KR20020024665A - Dlc coated implants composite and manufacturing method thereof - Google Patents

Abstract

PURPOSE: Provided is a transplantation complex with a DLC(Diamond-Like Carbon) film coated which deposits the DLC film on the surface of Ti or Ti alloy to produce artificial organs so that it prevents friction from being generated in a body when the artificial organs are placed in the body. CONSTITUTION: The production process of the transplantation complex with the DLC(Diamond-Like Carbon) film coated comprises the steps of: (i) inserting a Ti base plate into a deposition instrument and injecting SiH4 gas at 20 mtorr to cause plasma for 2 and 1/2 minutes at 200 bias voltage and then deposit a Si intermediate layer; and (ii) inserting the Ti base plate with the Si intermediate layer deposited into the deposition equipment and injecting C6H6 gas at 10 mtorr to cause plasma for 10 minutes and deposit the DLC film on the surface of the Si intermediate layer.

Description

Biotransplantation composite coated with DLC and its manufacturing method {DLC COATED IMPLANTS COMPOSITE AND MANUFACTURING METHOD THEREOF}

The present invention relates to a biomaterial for manufacturing an artificial organ that can replace an aged part of the human body, and in particular, to improve the wear resistance of biomaterials such as artificial teeth or hip joints that are constantly stressed in the human body. It relates to a bio-grafted composite coated with an EL and a method for producing the same.

In modern society, due to the development of science and technology, the average life expectancy of human beings is getting longer and aging, and accordingly, efforts are being actively made to replace the parts where the aging of the human body is progressing rapidly by using artificially made devices. It is becoming. Among them, teeth and joints are easily broken into stressed parts in daily life compared to other artificial organs, and thus, attempts are being made to increase the physical properties and biocompatibility of artificial hips or artificial teeth for their replacement.

Wear is the main cause of breakage of artificial teeth and hips, and the improvement of wear resistance rather than mechanical strength is of very little interest, and many researchers are steadily researching to improve such wear resistance. In addition, the biomaterial should have excellent biocompatibility and have mechanical properties suitable for the application. Especially in the case of artificial teeth or hip joints, sufficient mechanical properties are important because they are always exposed to a heavily loaded environment.In the case of aluminum oxide, HAp (Hydroxyapatite), or their complexes, which are currently being studied as an implant material In spite of excellent biocompatibility, there is a disadvantage of poor workability, and in the case of metal artificial organs, there is an advantage in that it is easy to process, but there is a disadvantage that wear resistance is not as desired, and chemical resistance is slightly lower than that of ceramic. Have

The object of the present invention devised in view of the above problems is that by coating a material having excellent abrasion resistance and excellent biocompatibility on the base material of artificial organs such as artificial hips or artificial teeth, debris fall during use or It is to provide a bio-transplantable composite and a method of manufacturing the same is coated with a dieel suitable for preventing the generation of all adverse effects such as dissolution in vivo.

1 is a graph showing the wear life of the composite specimen according to the present invention.

2 is a graph comparing the wear volume of the composite specimen according to the present invention.

Figure 3 is a photograph of the wear test in a dry state of the composite of the present invention 3000cyle, 6000cyle, 9000cyle.

Figure 4 is a graph of the wear test in the wet conditions of the composite of the present invention.

5 is a graph comparing the chemical resistance of the composite according to the present invention.

Figure 6 is a table showing the cytotoxicity test results of the complex according to the present invention.

In order to achieve the object of the present invention as described above, a die-like film (DLC: Diamond-like Carbon) for improving wear resistance is deposited on the surface of the Ti substrate which is a basic material of an artificial organ mounted on a human body. Provided is a biograft composite coated with an EL.

In addition, there is provided a bio-composite composite coated with a DLC, characterized in that a DLC film is deposited on the surface of the Ti-6Al-4V substrate which is a basic material of an artificial organ mounted on a human body.

In addition, polishing the deposition surface of the Ti substrate, which is a basic material of the artificial organs mounted on the human body, placing the polished Ti substrate in an etching chamber and etching the polishing surface by generating a plasma using argon gas; Depositing the etched Ti substrate in a deposition apparatus and injecting SiH 4 gas to deposit an Si intermediate layer on the polishing surface, and inserting a Ti substrate on which the Si intermediate layer was formed into the deposition apparatus and injecting C6H6 using plasma. There is provided a method for producing a bio-composite composite coated with a DLC characterized in that the step of sequentially depositing a DLC (Diamond-like Carbon) for improving the wear resistance.

In addition, polishing the deposited surface of the Ti-6Al-4V substrate, which is the basic material of the artificial organs mounted on the human body, and putting the polished Ti-6Al-4V substrate into an etching chamber to generate plasma using argon gas, thereby polishing Etching the surface; depositing the etched Ti-6Al-4V substrate in a deposition apparatus while injecting SiH ₄ gas to deposit an intermediate Si layer on the polishing surface; and forming the intermediate Si-6 layer on Ti-6Al. Placing a -4V substrate in a deposition apparatus and depositing a DL-like film (DLC: Diamond-like Carbon) to improve abrasion resistance by using plasma while injecting C ₆ H ₆ . Provided is a method for preparing a biograft composite coated with DLC.

