CN113319283A - Airflow milling pretreatment and trace hydrogen auxiliary sintering method for titanium coating - Google Patents

Airflow milling pretreatment and trace hydrogen auxiliary sintering method for titanium coating Download PDF

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CN113319283A
CN113319283A CN202110625354.5A CN202110625354A CN113319283A CN 113319283 A CN113319283 A CN 113319283A CN 202110625354 A CN202110625354 A CN 202110625354A CN 113319283 A CN113319283 A CN 113319283A
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CN113319283B (en
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孙晓华
陈敏
王应静
牛永良
尹琳洁
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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
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    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • A—HUMAN NECESSITIES
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    • B22F2009/044—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by jet milling
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Abstract

The invention discloses a jet mill pretreatment and trace hydrogen auxiliary sintering method for a titanium coating, and relates to a jet mill treatment and trace hydrogen auxiliary sintering cooperative processing method for improving the bonding strength of titanium particles and a matrix. The method comprises the following two steps: firstly, putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon, then introducing 4N high-purity hydrogen to 0.105-0.110 MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, carrying out jet milling for 10-120 minutes at the speed of 300-500 m/s on airflow in a fluidized bed, and screening titanium powder particles with proper particle size as powder particles for coating for later use after the jet milling is finished; and secondly, placing titanium powder particles meeting the technical requirements of the implant on the surface of the cleaned implant, transferring the treated implant into a vacuum furnace, opening a high vacuum system, heating to the sintering temperature of 1000-1400 ℃, preserving heat at the sintering temperature, cooling to room temperature, taking out the implant with the sintered titanium bead coating, cleaning and packaging.

Description

Airflow milling pretreatment and trace hydrogen auxiliary sintering method for titanium coating
Technical Field
The invention discloses an airflow mill pretreatment and trace hydrogen auxiliary sintering method for a titanium coating, relates to an airflow mill treatment and trace hydrogen auxiliary sintering cooperative processing method for improving the bonding strength of titanium particles and a matrix, is a preparation method of an open type porous titanium coating, and belongs to the field of powder metallurgy materials and biological materials. The titanium alloy coating is suitable for improving the performance of implants in orthopaedics, dentistry and the like, and particularly improves the bonding strength of the porous titanium coating on the surface of the implant and a titanium alloy matrix.
Background
Implant coating technology has matured over the years. Taking an artificial joint as an example, the current mature process mainly comprises an air plasma spraying process, a vacuum sintering process and an electrochemical process, and the coating material mainly comprises titanium, hydroxyapatite (HA for short) and the combination of the titanium and the hydroxyapatite. The current major bio-coating technology for bio-type artificial joints, which uses vacuum sintering of titanium coating and plasma spraying of HA on the titanium coating, HAs found a number of applications in bio-type artificial joints due to its excellent bone ingrowth clinical effect and low cost, such as SUMMIT total hip prosthesis and PFC total knee prosthesis of DEPUY, NEXGEN total knee prosthesis of ZIMMER, PROFIX total knee prosthesis of SMITH-NEPHEW, and MAXIN total knee prosthesis of BIOMET.
The titanium coating is formed on the surface of the titanium alloy substrate through vacuum sintering, the bonding strength of the titanium coating and the titanium alloy substrate determines whether the workpiece can enter a subsequent process, and on the premise that the titanium coating is ensured to have proper porosity, the titanium coating and the titanium alloy substrate need to have enough connection strength, which is the premise that the safety of an implant, the bone bonding strength and the bone growth effect are guaranteed. However, the connection strength between the titanium coating prepared by the conventional sintering process and the titanium alloy substrate is often low under the condition of ensuring the porosity, so that the reliability of the coating is reduced. The powder adopted by the vacuum sintering titanium coating mainly comprises spherical titanium powder and irregular titanium powder, and the problem of low connection strength of the coating and the substrate is particularly prominent when the irregular titanium powder is adopted. Therefore, subsequent analysis and experiments mainly focus on the situation when irregular titanium powder is selected for the coating, and the invention for solving the problem is obviously also applicable to spherical titanium powder.
Disclosure of Invention
Aiming at the defects, the invention provides the jet mill pretreatment and trace hydrogen auxiliary sintering method of the titanium coating, and is a jet mill treatment and trace hydrogen auxiliary sintering synergistic processing method for improving the bonding strength of titanium particles and a matrix.
