KR20040013979A - The generation method of TixOy system material and the oxidation material of Ti system used micro-hallow emission - Google Patents

Abstract

PURPOSE: Provided is a method for producing titanium oxide-based materials using micro-hollow cathode emission, which is processed under atmospheric pressure, and reduces the cost and increases the productivity in the field of advanced materials. CONSTITUTION: The method comprises the steps of generating oxygen plasma or ozone by micro-hollow cathode emission, and oxidizing a titanium-based substance by the oxygen plasma or ozone to form a titanium oxide-based material(TixOy). In particular, the titanium oxide-based material(TixOy) is titanium dioxide(TiO2). In the case of a dental implant material, the method further comprises the step for forming an implant having a desired shape from a titanium-based material. Then, the implant is coated with the stable TixOy layer produced by the aforesaid method.

Description

The generation method of TixOy system material and the oxidation material of Ti system used micro-hallow emission}

The present invention relates to a material processing process technology related to a new material, and more specifically, to produce an oxygen plasma or ozone using micro-hallow emission, and again to oxidize a titanium plant using titanium oxide based In order to form a material (Ti _x O _y ), a method of generating a titanium oxide-based material using a microporous discharge and a titanium-based oxidation treatment material are provided.

As the industry becomes more specialized and the information industry systems and technologies are developed, countries around the world are aware of the need for new materials and are devoted to developing technologies in the field of advanced materials.

In general, new materials are more advanced new materials, which means a great leap in technology as well as new industries and added value.The importance of high-tech and new materials is a core industry that must be achieved. can do.

The new material is so effective that it affects almost all industries. It is used in almost all fields such as electronic, electrical and information equipment products, transportation structures such as automobiles, ships and aircrafts, various biomedical devices and implant materials, and mechanical structural plant materials.

Therefore, new materials of higher quality, which show better efficiency than those developed so far, are required, and researches for developing such new materials continue to be carried out in many research institutes around the world.

Therefore, the present invention for presenting a new material and a new processing technology, by using the micro-hallow emission (micro-hallow emission) to produce oxygen plasma or ozone and again using this to oxidize the titanium-based plant by using a titanium oxide-based material ( Not only to form Ti _x O _y ), but also to provide a process for producing a titanium oxide-based material and a titanium-based oxidation treatment material using a micro-cathode discharge, which can be processed at ordinary pressure (atmospheric pressure) unlike the conventional art. .

1 is a structural diagram of a titanium-based oxidation treatment apparatus using a microhallow (microhallow) according to an embodiment of the present invention.

2 is a structural diagram of a microporous cathode according to the practice of the present invention;

3 is a view showing a state in which discharge occurs in the microcavity.

Figure 4 is another device structure for producing a titanium oxide-based material according to an embodiment of the present invention.

FIG. 5 is a structural diagram illustrating an embodiment in which a bias is applied to the microhallow cathode triode of FIG. 4. FIG.

<Description of Symbols for Major Parts of Drawings>

110: microhallow cathode structure

110a: anode (anode)

110c: micro-hallow cathode

110h: micro hallow

110i: dielectric

120: RF power

40: triode

40r: variable resistor

401: anode 1

402: second anode (anode 2)

403: cathode

451: anode

452: cathode 1

453: second cathode (cathode 2)

501 power supply

502: current regulator

503: voltage regulator

510: rotary pump

520 gas supply device

Titanium oxide-based material generation method using a micro-cathode discharge of the present invention for achieving the above object,

Oxygen plasma or ozone is generated by using a microcathode discharge, and a titanium oxide material is oxidized using the generated oxygen plasma or ozone to form a titanium oxide-based material (Ti _x O _y ).

In addition, a method of producing a titanium oxide-based material using the microporous discharge of the present invention for achieving another object,

(1) forming an implant of a required shape using a titanium-based material,

(2) generating oxygen plasma or ozone using microporous discharge;

(3) oxidizing the titanium-based material with the generated oxygen plasma or ozone to produce a titanium oxide-based material (Ti _x O _y ).

The titanium-based oxidation treatment material using the microporous discharge of the present invention for achieving another object, generates oxygen plasma or ozone by using the microporous discharge and oxidizes the titanium-based object with the generated oxygen plasma or ozone To produce a titanium oxide-based material (Ti _x O _y ).

