阅读说明：本技术 一种通过化学气相沉积法制备的医用钽金属骨小梁材料及其制备方法 (Medical tantalum metal bone trabecula material prepared by chemical vapor deposition method and preparation method thereof ) 是由 解凤宝 史春宝 欧阳兆逸 于 2020-05-15 设计创作，主要内容包括：本发明涉及医用器械的技术领域,更具体地说,涉及一种通过化学气相沉积法制备的医用钽金属骨小梁材料及其制备方法,具体包括以下工艺：五氯化钽气体与高纯氢气在900-1050℃的真空环境下反应6-9 h,置换出的钽金属层沉积在基体表面,基体以及沉积在基体表面的钽金属层即为钽金属骨小梁材料；其中,所述五氯化钽气体入真空环境的通入速率为10000~13000 ml/min,所述高纯氢气入真空环境的通入速率为530~570 ml/min,所述真空环境的真空度大于等于4Pa小于等于13.3Pa。在本发明提供的各种反应条件的共同配合下,提高了医用钽金属骨小梁材料的制备效率,且通过上述制备方法制备出的钽金属骨小梁材料孔隙率高、生物相容性好、摩擦系数高,与人体松质骨高度相似,是更为理想的骨植入材料。(The invention relates to the technical field of medical instruments, in particular to a medical tantalum metal trabecular bone material prepared by a chemical vapor deposition method and a preparation method thereof, which specifically comprise the following processes: reacting tantalum pentachloride gas with high-purity hydrogen for 6-9h in a vacuum environment at the temperature of 900-; the introduction rate of the tantalum pentachloride gas into the vacuum environment is 10000-13000ml/min, the introduction rate of the high-purity hydrogen gas into the vacuum environment is 530-570ml/min, and the vacuum degree of the vacuum environment is more than or equal to 4Pa and less than or equal to 13.3 Pa. Under the common cooperation of various reaction conditions provided by the invention, the preparation efficiency of the medical tantalum metal bone trabecula material is improved, and the tantalum metal bone trabecula material prepared by the preparation method has high porosity, good biocompatibility and high friction coefficient, is highly similar to human cancellous bone, and is a more ideal bone implant material.)

1. A preparation method for preparing a medical tantalum metal trabecular bone material by a chemical vapor deposition method is characterized by comprising the following steps: reacting tantalum pentachloride gas with high-purity hydrogen for 6-9h in a vacuum environment at the temperature of 900-; the introduction rate of the tantalum pentachloride gas into the vacuum environment is 10000-13000ml/min, the introduction rate of the high-purity hydrogen gas into the vacuum environment is 530-570ml/min, and the vacuum degree of the vacuum environment is more than or equal to 4Pa and less than or equal to 13.3 Pa.

2. The method for preparing the medical tantalum metal trabecular bone material by the chemical vapor deposition method according to claim 1, which is characterized in that: the tantalum pentachloride gas is prepared by reacting medical pure tantalum and high-purity chlorine gas under the vacuum condition of 1050 ℃ at 900-.

3. The method for preparing the medical tantalum metal trabecular bone material by the chemical vapor deposition method according to claim 1, which is characterized in that: the matrix is a porous carbon matrix, the average pore diameter of the porous carbon matrix is 800 microns from 600 to 250 microns from 100, and the average porosity is 81-90%.

4. The method for preparing the medical tantalum metal trabecular bone material by the chemical vapor deposition method according to claim 1, which is characterized in that: the thickness of the tantalum metal layer deposited on the surface of the substrate is 40-100 mu m.

5. The method for preparing a tantalum metal trabecular bone material for medical use by chemical vapor deposition according to any one of claims 1 or 2, wherein: before the reaction, argon is introduced into the reaction environment, and the introduction rate of the argon is 10000-13000 ml/min.

6. The method for preparing the medical tantalum metal trabecular bone material by the chemical vapor deposition method according to claim 1, which is characterized in that: and introducing tail gas generated in the reaction process into a sodium hydroxide solution for tail gas treatment.