The airflow milling pretreatment and trace hydrogen auxiliary sintering method of the titanium coating is realized by adopting the following technical scheme:
the airflow milling pretreatment and trace hydrogen auxiliary sintering method of the titanium coating comprises two steps:
firstly, putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, then introducing 4N high-purity hydrogen gas to be 0.105-0.110 MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, jet milling the gas flow in a fluidized bed for 10-120 minutes at the speed of 300-500 m/s, and screening titanium powder particles with proper particle size as powder particles for coating for later use after the jet mill is finished.
Secondly, titanium powder particles which meet the technical requirements of the implant are placed on the surface of the cleaned implant, titanium powder particles with the average thickness of 600-800 mu m are placed on the surface of the titanium alloy implant, the treated implant is moved into a vacuum furnace and is vacuumized to 10 DEG, and the surface of the implant is cleaned-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to 500-600 ℃ at the speed of 1-30 ℃/min, then cooling to 320-380 ℃, closing the high vacuum system, only starting the mechanical pump, introducing micro-flow hydrogen to keep the pressure in the furnace at 30-60 Pa, preserving the heat for 30-80 minutes, opening the high vacuum system, and vacuumizing to less than 5 x 10-2Heating to 1000-1400 ℃ at the speed of 15-30 ℃/min, preserving the heat at the sintering temperature for 0.5-10 hours, cooling from the sintering temperature to room temperature at the speed of 1-10 ℃/min, taking out the implant with the sintered titanium bead coating, cleaning with distilled water and medical alcohol, and packaging.
The particle size of the pretreated titanium powder particles is 50-250 micrometers (mum).
After the jet mill treatment and the trace hydrogen treatment are cooperatively adopted, the bonding strength of the titanium alloy particle coating and the matrix is further effectively improved: if no treatment is carried out, the bonding strength is 40-55 MPa; the jet milling treatment is independently carried out, and the bonding strength is improved to 65-80 MPa; carrying out micro hydrogen treatment independently, and improving the bonding strength to 68-78 MPa; after the jet mill treatment and the trace hydrogen treatment are cooperatively adopted, the bonding strength of the titanium alloy particle coating and the matrix can be improved to 100-115 MPa. The coating keeps a good space structure of the high vacuum sintering titanium coating, and greatly improves the bonding strength of the titanium coating on the surface of the implant and the titanium alloy matrix through synergistic treatment, thereby improving the reliability and safety of the implant. And the process has low cost.
The invention has the advantages that:
the porous titanium coating is made on the surface of the implant, so that new bone tissues grow into pores of the porous titanium bead coating, and the implant and the bone tissues are fixed together. This manner of implant fixation by bone growth into porous surfaces is called biological fixation. Due to the fact that bone tissues grow into the pores, the area of the interface between the bone and the implant is greatly increased, and due to the mechanical embedding effect between the bone and the porous surface, the shearing strength of the interface between the implant and the bone is also greatly increased. However, in the process of vacuum sintering of the porous titanium coating, it is found that the connection strength between the titanium coating prepared by the conventional sintering process and the titanium alloy substrate is often low under the condition of ensuring the porosity, so that the reliability of the coating is insufficient. The powder adopted by the vacuum sintering titanium coating mainly comprises spherical titanium powder and irregular titanium powder, and the problem of low connection strength of the coating and the substrate is particularly prominent when the irregular titanium powder is adopted.
