the lack of manganese in green plants reduces the production of chlorophyll, coexists with iron in animal tissues, but is widely distributed in humans. There is a lot of liver, pancreas and hair. It is observed that when manganese is deficient, the amount of acidic mucopolysaccharides of cartilage decreases significantly, the egg hatching rate of chickens, etc. decreases, and skeletal development of chicks significantly decreases. In addition, it is necessary for normal skeletal growth and development and is involved in radical elimination as an element important for enzymes such as superoxide dismutase in the body. Thus, manganese ions are less toxic than aluminum and vanadium and, when doped with alloys, increase the corrosion resistance and mechanical properties of biomaterials. Manganese is added to tricalcium phosphate bioceramic to show sufficient cellular compatibility, and the addition of manganese to titanium alloy improves cell adhesion characteristics.

The polishing is performed with silicon carbide abrasive paper, and is stepwise polished with abrasive paper composed of 100, 600, 800, 1200, 2000 grit.

The micropolishing is performed using 0.3 μm alumina powder, and ultrasonic cleaning is performed for 10 minutes in ethyl alcohol to remove the alumina powder. The electrolyte solution is added to the positive electrode before installation of the magnetic bar. It is preferable to use agitated at 200 rpm, and the distance between the two electrodes of the positive electrode and the negative electrode is spaced apart from 20 to 40 mm.

The electrolyte solution is selected from magnesium acetate tetrahydrate, zinc acetate, zinc acetate, strontium acetate and manganese acetate, and calcium acetate monohydrate and calcium glycerate. Calcium glycerophosphate) and sodium metasilicate nonahydrate are prepared by mixing in distilled water.

The electrolyte solution is 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerate and metasilicate so that the metal ion is 20 mol% relative to the calcium ion and the silicon ion is 5 mol% relative to the phosphorus ion. Sodium 0.001 mol L ^-1 and the metal ion 0.03 mol L ^-1 selected from magnesium acetate, zinc acetate, strontium acetate and manganese acetate.

The voltage and current density and the available time is 250 ~ 280V, 50 ~ 100 mA / cm ^-2 and 3 minutes, but by installing a separate cooling system to maintain the temperature of the electrolysis tank at 25 ℃ to carry out the plasma electrolytic oxidation process After the formation of the oxide film and washing, it is preferable to dry using warm air.

Example: Preparation of dental implant coated with apatite hydroxide containing metal ions and silicon ions by plasma electrolytic oxidation

Ti-6Al-4V disc (grade 5, Timet Co.Ltd, japan diameter; 10mm, thickness; 3mm) test specimens with silicon carbide abrasive paper, step by step with abrasive paper composed of 100, 600, 800, 1200, 2000 grit Polishing, fine polishing with 0.3 μm particle size aluminum oxide (Al ₂ O ₃ ), ultrasonic cleaning, magnesium ions, zinc ions, strontium ions, and manganese ions in the electrolyte solution (1L of distilled water) To 5, 10, 20 mol% compared to, and the silicon ions to 5 mol% compared to the phosphorus ion Table 1 (Magnesium), Table 2 (Zinc), Table 3 (Strontium) and Table 4 (Manganese) Calcium acetate monohydrate, Calcium glycerophosphate, Magnesium acetate tetrahydrate and Sodium metasilicate nonahydrate, as described in the design described in 3rd After loading the reagent is designed to ryusu using a magnetic bar stirrer was prepared in such that a homogeneous solution was stirred for at least 30 minutes at 200 rpm. The prepared electrolytic solution was filled in an electrolysis tank, and the ultrasonically cleaned specimen was installed on the positive electrode, and the negative electrode was coated with platinum and then subjected to plasma electrolytic oxidation by applying 280V, 70 mA / cm ^-2 and 3 minutes. It was.

Further, the dental implant made of titanium alloy of the same material was produced under the same conditions as the specimen subjected to the plasma electrolytic oxidation process in the above embodiment.

Test Example 1: Surface Porosity of Specimen According to Ca (Mg, Zn, Sr, Mn) / P (Si) Mol% Ratio

In the above embodiment, the surface of the electrolytically oxidized specimens and dental implants were measured by electron microscopy, but magnesium, zinc, strontium and manganese ions were 5, 10, 20 mol% compared to calcium ions, and silicon ions were compared to phosphorus ions. Each porosity of the treated surface was examined by giving a difference of 5 mol%.