7. The method for preparing a tantalum metal trabecular bone material for medical use by chemical vapor deposition according to any one of claims 1 or 2, wherein: the material of the vacuum environment is any one of a quartz material or a high-purity graphite material.

8. The method for preparing the medical tantalum metal trabecular bone material by the chemical vapor deposition method according to claim 1, which is characterized in that: the above reaction is repeated 3-4 times, and the tantalum metal displaced by each reaction is deposited on the surface of the same substrate.

9. A medical tantalum metal bone trabecula material prepared by a chemical vapor deposition method is characterized in that: the tantalum metal trabecular bone material is prepared by the preparation method of any one of claims 1-8.

Technical Field

The invention relates to the technical field of medical instruments, in particular to a medical tantalum metal trabecular bone material prepared by a chemical vapor deposition method and a preparation method thereof.

Background

Bone implant materials (bone grafts) are mainly used for repairing and filling bone defects or fixing and supporting fractured ends, and comprise autogenous bones, allogenic bones, metal materials, high polymer materials, inorganic non-metal materials and the like. As a human implant, the implant should have good biocompatibility, biocompatibility and human safety biologically; the mechanical aspect needs to have certain strength and elastic modulus close to that of bones, and is wear-resistant and ageing-resistant; stable performance, corrosion resistance, easy disinfection and sterilization, etc. are chemically required. Different implant materials are often selected according to different disease requirements in clinical treatment.

The traditional bone implant materials such as cobalt chromium molybdenum, titanium alloy and the like have the problems of bone dissolution caused by abrasive particles generated by abrasion of joint surfaces, stress shielding of a broach or poor immediate fixing effect after operation and the like, and the reasons are that the materials have poor biocompatibility, high elastic modulus and low friction coefficient. Compared with the traditional bone implant material, the tantalum metal bone trabecula product as a new biomedical material has the advantages of high porosity, good biocompatibility, low elastic modulus, high friction coefficient, high strength and the like, and the structure of the tantalum metal bone trabecula product is highly similar to that of human cancellous bone, so that the tantalum metal bone trabecula product is a more ideal bone implant material. The tantalum metal trabecular bone material is used as a bone implant material, so that the problems can be solved, the postoperative revision rate can be greatly reduced, the service life of the prosthesis is prolonged, and the pain of a patient is reduced.

The common preparation technology of the existing tantalum metal bone trabecula product comprises the following steps: laser sintering techniques, foam impregnation techniques, and chemical vapor deposition techniques. Wherein, because the melting point of tantalum metal is extremely high and can reach 3000 ℃, the power of equipment used in the laser sintering technology is higher, the energy consumption is larger, and the method is not suitable for large-scale industrial production; as a new technology, the foam impregnation technology is difficult to realize batch production at the laboratory preparation stage at present; the chemical vapor deposition technology is the most stable chemical vapor deposition technology, is most suitable for industrial production and is the most feasible tantalum metal trabecular bone material preparation technology for the current industrial production because of low process difficulty, simple operation and high yield. The tantalum metal trabecula bone is used as a new medical material, and the large-scale preparation process is still in the research and development stage.

Disclosure of Invention

Aiming at the defects in the prior art, the first purpose of the invention is to provide a preparation method for preparing a medical tantalum metal trabecular bone material by a chemical vapor deposition method, aiming at the problem that the preparation process for the medical tantalum metal trabecular bone material in the prior art is still in a research and development stage, the preparation process for preparing the medical tantalum metal trabecular bone material by the chemical vapor deposition method is deeply researched, the preparation efficiency of the medical tantalum metal trabecular bone material is improved under the common cooperation of various reaction conditions provided by the invention, and the optimal preparation process condition for preparing the medical tantalum metal trabecular bone material is obtained through research. The tantalum metal bone trabecula material prepared by the preparation method has high porosity, good biocompatibility, high friction coefficient and high strength, is highly similar to human cancellous bone, and is a more ideal bone implant material.