Aiming at the defects, the invention provides a jet mill treatment and trace hydrogen-assisted sintering synergistic processing method for improving the bonding strength of titanium particles and a matrix. The method comprises two steps: firstly, putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, then introducing 4N high-purity hydrogen gas to be 0.105-0.110 MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, jet milling the gas flow in a fluidized bed for 10-120 minutes at the speed of 300-500 m/s, and screening titanium powder particles with proper particle size as powder particles for coating for later use after the jet mill is finished. Secondly, titanium powder particles which meet the technical requirements of the implant are placed on the surface of the cleaned implantThe surface of the implant is treated, the treated implant is moved into a vacuum furnace and is vacuumized to 10 DEG-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to 500-600 ℃ at the speed of 1-30 ℃/min, then cooling to 320-380 ℃, closing the high vacuum system, only starting the mechanical pump, introducing micro-flow hydrogen to keep the pressure in the furnace at 30-60 Pa, preserving heat for 30-80 minutes, opening the high vacuum system, heating to the sintering temperature of 1000-1400 ℃ at the speed of 15-30 ℃/min, preserving heat for 0.5-10 hours at the sintering temperature, cooling from the sintering temperature to room temperature at the speed of 1-10 ℃/min, taking out the implant with the sintered titanium bead coating, cleaning with distilled water and medical alcohol, and packaging. The coating keeps a good space structure of a high vacuum sintering titanium coating, and greatly improves the bonding strength of the titanium coating on the surface of the implant and a titanium alloy matrix through synergistic treatment, no hydride exists in a final finished product, and the product meets all requirements of biological performance detection such as cytotoxicity test, sensitization test, intradermal reaction test, acute systemic toxicity (venous approach), genetic toxicity test (Ames) and the like.
The jet mill treatment and trace hydrogen-assisted sintering cooperative processing method for improving the bonding strength of the vacuum sintering titanium alloy particle coating and the matrix effectively improves the bonding performance of the titanium alloy coating and the matrix, improves the reliability and safety of the implant, and has low process cost.
Detailed Description
The airflow milling treatment and trace hydrogen auxiliary sintering method of the titanium powder particle coating comprises two steps:
firstly, putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, then introducing 4N high-purity hydrogen gas to be 0.105-0.110 MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, jet milling the gas flow in a fluidized bed for 10-120 minutes at the speed of 300-500 m/s, and screening titanium powder particles with proper particle size as powder particles for coating for later use after the jet mill is finished.
The particle size of the pretreated titanium powder particles is 50-250 micrometers (mum).
Secondly, placing titanium powder particles meeting the technical requirements of the implant on the surface of the cleaned implant, placing titanium powder particles with the average thickness of 800 mu m on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10 DEG C-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to 500-600 ℃ at the speed of 1-30 ℃/min, then cooling to 320-380 ℃, closing the high vacuum system, only starting the mechanical pump, introducing micro-flow hydrogen to keep the pressure in the furnace at 30-60 Pa, preserving the heat for 30-80 minutes, opening the high vacuum system, and vacuumizing to less than 5 x 10-2Heating to 1000-1400 ℃ at the speed of 15-30 ℃/min, preserving the heat at the sintering temperature for 0.5-10 hours, cooling from the sintering temperature to room temperature at the speed of 1-10 ℃/min, taking out the implant with the sintered titanium bead coating, cleaning with distilled water and medical alcohol, and packaging.
After the jet mill treatment and the trace hydrogen treatment are cooperatively adopted, the bonding strength of the titanium alloy particle coating and the matrix is further effectively improved: if no treatment is carried out, the bonding strength is 40-55 MPa; the jet milling treatment is independently carried out, and the bonding strength is improved to 65-80 MPa; carrying out micro hydrogen treatment independently, and improving the bonding strength to 68-78 MPa; after the jet mill treatment and the trace hydrogen treatment are cooperatively adopted, the bonding strength can be improved to 100-115 MPa. The coating keeps a good space structure of the high vacuum sintering titanium coating, and greatly improves the bonding strength of the titanium coating on the surface of the implant and the titanium alloy matrix through synergistic treatment, thereby improving the reliability and safety of the implant. And the process has low cost.
The invention will be further illustrated with reference to the following examples:
comparative example 1:
screening titanium powder particles with proper particle size by using a standard sieve to serve as coating powder, placing titanium particles with average thickness of 800 mu m on the surface of a titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10 DEG-2Heating above PaAnd (5) sintering. The sintering system is as follows: heating from room temperature to 1400 ℃ at the speed of 5 ℃/min, preserving the heat at the sintering temperature for 0.5 hour, then cooling from the sintering temperature to room temperature at the speed of 1 ℃/min, and taking out the implant with the sintered titanium bead coating and the furnace strength test sample. Cleaning with distilled water and medical alcohol, and packaging. The tensile strength of the titanium granule coating of the strength test specimen was measured according to the ASTM F1147 or EN 582 standard, and the tensile strength was 48 MPa.
