CN116200702A - Medical biological gradient hard coating and preparation method thereof - Google Patents
Medical biological gradient hard coating and preparation method thereof Download PDFInfo
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- CN116200702A CN116200702A CN202310010758.2A CN202310010758A CN116200702A CN 116200702 A CN116200702 A CN 116200702A CN 202310010758 A CN202310010758 A CN 202310010758A CN 116200702 A CN116200702 A CN 116200702A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 238000000576 coating method Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- 238000000151 deposition Methods 0.000 claims description 40
- 229910045601 alloy Inorganic materials 0.000 claims description 29
- 239000000956 alloy Substances 0.000 claims description 29
- 230000008021 deposition Effects 0.000 claims description 29
- 229910052786 argon Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 229910010169 TiCr Inorganic materials 0.000 claims description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000531 Co alloy Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 29
- 239000002356 single layer Substances 0.000 description 4
- 239000007943 implant Substances 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000001145 finger joint Anatomy 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/045—Cobalt or cobalt alloys
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0084—Producing gradient compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- 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
- A61L2420/08—Coatings comprising two or more layers
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- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Inorganic Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a medical biological gradient hard coating and a preparation method thereof, belonging to the technical field of medical treatment. The coating comprises a Cr coating, a CrN coating, a TiCrN coating, a TiN coating and a TiNbN coating which are sequentially laminated. According to the invention, the chemical composition gradient hard coating is prepared on the surface of the cobalt alloy, so that the bonding strength of the film layer and the substrate is enhanced.
Description
Technical Field
The invention relates to the technical field of medical treatment, in particular to a medical biological gradient hard coating and a preparation method thereof.
Background
The prior art discloses a method for improving the service life and biocompatibility of an implant, which is to prepare a TiNbN coating on the outer surfaces of a bone plate body and a bone screw body by using a physical vapor deposition technology, wherein the thickness of the coating is 3-5 mu m, the adhesive strength between the coating and a substrate is HF1-2 mass, and the hardness is HV >2000.
But a single layer TiNbN coating is deposited on the surface of the implant, and the single layer film has certain internal stress, if the film layer cracks in use, the cracks can rapidly expand, so that the film layer fails. Before the hard material coating is prepared, a TiNb bonding layer is prepared on the substrate, but the bonding force between the coating and the substrate is not obviously enhanced from the bonding force result,
disclosure of Invention
Aiming at the problems in the background technology, the invention provides a medical biological gradient hard coating and a preparation method thereof. The preparation method prepares the hard coating with gradient change of chemical components on the surface of the cobalt alloy, so that the bonding strength of the film layer and the substrate is enhanced.
The technical scheme of the invention is realized in such a way,
a medical bio-gradient hard coating comprises a Cr coating, a CrN coating, a TiCrN coating, a TiN coating and a TiNbN coating which are sequentially laminated.
The preparation method of the medical biological gradient hard coating is used for preparing the medical biological gradient hard coating, and is realized by a magnetron sputtering technology, and specifically comprises the following steps of:
step 1, respectively placing a Cr metal target, a TiCr alloy target, a Ti metal target and a TiNb alloy target into corresponding cabins of a magnetron sputtering deposition cavity, keeping the doors of the cabins open, and placing a sample to be plated on a sample rack of the magnetron sputtering deposition cavity;
step 2, continuously vacuumizing the magnetron sputtering deposition cavity, and starting a heating device when the vacuum is pumped to 2X 10 < -3 > Pa so as to increase the temperature of the deposition cavity to 400 ℃;
step 3, continuously vacuumizing, setting the temperature to 300 ℃ when the vacuum degree reaches 1X 10 < -4 > Pa, introducing argon to 100sccm, closing an argon valve when the temperature is reduced to 300 ℃, and continuously vacuumizing for 20min;
and 4, introducing 100sccm of argon into the deposition cavity for 30min.