In order to achieve the first object, the invention provides the following technical scheme: a preparation method for preparing a medical tantalum metal trabecular bone material by a chemical vapor deposition method is characterized by comprising the following steps: reacting tantalum pentachloride gas with high-purity hydrogen for 6-9h in a vacuum environment at the temperature of 900-; the introduction rate of the tantalum pentachloride gas into the vacuum environment is 10000-13000ml/min, the introduction rate of the high-purity hydrogen gas into the vacuum environment is 530-570ml/min, and the vacuum degree of the vacuum environment is more than or equal to 4Pa and less than or equal to 13.3 Pa.

Through the technical scheme, the tantalum metal in the tantalum pentachloride gas is replaced by utilizing the high-purity hydrogen in the vacuum environment, the replaced tantalum metal is deposited on the surface of the substrate and forms a medical tantalum metal trabecular bone material together with the substrate, and through multiple trials and experimental researches, the reaction temperature of the tantalum pentachloride gas and the high-purity hydrogen is 900-1050 ℃, the reaction time is within the range of 6-9h, and the efficiency of the tantalum metal layer replaced by the reaction is the highest under the mutual matching of the reaction temperature and the reaction time, so that the reaction conditions are controlled within 900-1050 ℃ and 6-9 h; in addition, through practice and attempt for many times, under the reaction condition of the method, when the introduction rate of the high-purity hydrogen is 530-570ml/min and the introduction rate of the tantalum pentachloride gas is 10000-13000ml/min, the method is favorable for improving the replacement efficiency of the whole reaction on the tantalum metal in the tantalum pentachloride gas; in addition, in the reaction process, the vacuum degree of the reaction environment is controlled to be more than or equal to 4Pa and less than or equal to 13.3Pa, and if the vacuum degree is more than 13.3Pa, the tantalum pentachloride gas can react with water in the air in the reaction process to generate a by-product tantalum oxychloride (TaOCl)₃) Because the tantalum in the tantalum oxychloride can not be replaced by the high-purity hydrogen, the content of the tantalum which can be replaced in the reaction can be reduced, and the overall reaction efficiency is reduced, therefore, the vacuum degree is required to be kept to be more than or equal to 4Pa and less than or equal to 13.3Pa in the reaction environment, the moisture in the reaction environment is reduced as much as possible, the occurrence of side reactions is avoided as much as possible, and the preparation efficiency of the medical tantalum trabecular metal bone material is improved.

The main function of the substrate is as a carrier coated by the deposition of the replaced tantalum metal, and the medical tantalum metal layer finally attached to the surface of the substrate and the substrate are used together as a tantalum metal trabecular bone material for clinical application. Therefore, the substrate is placed in the reaction environment, the preparation of the medical tantalum metal trabecular bone product is synchronously carried out while the replacement reaction is carried out, the tantalum metal replaced by the replacement reaction is continuously deposited on the surface of the substrate, and the porous tantalum metal layer is formed on the surface of the substrate. According to the clinical requirement on the shape of the tantalum metal trabecular bone product, a substrate with a corresponding shape can be placed in a reaction environment to prepare the medical tantalum metal trabecular bone material with a corresponding shape so as to adapt to the clinical requirement on the tantalum metal trabecular bone material. And because the replacement reaction is continuously carried out, the replaced tantalum metal is continuously deposited on the surface of the porous substrate, the porous property of the tantalum metal trabecular bone material is formed, and the porosity is high. The preparation method of the invention has low difficulty and simple operation, and improves the preparation efficiency of the medical tantalum metal bone trabecula material under the condition of the reaction temperature, the reaction time, the vacuum degree, the introduction rate of the tantalum pentachloride gas and the high-purity argon gas and the like, and the tantalum metal bone trabecula material prepared by the preparation method has high porosity, good biocompatibility, high friction coefficient and high strength, is highly similar to human cancellous bone, and is a more ideal bone implantation material.