Comparative example 2:
putting titanium powder particles to be treated into fluidized bed type jet mill equipment, introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, introducing 4N high-purity hydrogen gas to be 0.108MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, carrying out jet milling on the air flow in a fluidized bed for 55 minutes at the speed of 400 m/s, and screening the titanium powder particles with proper particle size to be used as coating powder particles for later use after the jet mill is finished. Placing titanium particles with the average thickness of 800 mu m on the surface of a titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10 DEG-2Heating and sintering above Pa. The sintering system is as follows: heating from room temperature to 1400 ℃ at the speed of 5 ℃/min, preserving the heat at the sintering temperature for 0.5 hour, then cooling from the sintering temperature to room temperature at the speed of 1 ℃/min, and taking out the implant with the sintered titanium bead coating and the furnace strength test sample. Cleaning with distilled water and medical alcohol, and packaging. The tensile strength of the titanium granule coating of the strength test specimen was measured according to ASTM F1147 or EN 582 standard, and the tensile strength was 71 MPa.
Comparative example 3:
screening titanium powder particles with proper particle size by using a standard sieve to serve as coating powder, placing titanium particles with average thickness of 800 mu m on the surface of a titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10 DEG-2Heating and sintering above Pa. The sintering system is as follows: heating from room temperature to 550 deg.C at a speed of 15 deg.C/min, cooling to 350 deg.C, closing high vacuum system, starting mechanical pump, introducing trace flow hydrogen gas to maintain pressure in furnace at 45 Pa, maintaining for 50 min, opening high vacuum system, and heating at 22 deg.CHeating to the sintering temperature of 1200 ℃ at a speed of/min, preserving the heat at the sintering temperature for 5 hours, cooling from the sintering temperature to room temperature at a speed of 5 ℃/min, and taking out the implant with the sintered titanium bead coating and the furnace strength test sample. Cleaning with distilled water and medical alcohol, and packaging. The tensile strength of the titanium granule coating of the strength test specimen was measured according to the ASTM F1147 or EN 582 standard, and the tensile strength was 72 MPa.
Example 1:
putting titanium powder particles to be treated into fluidized bed type jet mill equipment, introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, introducing 4N high-purity hydrogen gas to be 0.108MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, carrying out jet milling on the air flow in a fluidized bed for 55 minutes at the speed of 400 m/s, and screening the titanium powder particles with proper particle size to be used as coating powder particles for later use after the jet mill is finished.
Placing titanium powder particles with the average thickness of 600 mu m on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10 DEG-2Heating and sintering above Pa. The sintering system is as follows: heating from room temperature to 550 deg.C at a speed of 15 deg.C/min, cooling to 350 deg.C, closing the high vacuum system, starting the mechanical pump, introducing micro-flow hydrogen gas to maintain the pressure in the furnace at 45 Pa, maintaining the temperature for 50 min, opening the high vacuum system, and vacuumizing to less than 5 x 10-2Heating to the sintering temperature of 1200 ℃ at the speed of 22 ℃/min, preserving the heat at the sintering temperature for 5 hours, cooling from the sintering temperature to the room temperature at the speed of 5 ℃/min, and taking out the implant with the sintered titanium bead coating and the furnace strength test sample. Cleaning with distilled water and medical alcohol, and packaging. The tensile strength of the titanium granule coating of the strength test specimen was measured according to the ASTM F1147 or EN 582 standard, and the tensile strength was 110 MPa.
Example 2:
putting titanium powder particles to be treated into fluidized bed type jet mill equipment, introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, introducing 4N high-purity hydrogen gas to be 0.105MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, carrying out jet milling on the air flow in a fluidized bed for 120 minutes at the speed of 300 m/s, and screening the titanium powder particles with proper particle size as coating powder particles for later use after the jet mill is finished.