FIG. 3 is a perspective view of a surface of a titanium alloy subjected to plasma electrolytic oxidation in a solution containing metal ions and silicon ions according to an exemplary embodiment of the present invention, and FIG. 4 is magnesium and silicon according to an exemplary embodiment of the present invention. A dental implant surface realistic treatment treated with plasma electrolytic oxidation in a solution containing ions will be described in detail with reference to FIGS. 3 to 4.

FIG. 3 shows pores having micrometer size pores on the surface of the oxide film of metal ions and silicon ions on a surface of a specimen subjected to plasma electrolytic oxidation in a solution containing magnesium, zinc, strontium and manganese ions and silicon ions. It was found that the formation was uniform, showing a smaller pore morphology with increasing concentration of metal ions. Therefore, as the concentration of metal ions (20Mg / 5Si) was increased, a lot of small pores were generated, and accordingly, it was found that it made a favorable state for bone bonding.

On the other hand, Figure 4 shows a uniform pore shape as shown in Figure 3 above in a realistic view showing that the magnesium ion (20Mg / 5Si) the highest dental implant surface in the embodiment by an electron microscope x 50 times, x 1000 times I could confirm that it formed.

Test Example 2: EDS and EDS mapping of plasma alloyed titanium alloy specimen

Energy Dispersive X-ray Spectrscopy (EDS) is used as an additional device attached to a scanning electron microscope device, which collects specific X-rays of a sample generated by an electron beam of a scanning electron microscope. More specifically, scanning an electron beam onto a sample (in the embodiment, a plasma electrolytic oxidation-titanium alloy specimen) causes electrons in atoms to absorb energy and become excited and release the excited X-rays while stabilizing the excited electrons again. In this case, since the emitted X-rays have a unique energy value for each material, X-rays were collected by using a detector, and the collected X-rays were classified by intensity to conduct a qualitative analysis on the sample.

FIG. 5 is a graph showing results of Energy Dispersive X-ray Spectroscopy (EDS) of a plasma electrolytic oxidation-treated titanium alloy using an electrolyte solution containing magnesium, zinc and strontium according to an exemplary embodiment of the present invention, and FIG. EDS mapping of the titanium alloy subjected to plasma electrolytic oxidation using an electrolyte solution containing magnesium, strontium and manganese according to an exemplary embodiment of the present invention will be described in more detail below with reference to FIGS. 5 to 6.

FIG. 5 shows that the components used in the electrolytic solution are evenly distributed as a result of EDS analysis of the calcium, phosphorus and silicon ions and the components of magnesium, zinc and strontium ions on the surface where the titanium alloy oxide film is formed. FIG. 6 shows EDS mapping for observing the distribution of calcium, phosphorus and silicon ions, magnesium ions, strontium ions, and manganese ions on the surface of a titanium alloy specimen. It was confirmed that they were evenly distributed.

In addition, Figure 11 is a table showing the ion distribution in the surface and pores of the specimen of the plasma electrolytic oxidation-treated titanium alloy using the strontium-containing electrolyte solution in accordance with a preferred embodiment of the present invention with reference to FIG. It was shown that the components of calcium, strontium, phosphorus and silicon ions were evenly distributed on the surface and the pores of the specimen, and the ions were better observed on the metal surface. The distribution of ions from the pores to the surface was further confirmed.

Test Example 3: XRD of Titanium Alloy Specimen Treated by Plasma Electrolytic Oxidation

X-ray diffractometer (XRD) is an X-ray diffractometer that measures the intensity of diffraction lines with a counter tube while changing the diffraction angle of monochromatic X-rays by a single crystal or powder sample, and records the intensity and angle automatically. It is also called a deflectometer and uses X-ray tube, which is a sealed tube with a stable power source, and combines solar slits to make a beam having a proper opening angle. In the case of powder samples, the goniometer (angle measuring device) which interlocks the sample and the counter tube rotates the plate shaped part in the form of a plate at an angular velocity ω and rotates the counter tube at 2 ω using a line focus parallel to the axis of rotation. The cutting lines are collected directly in front of the counter, usually using Geiger-Müller counters, and when precision is required, a proportional counter or scintillation counter is used in combination with the crest analyzer. In addition to the linear diffraction system, there are also four-axis diffractometers which are controlled by a computer, process the measurement result to make a decision, and then transfer to the next measurement.

FIG. 7 is a graph showing an X-ray diffractometer (XRD) result of a titanium electrolytically treated titanium alloy using an electrolyte solution containing magnesium, zinc, and strontium according to an exemplary embodiment of the present invention.