Hereinafter, a method of generating a titanium oxide-based material and a titanium-based oxidation treatment material using the microporous discharge of the present invention will be described in detail with reference to the accompanying drawings.

As described above, the present invention relates to the treatment of titanium (Ti, titanium) or titanium (Ti) -based alloying materials, and is related to a new material or a new material processing technology.

The biggest characteristic of titanium (Ti, titanium) is the corrosion resistance. It is heavily influenced by an oxide film formed on the surface of titanium (Ti), which is very strong and easily regenerated when the film is broken, and this property is the basis for better corrosion resistance than ordinary stainless steel. .

In addition, titanium (Ti) has a specific gravity of about 4.51, which is about 1/2 of that of nickel (Ni, Nickel), and about 60% of stainless steel or iron, so that it is easy to assemble, install, and move, and its strength is special steel. Comparable to

In addition, since titanium (Ti) has a strong affinity for oxygen and nitrogen, it forms stable oxides and nitrides when reacting with oxygen or nitrogen. The thin oxide film formed by reacting with oxygen improves the corrosion resistance of titanium (Ti), and the nitride film formed by reaction with nitrogen improves wear resistance. In addition to this, when oxygen and nitrogen are successively dissolved into titanium, titanium also hardens.

As such, titanium (Ti) and titanium (Ti) alloys have high specific strengths (strength-specific gravity), high temperature properties up to about 550 ° C, and especially alloys that are resistant to acid and chloride media and most natural environments. to be. As a result, applications in space and aviation, where the specific strength and high temperature characteristics are important, are increasing significantly. Not only are they expected to be applied in the chemical, food, and medical industries that require excellent corrosion resistance, but also new applications. Is an alloy that is still being developed.

In the present invention will be described as an example of the pharmaceutical field in the various uses of such excellent titanium (Ti) or titanium (Ti) alloy, as described above, the present invention is not only in the pharmaceutical field but also where the titanium (Ti) alloy is used Can be applied.

There are many different fields in medicine, but one of them is a new method, which is different from conventional methods such as dentures and bridges.In the case of a missing tooth, an artificial tooth is planted on the jawbone at that location and an artificial tooth is created on it. It's the same treatment.

As described above, titanium (Ti) is easy to process and relatively light in comparison with other metals, and can be improved in strength by alloying or processing, and titanium oxide based on oxygen (Ti _x O _y ), for example. Titanium oxide (TiO ₂ , titanium dioxide) coatings are known to have biocompatibility with high corrosion resistance (corrosion resistance).

In general, the oxide film in vivo is required to be chemically stabilized. If chemically unstable, corrosion occurs and metal ions are released to the environment, causing a tissue reaction. From this point of view, the titanium alloy is an implant material because it satisfies the conditions to be used as a biomaterial, that is, biocompatibility, chemical compatibility, and mechanical compatibility. It is a very suitable material.

In general, metal materials alone do not appear to satisfy these various conditions, but various kinds of bioceramic materials have been developed to satisfy these conditions, but there are almost no ceramics that satisfy the above conditions. In addition, ceramics are not suitable for manufacturing implants alone because ceramics are less susceptible to impact and difficult to machine than titanium oxide based materials.

Moreover, the adhesion between the ceramic coating layer and the metal base interface is significantly reduced due to the different surface energy characteristics. On the other hand, metal oxides such as metal bases have excellent adhesion at the interface. In particular, titanium oxide (TiO ₂ , titanium dioxide) coating, which is a type of titanium oxide-based coating, has high corrosion resistance as described above, and has excellent biocompatibility, so that bone adhesion occurs well. Therefore, according to the present invention, it is understood that many problems can be solved when a stable titanium oxide (Ti _x O _y ) film is formed on a titanium (Ti) implant material.

In addition, since titanium (Ti) is highly reactive and easily bonds with oxygen, damaged oxygen film is easily regenerated if any oxygen (ppm units) is present or moisture is present in the surroundings. In addition, the titanium oxide (Ti _x O _y ) coating acts as a stable ceramic contact surface that can be bonded to the reinforced bone matrix, and is easily bonded to the bone.

