CN113333133A - Jet milling pretreatment method for powder particles of vacuum sintering porous titanium coating - Google Patents
Jet milling pretreatment method for powder particles of vacuum sintering porous titanium coating Download PDFInfo
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- CN113333133A CN113333133A CN202110625099.4A CN202110625099A CN113333133A CN 113333133 A CN113333133 A CN 113333133A CN 202110625099 A CN202110625099 A CN 202110625099A CN 113333133 A CN113333133 A CN 113333133A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/06—Jet mills
- B02C19/068—Jet mills of the fluidised-bed type
Abstract
The invention discloses a powder particle jet mill pretreatment method for vacuum sintering of a porous titanium coating, and relates to a powder particle fluidized bed type jet mill pretreatment method for improving the bonding strength of a titanium powder particle coating and a substrate. Is suitable for improving the performance of implants in orthopedics, dentistry and the like. A powder particle jet mill pretreatment method for vacuum sintering of a porous titanium coating comprises the steps of firstly putting titanium powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon to enable the oxygen content of atmosphere in the jet mill equipment to be lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, then introducing 4N high-purity hydrogen to be 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 by air flow in a fluidized bed at the speed of 300-500 m/s, and screening the titanium powder particles with proper particle size as powder particles for the coating for later use after the jet mill is finished.
Description
Technical Field
The invention discloses a powder particle jet mill pretreatment method for vacuum sintering of a porous titanium coating, relates to a powder particle fluidized bed type jet mill pretreatment method for improving the bonding strength of a titanium powder particle coating 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 a powder particle jet mill pretreatment method for vacuum sintering of a porous titanium coating. The method comprises the steps of firstly putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to enable the oxygen content of the atmosphere in the jet mill equipment to be 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 movement, jet milling the gas flow in the fluidized bed for 10-120 minutes at the speed of 300-500 m/s, and screening titanium powder particles with proper particle sizes to serve as powder particles for coating for later use after the jet mill is finished. And then a vacuum sintering process is adopted to obtain the open porous titanium coating on the surface of the implant of orthopedics, dentistry and the like. The coating keeps a good space structure of a high vacuum sintering titanium coating, and on the other hand, the bonding strength of the titanium coating on the surface of the implant and a titanium alloy matrix is greatly improved through jet milling pretreatment of powder particles, so that the reliability and the safety of the implant are improved. And the process has low cost.
The powder particle jet mill pretreatment method for vacuum sintering of the porous titanium coating is realized by adopting the following technical scheme:
a powder particle jet mill pretreatment method for vacuum sintering of a porous titanium coating comprises the steps of firstly putting titanium powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to enable the oxygen content of the atmosphere in the jet mill equipment to be 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 movement, carrying out jet milling for 10-120 minutes by air flow in the fluidized bed at the speed of 300-500 m/s, screening the titanium powder particles with proper particle size after the jet mill is finished to serve as powder particles for the coating for later use, and then obtaining the open type porous titanium coating on the surface of implants such as orthopedics and dentistry by adopting a vacuum sintering process.
The particle size of the pretreated titanium powder particles is 50-250 micrometers (mum).
The vacuum sintering process of vacuum sintering porous titanium coating includes pre-treating the surface of cleaned implant, setting titanium powder grains in the required thickness of 600-1000 microns on the surface of the implant, setting titanium grains in the average thickness of 600-1000 microns on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuum pumping to 10 deg.c-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to sintering temperature of 1000-1400 ℃ at the speed of 1-30 ℃/min, preserving heat at the sintering temperature for 0-10 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 pretreatment is adopted, the bonding strength of the vacuum sintering titanium alloy particle coating and the matrix is effectively improved, and the bonding strength is improved from 40-55 MPa of the pretreatment to 65-80 MPa.
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 problems, the invention provides a jet milling pretreatment method for powder particles of a vacuum sintering porous titanium coating. The method comprises the steps of firstly putting powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to enable the oxygen content of the atmosphere in the jet mill equipment to be 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 movement, jet milling the gas flow in the fluidized bed for 10-120 minutes at the speed of 300-500 m/s, and screening titanium powder particles with proper particle sizes to serve as powder particles for coating for later use after the jet mill is finished. And then a vacuum sintering process is adopted to obtain the open porous titanium coating on the surface of the implant of orthopedics, dentistry and the like. On one hand, the coating keeps a good space structure of a high vacuum sintering titanium coating, on the other hand, the bonding strength of the titanium coating on the surface of the implant and a titanium alloy matrix is greatly improved through jet milling pretreatment of adding hydrogen, 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 powder particle jet mill pretreatment method for vacuum sintering of the porous titanium coating is a powder particle jet mill pretreatment 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 lower process cost.
Detailed Description
A powder particle jet mill pretreatment method for vacuum sintering of a porous titanium coating comprises the steps of firstly putting titanium powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon to enable the oxygen content of atmosphere in the jet mill equipment to be lower than 2000ppm, keeping the air pressure in the jet mill to be 0.101MPa, then introducing 4N high-purity hydrogen to be 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 by air flow in a fluidized bed at the speed of 300-500 m/s, and screening the titanium powder particles with proper particle size as powder particles for the coating for later use after the jet mill is finished.