Further, the tantalum pentachloride gas is prepared by reacting medical pure tantalum and high-purity chlorine gas under the vacuum condition of 900-1050 ℃, the introducing speed of the high-purity chlorine gas is 200-240ml/min, and the vacuum degree of the reaction environment is more than or equal to 4Pa and less than or equal to 13.3 Pa.

By adopting the technical scheme, the tantalum pentachloride gas is taken as the replacement gas for replacing the tantalum metal, and the obtaining mode of the tantalum pentachloride gas is two, wherein one is directly purchased from the market, and the other is used for the current preparation. The medical pure tantalum and the high-purity chlorine gas are used for preparing the tantalum pentachloride gas, and the chlorine gas is active and can react with the tantalum under certain conditions to generate the tantalum pentachloride, and the boiling point of the tantalum pentachloride is 242 ℃, so the tantalum pentachloride is in a gaseous state in the reaction process. The tantalum pentachloride gas generated by the reaction is used as replacement gas for preparing the trabecular bone material of the tantalum metal and is prepared with high-purity hydrogen under certain conditions. In the reaction environment for preparing the tantalum pentachloride gas, the vacuum degree is required to be kept to be more than or equal to 4Pa and less than or equal to 13.3Pa, so that the tantalum pentachloride gas is prevented from reacting with water in the air to generate a by-product tantalum oxychloride, and the replacement efficiency of tantalum metal in the final replacement reaction is reduced; on the other hand, the material of the substrate and the reaction chamber may be flammable, and the isolation of air is effective to prevent the reaction chamber and the substrate in the reaction chamber from burning due to the presence of oxygen in the air.

Further, the substrate is a porous carbon substrate, the average pore diameter of the porous carbon substrate is 600-800 μm, the average filament diameter is 100-250 μm, and the average porosity is 81-90%.

By adopting the technical scheme, the carbon material is relatively stable, cannot react with the replaced tantalum metal, and can be used as an ideal carrier for tantalum metal deposition and coating. The tantalum metal replaced by the reaction is deposited on the surface of the porous carbon substrate, and due to the porous structure of the porous carbon substrate, the tantalum metal forms a porous structure which is adaptive to the shape of the porous carbon substrate on the surface of the porous carbon substrate, and the porous carbon substrate and the tantalum metal layer deposited on the surface of the porous carbon substrate jointly form a combination of carbon and tantalum, and the combination is used as a medical tantalum metal bone trabecula material to be applied to clinical medical treatment. The porous carbon substrate has various shapes, and a porous carbon substrate having an appropriate shape can be selected according to the shape of the medical tantalum metal trabecula which is actually required.

Further, the thickness of the tantalum metal layer deposited on the surface of the substrate is 40-100 μm.

By adopting the technical scheme, through experimental analysis, the thickness of the tantalum metal layer which is displaced from the tantalum pentachloride gas by utilizing the high-purity hydrogen and is deposited on the surface of the porous carbon substrate by utilizing the preparation method is within the range of 40-100 mu m. In practical clinical application, medical tantalum metal trabecular bone materials with tantalum metal layers with different thicknesses can be prepared according to requirements.

Further, argon is introduced into the reaction environment before the reaction, and the introduction rate of the argon is 10000-13000 ml/min.