Titanium-based general oxidation by (Ti _x O _y) the implant material is divided into a rutile (Rutile) is anatase (Anatase) phase and, when heat-treating them at least 700 ℃ generated having a tetrahedral structure, titanium-based oxide (Ti _x It is known that the surface shape and biocompatibility of O _y ) have a great influence on cell formation and bonding strength during bone adhesion. And it has been reported to exhibit a heat-treated rutile (Rutile) different than the good effect and then at a high temperature of these titanium-based oxide (Ti _x O _y) the implant material.

In addition, conventional methods for forming a TiO ₂ film include thermal oxidation by heat treatment, ion assisted deposition using ions, and reactive sputtering. However, thermal oxidation has a high temperature process. There are problems such as dimensional change and thermal deformation, and in the case of ion assisted deposition or reactive sputtering, there are many problems in the process until mass production, such as high vacuum.

In the present invention, by introducing a technique capable of forming a titanium oxide (Ti _x O _y ) film at atmospheric pressure (atmospheric pressure) to propose a new process technology to solve the conventional problems and the resulting titanium-based oxidation treatment material .

1 is a structural diagram of a titanium-based oxidation treatment apparatus using a microhallow (microhallow) according to an embodiment of the present invention.

As described above, the present invention is operated at atmospheric pressure (atmospheric pressure), and it is also possible to operate in a chamber in situations where there is no benefit. 3 shows an example of the apparatus structure of oxygen plasma generation and ozone generation at atmospheric pressure together with the example of FIG.

As shown in the drawing, when the RF power supply 120 of about 14 Mhz is supplied to the microcavity (microhallow, 110), the air introduced into one side of the microcavity (110) is oxygen plasma inside the microcavity (110). As the oxygen atoms and oxygen molecules react with each other, ozone (O ₃ ) is eventually formed.

Therefore, when a titanium-based material such as a titanium implant or a titanium-based molded product is placed at the exit side of the microcavity 110, ozone (O ₃ ) generated in the microcavity 110 causes an oxidation reaction to cause a type of titanium oxide-based coating. Phosphorus titanium oxide (TiO ₂ , titanium dioxide) film is produced.

FIG. 2 is a structural diagram of a microcavity electrode related to the practice of the present invention, and FIG. 3 shows a state in which a discharge occurs in the microcavity electrode.

As shown, the microporous structure has a positive electrode (anode 110a) on the top and a micro-hallow cathode 110c on the opposite side. In addition, a dielectric (110i) is applied to the surface of the microcavity (110c) to take the structure of the dielectric barrier discharge (dielectric barrier discharge) concept. In addition, by applying the dielectric 110i, the inside thereof forms micro-pores 110h.

In such a microporous structure, the electrons present in each of the micropores 110h are accelerated by the cathode drops that are symmetrically present to ionize and excite the neutral state gas therein. In this process, the electrons inside the micropores 110h generate strong vibrations and are accelerated by the voltage drop applied to the micropores 110c and the anode 110a. Therefore, when the fluorescent material is applied to the surface of the anode 110a, the efficiency of fluorescence or light emission is increased.

In addition, as in the present invention, oxygen plasma is generated at atmospheric pressure inside, and oxygen atoms and oxygen molecules react to generate ozone at the outlet side of the microcavity 110 as shown in FIG. 1.

As a result, in the present embodiment, the electrons emitted from the micropores 110h of the microcavity 110c are subjected to electron oscillation as shown in [B] of FIG. 2 after the initial radiation as shown in FIG. In this case, the plasma density in the microcavity structure is greatly increased, and the plasma density in the microcavity 110h is increased.

In the process of operating in the microporous structure, as shown in FIG. 3, it can be seen that the electromagnetic vibration is strongly formed between the micropore 110c and the anode 110a.

Figure 4 is another device structure for producing a titanium oxide-based material according to an embodiment of the present invention.

As shown, the device structure for producing a titanium oxide-based material according to the present invention may be referred to as a triode form of the microhallow cathode structure.

[A] form on the left is an A-AC structure, and is composed of a first anode 401, anode 1, a second anode 402, anode 2, and a cathode 403. In addition, a microhallow cathode is formed at the center of contact between the second anode 402 and the cathode 403 to form a plasma in the direction of the arrow to discharge.

[B] form on the right is a C-CA type structure and consists of an anode 451, a first cathode 452, cathode 1, and a second cathode 453, cathode 2. In the C-CA type structure, a microhallow cathode is formed at the center where the anode 451 and the first cathode 452 contact each other, and unlike the [A] type, the second cathode A plasma discharge is formed in the direction of (453, cathode 2).