Referring to the embodiment of the bio-composite composite and the method for manufacturing the coated with the DLC of the present invention as described above are as follows.

Example

A substrate made of Ti (CP-Ti) and Ti alloy (Ti-6Al-4V) is placed in a process chamber of a chemical vapor deposition apparatus (CVD), and a process gas, C ₆ H ₆ gas, is injected into the chamber. When 13.56MHz RF plasma (radio frequency plasma) is generated, the plasma is generated inside the chamber and the atomic array of graphite and diamond mixed on the upper surface of the substrate (DLC: Diamond-like Carbon) ) Is deposited.

On the other hand, the substrate is in the form of a disk (disk) having a diameter of 1inch, thickness 1.5mm, and polished the deposition surface to 1μm, and then washed with ultrasonic equipment in ethanol and acetone.

Put the cleaned substrate in the chamber of the etching equipment, while maintaining the internal pressure of the chamber at 3.6 mtorr while injecting argon gas into the chamber, and applying a 750 bias voltage to the plasma inside the chamber. Is generated and etched, which is then etched for 1 hour in such a state to improve the adhesion in the subsequent process.

In the case of the DLC film, it is known that the adhesion with the substrate is not good due to the high compressive stress. In this experiment, Si is deposited in consideration of biocompatibility among materials that can increase the adhesion between the substrate and the DLC film. In the deposition method, SiH ₄ (90% diluted) gas was deposited for 2 minutes and 30 seconds at 200 bias voltage under a pressure of 20 mtorr to form a Si intermediate layer. In this state, C ₆ H ₆ gas was deposited on the Si interlayer under a pressure of 10 mtorr for 10 minutes at 500 bias voltages (DLC). As a result of measuring the adhesive force of the specimen deposited by the combination of DLC-Si-Ti and DLC-Si-Ti alloy using the adhesion tester (Sevastian-5), it was found that the adhesion was about 90.2 MPa.

The thickness of the DLC film was 1 μm as a result of measuring the thickness using a surface profiler.

In order to examine the wear resistance of the DLC film, a wear test was performed using a tribolometer of a pin-on-disk type. A ruby ball with a diameter of 5 mm was used and experimented under 5N and 32N. Since the body is not as dry as in the air, abrasion test was performed in physiological saline and compared with dry condition. After the wear test, the specimens were measured for wear depth and wear volume using a surface profiler, and the shape of the tracks was observed by SEM.

In order to determine the chemical resistance of the DLC film, an electrochemical test was conducted.

In addition, the cytotoxicity test was performed by the agar overlay method (Agar-Overlay, ISOTR7405) to determine the biocompatibility. Specimens were prepared with a diameter of 10 mm x 2 mm and washed with sterile distilled water. As a control group, sterilized filter paper soaked with 0.5 ml of the positive control group (Nitroso Guadine) and the negative control group (PBS) was used. All materials were washed with ethylene oxide (Ethylene Oxide) after washing. After the suspension of L-929 cells was made, 10 ml of cell suspension was added, and the cells were cultured for 24 hours. After 30 minutes after the addition of the dye, the dye was removed and incubated for 24 hours.

FIG. 1 is a graph showing data of abrasion test on a Ti-based substrate and a specimen on which a DL film was deposited on a Ti alloy substrate at a load of 32 N. FIG. In the case of using a substrate, since Ti is a ductile, plastic deformation occurs under a load of 32N. However, the DLC film was a very brittle material, and the plastic deformation was relatively less than that of the substrate, and eventually, cracks were generated along the recessed portion of the substrate. That is, the occurrence of cracking serves to greatly reduce the life time of the DL film.

When the DL film is deposited on the Ti alloy, since the Ti alloy has a strong ability to withstand the load, the DL film is cut off over time due to normal wear.

After the 3000 cycle abrasion test was performed on the substrate coated with the DLC film and the uncoated substrate, the wear volume was compared with that of Ti or Ti alloy as shown in the graph of FIG. 2. Remarkably small thing was confirmed.

In the wear test until the breakage of the film, the amount of wear was observed to be smaller in the case of the environment in solution than in the dry environment. This phenomenon is similar to the uncoated substrate because the solution acts as a lubricant in the early stage of the abrasion test and the sharp wear particles are removed from the wear track as the solution flows by centrifugal force. However, when the abrasion test was performed until the film was destroyed, it was observed that the film was shaved over time due to the wear of a conventional abrasive material in the dry condition. As the wear progresses and the die film is separated from the substrate, the die film is rapidly destroyed.