By adopting the technical scheme, the argon is colorless and tasteless inert gas, has stable chemical property and is inactive and difficult to react with other substances, the argon is used as protective gas for replacement reaction, the reaction of medical pure tantalum and high-purity chlorine and the reaction of tantalum pentachloride gas and high-purity hydrogen can be isolated from oxygen, the oxidation reaction of the tantalum-containing gas is prevented from occurring in the reaction, a tantalum-containing byproduct which cannot be replaced by the hydrogen is generated, the content of the tantalum metal which can be replaced in the reaction is reduced, and the overall reaction efficiency is reduced. In addition, the material of the substrate and the reaction cavity can be flammable, and the isolation of air can effectively prevent the reaction cavity and the substrate in the reaction cavity from burning due to the existence of oxygen in the air. Therefore, the argon is used as the protective gas in the reaction process of the medical pure tantalum and the high-purity chlorine and the reaction process of the tantalum pentachloride gas and the high-purity hydrogen, so that the integral reaction efficiency can be further ensured, the waste of the tantalum is reduced, and the deposition rate of the tantalum metal is improved. Another purpose of the argon gas during the reaction of the tantalum pentachloride gas and the high purity hydrogen gas is to push the tantalum pentachloride gas into the reactor. In addition, in order to ensure that the vacuum degree in the reactor meets the requirement of replacing the reaction, after the reactor is vacuumized to a certain degree, argon is introduced into the reaction cavity so as to meet the requirement of the vacuum degree in the reactor for the reaction.

And further, introducing tail gas generated in the reaction process into a sodium hydroxide solution for tail gas treatment.

By adopting the technical scheme, in the reaction process, the high-purity hydrogen gas reacts with the tantalum pentachloride gas to replace the tantalum metal in the tantalum pentachloride gas, and the tantalum metal is deposited on the surface of the substrate, so that hydrogen chloride gas and other gases with incomplete reaction can be generated in the reaction process. After the reaction is finished, the hydrogen chloride gas is taken as a typical representative of the residual tail gas and needs to be treated, the residual tail gas is introduced into a tail gas treatment device, a sodium hydroxide solution is arranged in the tail gas treatment device, substances in the tail gas can react with the sodium hydroxide solution to produce sodium chloride and water, and the tail gas is subjected to harmless treatment.

Further, the material of the vacuum environment is any one of a quartz material or a high-purity graphite material.

By adopting the technical scheme, as quartz and graphite have good chemical stability, thermal conductivity and corrosion resistance, the reactor is a better heat exchanger and reactor, and in the process of preparing the medical tantalum metal bone trabecula material, the quartz material and the graphite material are used as the reactor, so that the preparation efficiency of the medical tantalum metal bone trabecula material is further guaranteed.

Further, the above reaction is repeated 3 to 4 times, and the tantalum metal displaced by each reaction is deposited on the same substrate surface.

By adopting the technical scheme, in order to ensure the deposition thickness and the structural strength of the replaced tantalum metal on the surface of the substrate, the reaction is repeated for 3-4 times, the tantalum metal replaced by the reaction is deposited on the surface of the same substrate every time, and compared with the tantalum metal prepared by only one reaction, the tantalum metal replaced by multiple reactions is accumulated and deposited on the surface of the substrate, so that the deposition thickness and the structural strength of the tantalum metal on the surface of the substrate are improved.

The second purpose of the invention is to provide a medical tantalum metal trabecular bone material prepared by a chemical vapor deposition method, wherein the medical tantalum metal trabecular bone material is prepared by the preparation method.

By adopting the technical scheme, the medical tantalum metal bone trabecula material prepared by the method has high porosity, good biocompatibility, low elastic modulus, high friction coefficient and high strength, is applied to the manufacturing of tantalum metal bone trabecula products, has a structure similar to the height of human cancellous bone, and is a more ideal bone implantation material.

In conclusion, the invention has the following beneficial effects:

1. aiming at the fact that the preparation process of the medical tantalum metal trabecular bone material in the prior art is still in the research and development stage, the preparation process of the medical tantalum metal trabecular bone material prepared by the chemical vapor deposition method is deeply researched, the preparation efficiency of the medical tantalum metal trabecular bone material is improved under the common cooperation of various reaction conditions provided by the invention, and the optimal preparation process condition for preparing the medical tantalum metal trabecular bone material is obtained through the research. The tantalum metal bone trabecula material prepared by the preparation method has high porosity, good biocompatibility, high friction coefficient and high strength, is highly similar to human cancellous bone, and is a more ideal bone implant material.