Therefore, in the triode of [A] type, the titanium implant is placed on the first anode (401, anode 1) for oxidation treatment. In the [B] type, the titanium implant is placed on the second cathode (453, cathode 2). It is oxidized.

In addition, the intermediate variable resistor 40r is used to effectively generate plasma discharge by adjusting the main anode to have a higher bias than the main cathode.

FIG. 5 is a structural diagram illustrating an embodiment in which a bias is applied to the microhallow cathode triode of FIG. 4.

As shown, it is important to produce oxygen plasma in the triode 40 and then form ozone.

Therefore, when power is supplied from the power supply unit 501, the current regulator 502 regulates and supplies the current by the current resistor 502r, and the voltage regulator 503 regulates and supplies the voltage. .

This causes ozone to be generated in the triode 40 and the titanium implant standing on the opposite side is subjected to oxidation treatment.

As in the present embodiment, the present invention can be processed in a chamber separated into a predetermined space in a special situation, so that a rotary pump (510) may be attached and used for maintaining the vacuum in the chamber. In order to use the ion gas, the gas supply device 520 may also be attached and operated.

In the present invention, thereby forming a titanium-based oxide (Ti _x O _y) film by placing by placing the titanium or titanium-based implant structure across which the oxygen plasma or ozone emitted by this operation. In addition, as described above, the present invention operates in an atmospheric pressure (atmospheric pressure) state, so a titanium oxide-based (Ti _x O _y ) film is formed by oxygen plasma or ozone, and titanium nitride-based (TiO) is formed by nitriding by nitrogen in the air. _x N _y ) film is generated to increase the hardness (hardness) also occurs.

As described above, the present invention forms a titanium oxide based (Ti _x O _y ) film by using an atmospheric pressure (atmospheric) plasma technique to solve the conventional problems. Since the present invention uses electron oscillation in the microcavity, the ionization rate is several hundred times higher than that of the conventional plasma generator, and the process from low pressure to high pressure is possible depending on the size of the microcavity. Therefore, no expensive vacuum equipment is required, and the surface shape can be controlled by controlling plasma power and pressure conditions. In addition, since the present invention does not require a discharge gas required for plasma discharge, the configuration of the device is simple, and since air in the air is used, it is more economical than any atmospheric pressure (atmospheric) plasma system.

In addition, the present invention can implement the surface characteristics such as hydrophilicity, hydrophobicity by selectively controlling the surface energy of the surface layer by using highly reactive ions and active radical species, ultraviolet rays, and vacuum ultraviolet rays generated during plasma discharge. Therefore, it is possible to form an oxide film on the surface of the titanium-based material at a relatively low temperature (atmospheric pressure), and to control the adhesion strength and the surface shape of the titanium oxide-based (Ti _x O _y ) film to the implant at room temperature, compared to the conventional method. It is a revolutionary way to reduce the manufacturing cost by reducing the manufacturing process.

Therefore, the present invention, in addition to the above-mentioned medical implant processing, dry cleaning, low-temperature metal coating, polymer / rubber surface adhesion improvement, fiber surface modification, pathogenic bacteria sterilization, waste gas treatment, etc. Applicability to the field is very high.

Titanium oxide-based material generation method and titanium oxide-based material using the atmospheric pressure plasma of the micro-cathode discharge of the present invention is a technology that is still in the early stages in developed countries and in Korea as a technique for biomaterials using atmospheric pressure plasma The study has not been reported yet.

The inventors and the laboratory have been studying atmospheric pressure plasma for seven years, and have a patent on its electrode structure and generator. Based on the accumulated experience and technology, it was applied to the formation of a titanium oxide (Ti _x O _y ) film, for example, titanium oxide (TiO ₂ , titanium dioxide) film by using atmospheric pressure plasma technology.

The atmospheric pressure plasma proposed by this technology improves the adhesion between the implants by using hydrophilic effect on the surface by using only air in the air, as well as additional plasma discharge gas because it generates plasma by using nitrogen and oxygen in the air. There is no need at all, so it is very effective in cost reduction In addition, it does not require expensive vacuum equipment required in low pressure plasma process and requires little modification of the existing production line, so it is possible to obtain maximum utility with little facility investment and to be most economically applicable to mass production. It can be said to be technology.