As shown in FIG. 4, the electrolyte solution containing magnesium was able to obtain an apatite phase and an anatase phase. As the concentration of magnesium ions was increased, the apatite phase was shifted to the left, which is considered to be the effect of magnesium ions on the apatite phase. .

The electrolyte solution containing zinc showed a strong peak in the anatase phase, a weak peak in the rutile phase, and the intensity of the α peak decreased as shown in FIG. 7.

The electrolyte solution containing strontium was able to identify the anatase phase and the hydroxyapatite phase, and the HA peak was shifted from 38.65 to 38.51, thereby inferring Sr substitution into the HA grid.

Test Example 4: Apatite formed on the surface after immersion of plasma electrolytic oxidation titanium alloy in a bio-like solution

FIG. 8 is a SBF (simulated body) of the titanium alloy specimen prepared in Example 1 with an apatite due diligence produced on a surface after 12 hours of immersion in a plasma electrolytic oxidation-treated titanium alloy in accordance with a preferred embodiment of the present invention. Bone formation was evaluated through apatite formed after immersion in a fluid) solution.

Bio-like solutions were Na ⁺ (142.0 mM), K ⁺ (5.0 mM), Ca ²⁺ (2.5 mM), Cl ⁻ (103.0 mM), HCO ^{3 −} (10.0 mM), HPO ^{4 −} as shown in Table 6 below. (1.0 mM) and SO ₄ ^2- (0.5 mM) were prepared in 200 ml beakers and kept in a incubator at 36.5 ° C ± 1 ° C, pH 7.4, similar to the oral environment, for 12 hours. It was observed after immersion.

After immersion for 12 hours as shown in FIG. 8, it was found that apatite was formed on the surface containing silicon ions, magnesium ions, strontium ions, and manganese ions in the oxide film formed on the titanium alloy surface within a short time. The higher the metal ion concentration, the higher the amount produced. However, zinc ions among the metal ions showed that the amount of apatite formed at 20Zn / 5Si was not formed slightly compared with other comparisons.

Test Example 5: Adhesion of Cells on the Surface of Dental Implant Alloy Treated by Plasma Electrolytic Oxidation

9 is a realistic view showing the degree of cell adhesion on the surface of the plasma implanted dental implant alloy according to an embodiment of the present invention. Referring to FIG. 9, the cells use human embryonic kidney cells 293, and plasma Calcium, phosphorus, metal ions and silicon ions were incubated for 24 hours on the surface of the titanium alloy (Example) where the oxide film was formed by the electrolytic oxidation process, and it was observed by scanning electron microscopy that the magnesium ions were evaluated for bone (apatite) formation evaluation. As shown in the results, the cell growth and adhesion were good. Zinc ions increased the cell culture volume when zinc and silicon ions were added than Ca / P, but the cell culture capacity increased as the zinc content increased. Strontium ion was 1.5 million times magnified to observe cell adhesion. As a result, 5Sr / Si (a) is 18, 10Sr / 5Si (b) is 20, and 20Sr / Si (c) is 21, and as the Sr / Si content increases, the cell adhesion rate increases.

Test Example 6 XRD after Apatite Formation of Plasma Electrolytic Oxidized Titanium Alloy Specimen

10 is a graph showing an XRD (X-ray Diffractometer) result of a plasma electrolytic oxidation-treated titanium apatite using zinc ion-containing electrolyte solution according to an exemplary embodiment of the present invention. It appeared strong, and the peak on rutile was weak. In addition, the HA phase strength was higher on the surface of the apatite, and the overall deposition showed that the HA phase doped with zinc and silicon was transferred from pure HA.

Test Example 7 Biosafety by Metal Elution Level by Plasma Electrolytic Oxidation

12 is further described in detail as a result of a biostabilization test for evaluating the degree of dissolution of metal ions by plasma electrolytic oxidation using an electrolyte solution containing manganese according to an exemplary embodiment of the present invention.

Biostabilization tests are available by evaluating the degree of metal ions eluting and by corrosive testing. Corrosion behavior of each specimen is similar to the oral environment using potentiostat (Mdel PARSTAT 2273, EG & G, USA). The electrochemical corrosion behavior was investigated by the prepared potentiodynamic method, and the applied potential was applied at a scanning speed of 1.67 mV / min from -1500 mV to 2000 mV, and the body-like solution was 36.5. The test was performed in 0.9% NaCl solution at ± 1 ° C. From the polarization curves, the dissolution behavior of metals was investigated by the corrosion potential, corrosion current density and current density in the passivation region.