2. The tantalum metal trabecular bone material prepared by the method has the advantages of high porosity, good biocompatibility, low elastic modulus, high friction coefficient, high strength and the like, and is an ideal bone implant material. The medical tantalum metal bone trabecula material prepared by the preparation method has better application prospect.

3. The invention carries out harmless treatment on tail gas generated in the preparation process of the medical tantalum metal trabecula material, and accords with the concepts of environmental protection and sustainable development.

Detailed Description

The quartz reaction chamber involved in the invention is manufactured by CVD Equipment Corporation, and has the model number of N1213M 2103-00; a high-purity graphite reaction cavity, wherein the manufacturer is CVD Equipment Corporation, and the model is N1213M 2116; the tail gas treatment device is EE405 tail gas treatment Equipment, and the manufacturer is CVD Equipment Corporation; medical pure tantalum is available from Ningxia Oriental tantalum industry Co.

The invention provides a preparation method for preparing a medical tantalum metal trabecular bone material by a chemical vapor deposition method, which comprises the following steps:

(1) the medical pure tantalum is put into the first reaction cavity, the porous carbon substrate is put into the second reaction cavity, the first reaction cavity and the second reaction cavity are respectively sealed, the average pore diameter of the porous carbon substrate is 800 microns, the average filament diameter is 100 microns, the average porosity is 81-90%, and the first reaction cavity and the second reaction cavity can be any one of a quartz reaction cavity or a high-purity graphite reaction cavity;

(2) respectively vacuumizing the first reaction cavity and the second reaction cavity to a certain degree, then respectively introducing argon into the first reaction cavity and the second reaction cavity, wherein the flow rate of the introduced argon is 10000-13000ml/min, and ensuring that the vacuum degrees in the first reaction cavity and the second reaction cavity are more than or equal to 4Pa and less than or equal to 13.3 Pa;

(3) introducing high-purity chlorine into the first reaction cavity, wherein the introduction rate of the high-purity chlorine is 200-240ml/min, reacting at the temperature of 900-1050 ℃, and generating tantalum pentachloride gas from the high-purity chlorine and the medical pure tantalum;

(4) mixing the tantalum pentachloride gas generated in the step (3) and argon gas, introducing the mixed gas into a second reaction cavity at the introducing speed of 10000-13000ml/min, introducing high-purity hydrogen into the second reaction cavity at the introducing speed of 530-570ml/min, reacting at the temperature of 900-1050 ℃ for 6-9h, and replacing tantalum metal;

(5) depositing the tantalum metal replaced in the step (4) on the surface of the porous carbon substrate, wherein the thickness of the tantalum metal layer deposited on the surface of the porous carbon substrate is 40-100 mu m; meanwhile, with the generation of tail gas, introducing the tail gas into a tail gas treatment device with a sodium hydroxide solution for tail gas treatment, wherein the tail gas treated by the tail gas treatment device is discharged after meeting the discharge standard of the national standard (GB 31573-;

(6) repeating the step (4) and the step (5) for 3-4 times, depositing the tantalum metal replaced each time on the surface of the same porous carbon substrate, and finally obtaining the tantalum metal layer with better deposition thickness and structural strength on the surface of the porous carbon substrate, wherein the tantalum metal layer and the porous carbon substrate jointly form the tantalum metal bone trabecula material.

The invention also provides the medical tantalum metal bone trabecula material prepared by the method, the porosity of the prepared medical tantalum metal layer is 50-80%, the pore connectivity is more than 95%, and the thickness is within the range of 40-100 mu m. The friction force of the tantalum metal bone trabecula material on the cancellous bone can reach 0.88 to the maximum extent, compared with other materials in the prior art, the friction force on the cancellous bone is remarkably improved, the hardness of the prepared tantalum metal bone trabecula is 3GPa, the maximum bone grafting stress reaches 67 percent, and the tantalum metal bone trabecula material is highly similar to the cancellous bone of a human body and is a more ideal bone implantation material.

The present invention will be described in further detail with reference to examples 1 to 10, comparative examples 1 to 8, and the corresponding test results.