Placing titanium powder particles with the average thickness of 1000 mu m on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10 DEG-2Heating and sintering above Pa. The sintering system is as follows: heating from room temperature to 500 deg.C at a speed of 1 deg.C/min, cooling to 320 deg.C, closing the high vacuum system, starting the mechanical pump, introducing micro-flow hydrogen gas to maintain the pressure in the furnace at 30 Pa, maintaining the temperature for 30 min, opening the high vacuum system, and vacuumizing to less than 5 x 10-2Heating to 1000 ℃ at the speed of 15 ℃/min, preserving the heat at the sintering temperature for 0.5 hour, cooling from the sintering temperature to room temperature at the speed of 1 ℃/min, and taking out the implant with the sintered titanium bead coating and the furnace strength test sample. Cleaning with distilled water and medical alcohol, and packaging. The tensile strength of the titanium granule coating of the strength test specimen was measured according to the ASTM F1147 or EN 582 standard, and the tensile strength was 100 MPa.
Example 3:
putting titanium powder particles to be treated into fluidized bed type jet mill equipment, introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, introducing 4N high-purity hydrogen gas to be 0.110MPa, opening a high-pressure pump to enable the gas to generate internal circulation motion, carrying out jet milling on the air flow in a fluidized bed for 10 minutes at the speed of 500 m/s, and screening the titanium powder particles with proper particle size to serve as powder particles for coating for later use after the jet mill is finished.
Placing titanium powder particles with the average thickness of 800 mu m on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10 DEG-2Heating and sintering above Pa. The sintering system is as follows: heating from room temperature to 600 deg.C at 30 deg.C/min, cooling to 380 deg.C, closing the high vacuum system, starting the mechanical pump, introducing trace flow hydrogen gas to maintain the pressure in the furnace at 60 Pa, maintaining the temperature for 80 min, opening the high vacuum system, and vacuumizingAt 5 x 10-2Heating to 1400 deg.c at 30 deg.c/min, maintaining at the sintering temperature for 10 hr, cooling to room temperature at 10 deg.c/min, and taking out the sintered titanium bead coated implant and the furnace strength test sample. Cleaning with distilled water and medical alcohol, and packaging. The tensile strength of the titanium granule coating of the strength test specimen was tested according to ASTM F1147 or EN 582 standard, and the tensile strength was 115 MPa.
The biological performance of the treated implant was tested, and the test items included cytotoxicity test, sensitization test, intradermal reaction test, acute systemic toxicity (intravenous route), and genotoxicity test (Ames). The detection criteria according to are:
1) GB/T16886.5-2003 medical devices biology evaluation fifth part: in vitro cytotoxicity test;
2) the tenth part of the biological evaluation of GB/T16886.10-2005 medical devices: stimulation and delayed type hypersensitivity tests;
3) GB/T16886.11-1997 eleventh part of the Biol evaluation of medical devices: systemic toxicity test;
4) GB/T16886.3-1997 medical devices biology evaluation third part: genotoxicity, carcinogenicity, and reproductive toxicity tests;
5) the pharmacopoeia of the people's republic of China 2005 edition appendix XID pyrogen test.
The detection result shows that the treated implant meets the five standard requirements.
The invention relates to a preparation method for obtaining a high-bonding-strength, bioactive and open type porous non-spherical titanium powder particle coating on the surface of an implant. The implant is suitable for biological fixation type implants in orthopedics, dentistry and the like, and can improve the bone ingrowth effect of the implants, improve the bone combination strength and improve the reliability of the implants. The method comprises two steps: firstly, putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, then introducing 4N high-purity hydrogen gas to be 0.105-0.110 MPa, opening a high-pressure pump to ensure that the gas generates internal circulation motion,and (3) carrying out air flow milling for 10-120 minutes by air flow in the fluidized bed at the speed of 300-500 m/s, and screening titanium powder particles with proper particle sizes after the air flow milling is finished to be used as powder particles for coating for later use. Secondly, titanium powder particles which meet the technical requirements of the implant are placed on the surface of the cleaned implant, the treated implant is moved into a vacuum furnace and is vacuumized to 10 DEG-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to 500-600 ℃ at the speed of 1-30 ℃/min, then cooling to 320-380 ℃, closing the high vacuum system, only starting the mechanical pump, introducing micro-flow hydrogen to keep the pressure in the furnace at 30-60 Pa, preserving the heat for 30-80 minutes, opening the high vacuum system, and vacuumizing to less than 5 x 10-2Heating to 1000-1400 ℃ at the speed of 15-30 ℃/min, preserving the heat at the sintering temperature for 0.5-10 hours, cooling from the sintering temperature to room temperature at the speed of 1-10 ℃/min, taking out the implant with the sintered titanium bead coating, cleaning with distilled water and medical alcohol, and packaging. After the jet mill treatment and the trace hydrogen treatment are cooperatively adopted, the bonding strength of the titanium alloy particle coating and the matrix is further effectively improved: if no treatment is carried out, the bonding strength is 40-55 MPa; the jet milling treatment is independently carried out, and the bonding strength is improved to 65-80 MPa; carrying out micro hydrogen treatment independently, and improving the bonding strength to 68-78 MPa; after the jet mill treatment and the trace hydrogen treatment are cooperatively adopted, the bonding strength of the titanium alloy particle coating and the matrix can be improved to 100-115 MPa.