The particle size of the pretreated titanium powder particles is 50-250 micrometers (mum).
The vacuum sintering process of vacuum sintering porous titanium coating includes pre-treating the surface of cleaned implant, setting titanium powder grains in the required thickness of 600-1000 microns on the surface of the implant, setting titanium grains in the average thickness of 600-1000 microns on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuum pumping to 10 deg.c-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to sintering temperature of 1000-1400 ℃ at the speed of 1-30 ℃/min, preserving 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 pretreatment is adopted, the bonding strength of the vacuum sintering titanium alloy particle coating and the matrix is effectively improved, and the bonding strength is improved from 40-55 MPa of the pretreatment to 65-80 MPa.
The invention will be further illustrated with reference to the following examples:
comparative example:
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 1400 deg.C at a rate of 5 deg.C/min, maintaining at sintering temperature for 0.5 hr, and sintering at a rate of 1 deg.C/minAnd cooling to room temperature, 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.
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 particles with the average thickness of 800 μm on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10%-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 80 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 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 particles with average thickness of 1000 μm on the surface of titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10%-2Heating and sintering above Pa. The sintering system is as follows: at 30 ℃/mThe in speed is increased from room temperature to 1300 ℃, the temperature is kept at the sintering temperature for 10 hours, then the temperature is reduced from the sintering temperature to the room temperature at the speed of 5 ℃/min, and the implant with the sintered titanium bead coating and the furnace strength test sample are taken out. 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 75 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 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 particles with the average thickness of 600 μm on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and vacuumizing to 10%-2Heating and sintering above Pa. The sintering system is as follows: heating from room temperature to 1000 ℃ at the speed of 1 ℃/min, preserving the heat for 5 hours at the sintering temperature, then cooling from the sintering temperature to room temperature at the speed of 10 ℃/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 was 65 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 is to carry out fluidized bed type airflow mill pretreatment on the presintered titanium powder particles. The method comprises the steps of firstly putting titanium powder particles to be treated into fluidized bed type jet mill equipment, then introducing 4N high-purity argon gas to enable the oxygen content of atmosphere in the jet mill equipment to be 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 movement, jet milling the titanium powder particles with proper particle size for 10-120 minutes at the speed of 300-500 m/s in the fluidized bed, and screening the titanium powder particles with proper particle size as powder particles for coating for later use after the jet mill is finished. Placing titanium powder particles which meet the technical requirements of the implant on the surface of the cleaned 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 sintering temperature of 1000-1400 ℃ at the speed of 1-30 ℃/min, preserving 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 pretreatment is adopted, the bonding strength of the vacuum sintering titanium alloy particle coating and the matrix is effectively improved, and the bonding strength is improved from 40-55 MPa of the pretreatment to 65-80 MPa.
Claims (4)
1. A powder particle jet mill pretreatment method for vacuum sintering of a porous titanium coating is characterized in that titanium powder particles to be treated are placed into a fluidized bed type jet mill device, 4N high-purity argon is introduced to enable the oxygen content of the atmosphere in the jet mill device to be lower than 2000ppm, the air pressure in the jet mill is kept to be 0.101MPa, 4N high-purity hydrogen is introduced to be 0.105-0.110 MPa, a high-pressure pump is opened to enable the gas to generate internal circulation motion, the jet mill is performed for 10-120 minutes by air flow in the fluidized bed at the speed of 300-500 m/s, the titanium powder particles with proper particle size are screened after the jet mill is finished and used as powder particles for the coating for standby, and then the vacuum sintering process is adopted to obtain the open type porous titanium coating on the surfaces of orthopedic implants and dental implants.
2. The method of claim 1, wherein the vacuum sintering process comprises placing the pretreated titanium powder particles on the surface of the cleaned implant, placing titanium particles with an average thickness of 600-1000 μm on the surface of the titanium alloy implant, transferring the treated implant into a vacuum furnace, and evacuating to 10 μm-2Heating and sintering above Pa, wherein the sintering system is as follows: heating from room temperature to sintering temperature of 1000-1400 ℃ at the speed of 1-30 ℃/min, preserving heat at the sintering temperature for 0-10 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.
3. The method for pretreating the powder particles of the vacuum-sintered porous titanium coating by the jet mill as claimed in claim 2, wherein after the pretreatment by the jet mill, the bonding strength between the vacuum-sintered titanium alloy particle coating and the substrate is improved to 65-80 MPa.
4. The method of claim 1, wherein the pretreated titanium powder particles have a particle size of 50-250 micrometers (μm).
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| CN202110625099.4A CN113333133A (en) | 2021-06-04 | 2021-06-04 | Jet milling pretreatment method for powder particles of vacuum sintering porous titanium coating |
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| CN202110625099.4A CN113333133A (en) | 2021-06-04 | 2021-06-04 | Jet milling pretreatment method for powder particles of vacuum sintering porous titanium coating |
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