The corresponding values for the surface coating at 0, 5, 10 and 20 mol% were (-470 ± 3.0) mV (-650 ± 5.0) mV, (-820 ± 4.0) mV and (-690 ± 2.0) mV, respectively. The concentration of manganese added to the oxide film was lowered at 10 mol%, which indicates that the corrosion potential decreased as manganese ions increased after plasma electrolytic oxidation.

It was also confirmed that the active site of the pores contained chlorine ions from the solution, thus exhibiting a low corrosion potential on the surface where the pores were formed.

In a further aspect,

Silver nanoparticles may be added to the electrolyte solution to add silver ions to impart antimicrobial activity to the oxide film. Bacterial infections can occur during implant placement, resulting in periarthritis in the implanted tissue, which is characterized by the loss of bone adhesion at the site where the bone adhesion has been created and the cause of excessive occlusal force or infection. have. The subsidiary diseases of the peri-implant tissues can be divided into peri-implant mucositis and peri-implantitis. Peri-implntitis is characterized by edema, redness and bleeding during detection. Peri-implntitis causes a wider range of inflammatory symptoms, with purulent bone loss along with purulent.

On the other hand, the antimicrobial mechanism of silver ions due to the addition of silver nanoparticles shows that the cell membrane is composed of a phospholipid bilayer, and because the oxygen bound to the phospholipid contains negative ions, the cell membrane is characterized by negatively charged and eluted as a whole. The silver ions reach the cell membrane by diffusion, and at the same time, they adsorb on proteins such as cell membrane and destroy the structure of the cell. Silver ions adsorbed to proteins such as cell membranes and enzymes bind to the sulfide group (-SH) of cystein, a protein-constituting amino acid, and convert it into sulfides, causing energy metabolic disorders by modification of protein enzymes. In addition, silver ions are directly ingested by microorganisms and combined with DNA, RNA, celluara protein, and resporatory enzymes to disrupt migration, growth and division, or to inactivate metabolic disorders in the cytoplasm of bacteria. Deactivation of microorganisms by destroying cell walls or by delocalization of silver ions on cell membranes leads to delocalization of cytosolic anions.

By adding 0.03 mol L ⁻¹ of silver nanoparticles to the electrolyte solution, plasma-based electrolytic oxidation treatment of the titanium-based alloy has antimicrobial properties on the surface, and the effect of bone adhesion by magnesium and silicon ions is enhanced.

In addition, the present invention is carried out a plasma electrolytic oxidation process using the above-described anode or three electrodes using a DC voltage, but may also use an AC voltage, wherein the AC voltage may use an asymmetric pulsed voltage, Applying an asymmetrical pulsed voltage allows the positive portion of the pulse to establish the inverted surface, the oxide is formed and the surface converted at the early stages of the layer growth process has a dense structure and the thickness of the anodized coating Increasing the porosity in the coating can increase the bone bonding speed, and the thickness of the oxide film can be increased by performing a plasma oxidation process a plurality of times by changing the ratio of the current density given to the anode and cathode.

In addition, as described above, the attachment of osteoblasts to the implant depends on the surface characteristics of the implant.The chemical composition, surface energy and surface morphology have an important effect on the maturation as well as on the osteoblast adhesion form. The increase promotes early cell adhesion and expansion, thereby inducing a wider range of bone formation. In general, the difference in surface chemical composition and surface energy may appear as a difference in hydrophilicity, and this hydrophilicity is an important factor for adhesion and differentiation of early osteoblasts. Therefore, in order to increase the biocompatibility of the implant surface, the surface of the titanium alloy of the present invention, which is plasma electrolytically oxidized, may be treated with ultraviolet or ultraviolet-ozone, or may be irradiated with a laser to add a process that may have hydrophilicity on the implant surface. have.

When treating the ultraviolet ray and the ultraviolet-ozone, the surface of the titanium alloy after the plasma electrolytic oxidation process is formed in the present invention and then the ultraviolet ray or ultraviolet-ozone is treated on the surface of the titanium alloy after the drying step. Alternatively, after completing the drying step as described above, the biocompatibility is increased by using a CO ₂ laser or an Er-Cr.YSGG laser, but a recently used Er-Cr.YSGG laser is used. It is desirable to set the energy at 100-120 mJ and 20 Hz frequency for 2 minutes at distance.

As described above, an oxide film containing magnesium and silicon ions is formed on the surface of the titanium alloy dental implant by plasma electrolytic oxidation, but nanoporosity is provided to provide a large surface area of the nanostructure, which is more advantageously applied to bone adhesion. The porous space formed inside is used as a channel for delivering various chemicals, drugs, and biomolecules that reach the protein level, so it acts only on a specific site. May reduce side effects.