Claims (3)

1. A jet mill pretreatment and trace hydrogen auxiliary sintering method of a titanium coating is characterized by comprising two steps:
firstly, putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to ensure that the oxygen content of the atmosphere in the jet mill equipment is lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, then introducing 4N high-purity hydrogen gas to be 0.105-0.110 MPa, opening a high-pressure pump to ensure that the gas generates internal circulation motion, carrying out jet milling for 10-120 minutes at the speed of 300-500 m/s by air flow in a fluidized bed, and screening titanium powder particles with proper particle size as powder particles for coating for later use after the jet milling is finished;
secondly, titanium powder particles which meet the technical requirements of the implant are placed on the surface of the cleaned implant, titanium powder particles with the average thickness of 600-800 mu m are placed on the surface of the titanium alloy implant, the treated implant is moved into a vacuum furnace and is vacuumized to 10 DEG, and the surface of the implant is cleaned-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to 500-600 ℃ at the speed of 1-30 ℃/min, then cooling to 320-380 ℃, closing the high vacuum system, only starting the mechanical pump, introducing micro-flow hydrogen to keep the pressure in the furnace at 30-60 Pa, preserving the heat for 30-80 minutes, opening the high vacuum system, and vacuumizing to less than 5 x 10-2Heating to 1000-1400 ℃ at the speed of 15-30 ℃/min, preserving the heat at the sintering temperature for 0.5-10 hours, cooling from the sintering temperature to room temperature at the speed of 1-10 ℃/min, taking out the implant with the sintered titanium bead coating, cleaning with distilled water and medical alcohol, and packaging.
2. The method of claim 1, wherein the pretreated titanium powder has a particle size of 50 to 250 micrometers (μm).
3. The jet mill pretreatment and trace hydrogen-assisted sintering method for the titanium coating according to claim 1, wherein after the jet mill treatment and the trace hydrogen treatment are cooperatively adopted, the bonding strength of the titanium alloy particle coating and the substrate is improved to 100-115 MPa.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101138649A (en) * 2007-10-24 2008-03-12 常州天力生物涂层技术有限公司 Method for obtaining bioactivity and open type stephanoporate titanium coating from implant surface
CN103266319A (en) * 2013-05-21 2013-08-28 李建久 Method for preparing porous titanium coating on surface of titanium alloy
CN106623952A (en) * 2016-12-19 2017-05-10 南京理工大学 Preparation method of titanium or titanium alloy powder with micro-hydrogenated surface
CN110280760A (en) * 2019-07-01 2019-09-27 北京科技大学 A kind of activated sintering preparation method of high-compactness titanium article
EP3666932A1 (en) * 2018-12-14 2020-06-17 Nano-implant Sp. z o.o. Production method of a personalised, biocompatible and bioactive orthopaedic implant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101138649A (en) * 2007-10-24 2008-03-12 常州天力生物涂层技术有限公司 Method for obtaining bioactivity and open type stephanoporate titanium coating from implant surface
CN103266319A (en) * 2013-05-21 2013-08-28 李建久 Method for preparing porous titanium coating on surface of titanium alloy
CN106623952A (en) * 2016-12-19 2017-05-10 南京理工大学 Preparation method of titanium or titanium alloy powder with micro-hydrogenated surface
EP3666932A1 (en) * 2018-12-14 2020-06-17 Nano-implant Sp. z o.o. Production method of a personalised, biocompatible and bioactive orthopaedic implant
CN110280760A (en) * 2019-07-01 2019-09-27 北京科技大学 A kind of activated sintering preparation method of high-compactness titanium article

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