Step 5, closing an argon valve, continuously vacuumizing for 30min,
step 6, repeating the steps 4 to 5 twice;
step 7, setting the argon flow to be 80sccm, turning on a substrate bias power supply, setting the substrate voltage to be 150V, cleaning the surface of the sample for 20min, and then adjusting the substrate voltage to be 200V, and cleaning for 30min;
step 8, introducing argon gas to 30sccm, closing a cabin of the TiCr alloy target, the Ti metal target and the TiNb alloy target, and depositing a Cr film layer on the surface of the substrate under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 9, introducing argon gas 30sccm and nitrogen gas 60sccm into the magnetron sputtering deposition cavity, and depositing to obtain a CrN film under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 10, closing a cabin door of a Cr metal target, opening the cabin door of a TiCr alloy target, and depositing to obtain a TiCrN film under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 11, closing a cabin door of the TiCr alloy target, opening the cabin door of the Ti alloy target, and depositing to obtain a TiN film layer under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 12, closing a cabin door of the Ti metal target, opening the cabin door of the TiNb alloy target, and depositing to obtain a TiNbN film under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
and 13, closing a nitrogen valve, reducing the temperature to below 80 ℃, closing an argon valve, closing a vacuum system, cooling to room temperature, and taking out a sample to finish the coating.
Further, the thickness of the Cr film layer obtained in the step 8 is 0.5 μm, and the deposition temperature is 300-400 ℃.
Further, the thickness of the CrN film layer obtained in the step 9 is 1 μm, and the deposition temperature is 300-400 ℃.
Further, the thickness of the TiCrN film layer obtained in the step 10 is 1 μm, and the deposition temperature is 300-400 ℃.
Further, the thickness of the TiN film layer obtained in the step 11 is 1 μm, and the deposition temperature is 300-400 ℃.
Further, the thickness of the TiNbN film layer obtained in the step 12 is 1.5 μm, and the deposition temperature is 300-400 ℃.
Further, in the step 1, the ratio of the alloy elements in the TiCr alloy target is Ti: cr=80:20 (at%).
Further, in the step 1, the ratio of the alloy elements in the TiNb alloy target is Ti: nb=70:30 (at%).
Compared with the prior art, the invention has the following beneficial effects:
1. the design of the Cr/CrN/TiCrN/TiN/TiNbN gradient structure reduces the interface mismatch problem caused by the difference of chemical elements, improves the layer-to-layer association, and further improves the bonding strength of the coating and the substrate;
2. the gradient hard coating has more interfaces, can play a role in preventing crack growth, and prolongs the service life of the film;
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention utilizes the magnetron sputtering technology to prepare a biomedical gradient hard coating on the surface of cobalt alloy, the gradient hard coating system is divided into five layers, the first layer is a Cr coating, the first layer is deposited on the surface of cobalt alloy, the second layer is a CrN coating, the third layer is a TiCrN coating, the fourth layer is a TiN coating, and the fifth layer is a TiNbN coating, thus forming a CoCrMo/Cr/CrN/TiCrN/TiN/TiNbN gradient hard coating system. The total thickness of the coating in the present invention is about 5 μm.
Compared with a single-layer coating, the transition between the gradient coating film layers is gentle, the existence of the film layer interface prevents the expansion of film layer cracks, the coating can be endowed with certain toughness, and the stability of the coating is improved. In the invention, the gradient change of the chemical elements of the coating improves the matching degree of each interface, thereby improving the bonding strength of the interface and prolonging the service life of the implanted prosthesis. The coating deposition techniques of the present invention may be used with implants such as knee prostheses, hip prostheses, shoulder prostheses, toe prostheses, finger joints, wrist prostheses, and ankle prostheses, including but not limited to articular surfaces.
The specific implementation method comprises the following steps:
(1) Before the coating is deposited, ti and Cr metal targets and TiCr and TiNb alloy targets are replaced into the magnetron sputtering equipment, and before the film layer is not deposited, all targets are shielded by a baffle plate. The sample is placed on a sample holder.