FIG. 3 shows that the dry specimens were subjected to 3000 cyle, 6000 cyle, and 9000 cyle wear tests using the same specimens. The horizontal lines indicated by the arrows show the scratches on the substrate while the film was deposited on the scratches generated during polishing the substrate. The film is seen deposited along the curvature.

The curvature of the film is still clearly seen when the 3000 cyle is rotated, and after the 6000 cyle is rotated, the curvature is gradually cut off, and when the 9000 cyle is rotated, the curved surface is completely cut off, showing the state that the curvature is not seen. This is typical of conventional wear, which continues until the film is completely worn out and removed.

In a humid environment, as shown in FIG. 4, the wear progressed to a certain extent, and the film was partially dropped. This was not caused by wear, but the film was peeled off, and the surface was measured using a surface profiler. It could be confirmed that the film was peeled off.

The electrochemical test was performed to confirm the chemical resistance of the sample on which the DLC film was deposited. As a result, as shown in the graph of FIG. 5, in the physiological saline, the specimen not coated with the DLC film was more corroded than the coated specimen. As a result, there was no risk of cell death due to corrosion when the DLC film was coated on the artificial organs, and the DLC film had a sufficient role as a chemical barrier. It could be confirmed that it can be performed.

In order to confirm biocompatibility, cytotoxicity test was performed by Agar overlay method (Agar-Overlay, ISOTR7405). As shown in the table of FIG. 6, the substrate coated with the DLC film had a response index (= area index / killing index) of 0/0, indicating that cells were well cultured without cytotoxicity.

In the above embodiment, the wear resistance is improved by depositing a DL film on Ti or TI alloy, but the present invention is not limited thereto. Co-Cr alloy, stainless steel, polymer, ultra high, etc., which can be used as a material of artificial organs, are described. Although it is possible to use molecular weight polyethylene (UHMWPE) or the like as a material, and to form a DLC film by depositing a DLC film on such a material, the idea and scope of the present invention, such as crimping or fusion, have been described. Any number of applications can be made without departing.

As described in detail above, the present invention is a biograft composite coated with the present invention and the manufacturing method is a coating of the DLC film on the material of Ti or Ti alloy mainly used as a base material of biomaterials such as artificial hip joints or artificial teeth As a result, the wear resistance is remarkably improved compared to Ti or the Ti alloy which is not coated, and the chemical resistance and the biocompatibility are good.

Claims (8)

A bio-implanted composite coated with DLC (DLC: Diamond-like Carbon) for improving abrasion resistance on the surface of a Ti substrate which is a basic material of an artificial organ mounted on a human body. [Claim 2] The bio-transplantable composite of claim 1, wherein an intermediate Si layer is deposited between the Ti material and the DL film to improve adhesion of the DL film. Bio-implanted composite coated with DLC (DLC: Diamond-like Carbon) for improving abrasion resistance on the surface of Ti-6Al-4V substrate, which is a basic material of artificial organs mounted on the human body . 4. The biotransport composite of claim 3, wherein an intermediate Si layer is deposited between the Ti-6Al-4V substrate and the DLC film to improve adhesion of the DLC film. Depositing a Si intermediate layer by placing a Ti substrate, a basic material of an artificial organ mounted on a human body, into a deposition apparatus and injecting SiH 4 gas at a pressure of 20 mtorr for 2 minutes and 30 seconds with a 200 bias voltage; A DL film for improving wear resistance on the surface of the Si interlayer by inserting a Ti substrate on which the Si interlayer was deposited into a deposition apparatus and injecting C6H6 gas at a pressure of 10 mtorr for 10 minutes with a 500 bias voltage. : Diamond-like Carbon) A method for producing a bio-composite composite coated with DLC, characterized in that the step of sequentially depositing. The method of claim 5, wherein the Ti substrate is placed in an etching chamber before the Si intermediate layer is deposited, and the etching process is performed for 1 hour at 750 bias voltage under a pressure of 3.8 mtorr. Manufacturing method. Ti-6Al-4V substrate, which is the basic material of artificial organs mounted on the human body, is placed in the deposition equipment and the Si intermediate layer is deposited by generating plasma for 2 minutes and 30 seconds with 200 bias voltage while injecting SiH4 gas at a pressure of 20 mtorr. And a Ti substrate on which the Si intermediate layer is deposited, into a deposition apparatus, and injecting C6H6 gas at a pressure of 10 mtorr to generate a plasma at 500 bias voltage for 10 minutes to improve wear resistance on the surface of the Si intermediate layer. Method for producing a bio-composite composite coated with the DLC characterized in that the step of depositing a diamond film (DLC: Diamond-like Carbon) sequentially. The method of claim 7, wherein the Ti- 6 Al-4V substrate is placed in an etching chamber before the deposition of the Si intermediate layer is subjected to etching for 1 hour at 750 bias voltage under a pressure of 3.8 mtorr is coated. Method for producing a biograft complex.