Therefore, if the establishment of effective titanium oxide (TiO ₂ ) coating method through surface treatment using atmospheric pressure plasma to improve productivity and economic efficiency through expansion of environment-friendly facilities and removal of post-treatment process, the domestic dental material industry It is expected to serve as a driving force to advance one step further and contribute to the development of titanium-based material processing technology.

Claims (11)

Microporous discharge, characterized in that to generate oxygen plasma or ozone by using a microporous discharge, and to form a titanium oxide-based material (Ti _x O _y ) by oxidizing a titanium-based object with the generated oxygen plasma or ozone. Titanium oxide-based material generation method using. (1) forming an implant of a required shape using a titanium-based material, (2) generating oxygen plasma or ozone using microporous discharge; (3) oxidizing the titanium-based material with the generated oxygen plasma or ozone to produce a titanium oxide-based material (Ti _x O _y ), wherein the titanium oxide-based material is produced using a microporous discharge. Way. Microporous discharge, characterized in that to generate oxygen plasma or ozone by using a microporous discharge, and to produce a titanium oxide-based material (Ti _x O _y ) by oxidizing a titanium-based object with the generated oxygen plasma or ozone. Titanium-based oxidation treatment material. The method of claim 1 or 2, wherein the titanium oxide-based material (Ti _x O _y ) is Titanium oxide (TiO ₂ , titanium dioxide), characterized in that the titanium oxide-based material generation method using a micro-cathode discharge. The method of claim 1 or 2, wherein the microporous discharge is An anode (anode) located at one end, The microcavity is formed to be spaced apart from the anode (anode) by a certain distance, and the ionization and excitation (electron oscillation) is caused by applying power to the micro-hallow cathode to which the dielectric is applied. Method for producing a titanium oxide-based material using a micro-cathode discharge, characterized in that to discharge the plasma by excitation). The method of claim 1 or 2, wherein the microporous discharge is With the first anode (anode 1), A second anode (anode 2) spaced apart from the first anode (anode 1) by a variable resistance component therebetween and having a microcavity at the center thereof; Discharging the plasma by ionization and excitation in a structure including a cathode having a microcavity in the center and bonded to the second anode in an insulated state. Characterized in that the method for producing a titanium oxide-based material using a micro-cathode discharge. The method of claim 1 or 2, wherein the microporous discharge is An anode forming a microcavity in the center, A first cathode (cathode 1) is formed by forming a micro-porous cathode in the center and is bonded and formed in an insulated state to the anode, Plasma by ionization and excitation in a structure including a second anode (anode 2) which is spaced a predetermined distance from the first cathode (cathode 1) and the potential can be adjusted by a variable resistance component therebetween A method of producing a titanium oxide-based material using microporous discharge, characterized in that for discharging. The method of claim 3, wherein the titanium oxide-based material (Ti _x O _y ) is Titanium oxide (TiO ₂ , titanium dioxide), characterized in that the titanium-based oxidation treatment material using a micro-cathode discharge. 4. The microporous discharge of claim 3, wherein An anode (anode) located at one end, The microcavity is formed to be spaced apart from the anode (anode) by a certain distance, and the ionization and excitation (electron oscillation) is caused by applying power to the micro-hallow cathode to which the dielectric is applied. A titanium-based oxidation treatment material using microporous discharge, characterized in that to discharge the plasma by excitation). 4. The microporous discharge of claim 3, wherein With the first anode (anode 1), A second anode (anode 2) spaced apart from the first anode (anode 1) by a variable resistance component therebetween and having a microcavity at the center thereof; Discharging the plasma by ionization and excitation in a structure including a cathode having a microcavity in the center and bonded to the second anode in an insulated state. Titanium-based oxidation treatment material using a micro-cathode discharge, characterized in that. 4. The microporous discharge of claim 3, wherein An anode forming a microcavity in the center, A first cathode (cathode 1) is formed by forming a micro-porous cathode in the center and is bonded and formed in an insulated state to the anode, Plasma by ionization and excitation in a structure including a second anode (anode 2) which is spaced a predetermined distance from the first cathode (cathode 1) and the potential can be adjusted by a variable resistance component therebetween A titanium-based oxidation treatment material using microporous discharge, characterized in that for discharging.