(2) And (3) vacuumizing the deposition chamber, and starting a heating device after vacuumizing to 2X 10-3Pa so as to raise the temperature of the deposition chamber to 400 ℃.
(3) When the vacuum degree reaches 1X 10-4Pa, setting the temperature to 300 ℃, introducing argon to 100sccm, closing the ventilation valve when the temperature is reduced to 300 ℃, and vacuumizing for 20min.
(4) Argon was introduced at 100sccm for 30min.
(5) Closing the argon valve and vacuumizing for 30min,
(6) Repeating the steps (4) - (5) for 2 times, and adjusting parameters to prepare the coating.
(7) Setting the flow rate of argon to 80sccm, turning on a substrate bias power supply, setting the substrate voltage to 150V, cleaning the surface of a sample for 20min, then adjusting the substrate voltage to 200V, and cleaning for 30min;
(8) Argon is introduced to 30sccm, a Cr metal target baffle is opened, and a Cr film layer is deposited on the surface of a substrate under the conditions that the voltage is 50-150V, the pressure is 1-2 Pa and the target power is 150W, wherein the thickness of the obtained film layer is 0.5 mu m. The deposition temperature is 300-400 ℃;
(9) Argon is introduced into the reactor at 30sccm and nitrogen is introduced into the reactor at 60sccm, a Cr metal target baffle is opened, and a CrN film is deposited under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power, so that the thickness of the obtained film is 1 mu m. The deposition temperature is 300-400 ℃;
(10) Argon is introduced into the reactor at 30sccm and nitrogen is introduced into the reactor at 60sccm, a TiCr alloy target baffle is opened, and a TiCrN film is deposited under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power, so that the thickness of the obtained film is 1 mu m. The deposition temperature is 300-400 ℃. The ratio of alloy elements in the TiCr alloy target material is Ti:Cr=80:20 (at%).
(11) Argon gas of 30sccm and nitrogen gas of 60sccm are introduced, a Ti metal target baffle is opened, and a TiN film layer is deposited under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power, wherein the thickness of the obtained film layer is 1 mu m. The deposition temperature is 300-400 ℃.
(12) Argon is introduced into the reactor for 30sccm, nitrogen is introduced into the reactor for 60sccm, a TiNb alloy target baffle is opened, and a TiNbN film layer is deposited under the conditions that the voltage is 50-150V, the pressure is 1-2 Pa and the target power is 150W, wherein the thickness of the obtained film layer is 1.5 mu m. The deposition temperature is 300-400 ℃. The ratio of alloy elements in the TiNb alloy target material is Ti:Cr=70:30 (at%).
(13) The Cr/CrN/TiCrN/TiN/TiNbN gradient coating is obtained after the above steps are completed.
Example 1 is provided: the coating TiNbN was compared and the coating thickness was about 4.8. Mu.m. The prepared comparison coating is a single-layer TiNbN and is directly deposited on the surface of the cobalt alloy. The process steps are (1) to (6) and (13) above.
Example 2 is provided: the gradient hard coating Cr/CrN/TiCrN/TiN/TiNbN is about 4.9 mu m in thickness. (1) - (13),
referring to Table 1, the test criteria and hardness test results of examples 1 and 2 are shown
TABLE 1
Referring to table 2, the test standards and frictional wear test results of examples 1 and 2 are shown.
TABLE 2
Referring to table 3, the test standards and binding force test results of examples 1 and 2 are shown.
TABLE 3 Table 3
Claims (9)
1. The medical biological gradient hard coating is characterized by comprising a Cr coating, a CrN coating, a TiCrN coating, a TiN coating and a TiNbN coating which are sequentially laminated.