In addition, the surface treatment of dental implants using a plasma electrolytic oxidation process on titanium-based bioalloys simplifies the manufacturing process and reduces the implant manufacturing time and treatment period. Through the complex substitution, a biocompatible porous oxide film was produced, and a thicker and dense oxide film was prepared than the conventional metal coral film, and the initial fixation force of the dental implant was increased by rapidly increasing the biocompatibility including bioactive materials of magnesium and silicon ions. Increase treatment to shorten the duration.

As mentioned above, although this invention was demonstrated by the limited embodiment and drawing, this invention is not limited by this, The technique to which this invention belongs is within the equal range of the technical idea of the invention, and a claim to be described below. Various modifications and variations are possible, of course.

In the plasma electrolytic oxidation process according to the present invention, an electrolyte composition containing metal and silicon and a method for manufacturing a dental implant coated with a hydroxide of metal ions and silicon ions using the composition are prepared by using a plasma electrolytic oxidation process. It can be used in place of the existing implant manufacturing process by simplifying the implant surface treatment process for the implant, reducing the implant manufacturing time, and providing an oxide film thicker and denser than the conventional metal oxide film.

Claims (8)

1. In the electrolyte composition of the plasma electrolytic oxidation step,

   The electrolyte composition is

   Calcium acetate monohydrate, Calcium glycerophosphate, Sodium metasilicate nonahydrate and distilled water, Magnesium acetate tetrahydrate, Zinc acetate, Strontium acetate and An electrolyte composition containing metal and silicon in a plasma electrolytic oxidation process, comprising an electrolyte solution comprising one selected from manganese acetate.
2. According to claim 1,

   The electrolyte solution is 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerate and metasilicate so that the metal ion is 20 mol% relative to the calcium ion and the silicon ion is 5 mol% relative to the phosphorus ion. Electrolyte composition containing metal and silicon in a plasma electrolytic oxidation process comprising 0.001 mol L ^{-1 of} sodium and 0.03 mol L ^-1 of a metal ion selected from magnesium acetate, zinc aspartate, strontium acetate and manganese acetate .
3. In the dental implant manufacturing method consisting of a titanium alloy,

   The dental implant manufacturing method,

   a) titanium alloy preparation step of sequentially polishing, fine polishing and ultrasonic cleaning the dental titanium alloy;

   b) a titanium alloy prepared in the preparation step is installed in the electrolytic bath positive electrode, the negative electrode is platinum, and then the step of inputting an electrolyte solution containing metal 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 drying after washing with ethanol and distilled water; and drying the apatite hydroxide containing metal ions and silicon ions.
4. The method of claim 3, wherein

   The polishing is carried out with a silicon carbide abrasive paper, but a step of polishing with a polishing paper consisting of 100, 600, 800, 1200, 2000 grit, characterized in that the apatite hydroxide containing metal ions and silicon ions coated dental implants.
5. The method of claim 3, wherein

   The micropolishing is performed using 0.3 μm alumina powder, and the method for producing dental implants coated with apatite hydroxide containing metal ions and silicon ions, characterized in that the alumina powder is removed so as not to remain during ultrasonic cleaning.
6. The method of claim 3, wherein

   The electrolyte solution is selected from magnesium acetate tetrahydrate, zinc acetate, zinc acetate, strontium acetate and manganese acetate, and calcium acetate monohydrate and calcium glycerate. Calcium glycerophosphate) and sodium metasilicate nonahydrate (a sodium metasilicate nonahydrate) is a method for producing a dental implant coated dental hydroxide containing metal ions and silicon ions, characterized in that prepared by mixing in distilled water.
7. The method of claim 6,

   The electrolyte solution is 0.12 mol L ^{-1 of} calcium acetate, 0.02 mol L ^{-1 of} calcium glycerate and metasilicate so that the metal ion is 20 mol% relative to the calcium ion and the silicon ion is 5 mol% relative to the phosphorus ion. Dental coated with apatite hydroxide containing metal ions and silicon ions, characterized by consisting of 0.001 mol L ^{-1 of} sodium and 0.03 mol L ^-1 of one selected from magnesium acetate, zinc acetate, strontium acetate and manganese acetate Implant preparation method.
8. The method of claim 3, wherein

   The voltage and current density and the available time is 250 ~ 280V, 50 ~ 100 mA / cm ^-2 and 3 minutes apatite hydroxide coated metal implants containing silicon ions, characterized in that carried out for 3 minutes.

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