2. A method for preparing a medical bio-gradient hard coating, which is used for preparing the medical bio-gradient hard coating as claimed in claim 1, and is characterized by being realized by a magnetron sputtering technology, and specifically comprising the following steps:
step 1, respectively placing a Cr metal target, a TiCr alloy target, a Ti metal target and a TiNb alloy target into corresponding cabins of a magnetron sputtering deposition cavity, keeping the doors of the cabins open, and placing a sample to be plated on a sample rack of the magnetron sputtering deposition cavity;
step 2, continuously vacuumizing the magnetron sputtering deposition cavity, and starting a heating device when the vacuum is pumped to 2X 10 < -3 > Pa so as to increase the temperature of the deposition cavity to 400 ℃;
step 3, continuously vacuumizing, setting the temperature to 300 ℃ when the vacuum degree reaches 1X 10 < -4 > Pa, introducing argon to 100sccm, closing an argon valve when the temperature is reduced to 300 ℃, and continuously vacuumizing for 20min;
step 4, introducing argon gas of 100sccm into the deposition cavity for 30min;
step 5, closing an argon valve, continuously vacuumizing for 30min,
step 6, repeating the steps 4 to 5 twice;
step 7, setting the argon flow to be 80sccm, turning on a substrate bias power supply, setting the substrate voltage to be 150V, cleaning the surface of the sample for 20min, and then adjusting the substrate voltage to be 200V, and cleaning for 30min;
step 8, introducing argon gas to 30sccm, closing a cabin of the TiCr alloy target, the Ti metal target and the TiNb alloy target, and depositing a Cr film layer on the surface of the substrate under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 9, introducing argon gas 30sccm and nitrogen gas 60sccm into the magnetron sputtering deposition cavity, and depositing to obtain a CrN film under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 10, closing a cabin door of a Cr metal target, opening the cabin door of a TiCr alloy target, and depositing to obtain a TiCrN film under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 11, closing a cabin door of the TiCr alloy target, opening the cabin door of the Ti alloy target, and depositing to obtain a TiN film layer under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
step 12, closing a cabin door of the Ti metal target, opening the cabin door of the TiNb alloy target, and depositing to obtain a TiNbN film under the conditions of 50-150V voltage, 1-2 Pa pressure and 150W target power;
and 13, closing a nitrogen valve, reducing the temperature to below 80 ℃, closing an argon valve, closing a vacuum system, cooling to room temperature, and taking out a sample to finish the coating.
3. The method for preparing a bio-gradient hard coating for medical use according to claim 2, wherein the thickness of the Cr film obtained in the step 8 is 0.5 μm, and the deposition temperature is 300-400 ℃.
4. The method for preparing a medical bio-gradient hard coating according to claim 2, wherein the thickness of the CrN film obtained in the step 9 is 1 μm, and the deposition temperature is 300-400 ℃.
5. The method for preparing a medical bio-gradient hard coating according to claim 2, wherein the thickness of the TiCrN film obtained in the step 10 is 1 μm, and the deposition temperature is 300-400 ℃.
6. The method for preparing a bio-gradient hard coating for medical use according to claim 2, wherein the thickness of the TiN film layer obtained in the step 11 is 1 μm, and the deposition temperature is 300-400 ℃.
7. The method for preparing a bio-gradient hard coating for medical use according to claim 2, wherein the thickness of the TiNbN film obtained in the step 12 is 1.5 μm, and the deposition temperature is 300-400 ℃.
8. The method for preparing a bio-gradient hard coating according to claim 2, wherein in the step 1, the ratio of alloy elements in the TiCr alloy target is Ti: cr=80:20 (at%).
9. The method for preparing a bio-gradient hard coating for medical use according to claim 2, wherein in the step 1, the ratio of alloy elements in the TiNb alloy target is Ti: nb=70:30 (at%).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310010758.2A CN116200702A (en) | 2023-01-05 | 2023-01-05 | Medical biological gradient hard coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310010758.2A CN116200702A (en) | 2023-01-05 | 2023-01-05 | Medical biological gradient hard coating and preparation method thereof |
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