CN114525478A - Medical high-entropy alloy composite strengthening layer and preparation method thereof - Google Patents

Medical high-entropy alloy composite strengthening layer and preparation method thereof Download PDF

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Publication number
CN114525478A
CN114525478A CN202210119130.1A CN202210119130A CN114525478A CN 114525478 A CN114525478 A CN 114525478A CN 202210119130 A CN202210119130 A CN 202210119130A CN 114525478 A CN114525478 A CN 114525478A
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entropy alloy
power supply
plasma solid
state surface
source
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谭洪
杨纪洁
王成磊
谢映光
梁朝杰
刘伟杰
梁慕林
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Guilin University of Electronic Technology
Affiliated Hospital of Guilin Medical University
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Guilin University of Electronic Technology
Affiliated Hospital of Guilin Medical University
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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium 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
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • 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
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C23C14/3485—Sputtering using pulsed power to the target
    • 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
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/586—Nitriding
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • 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
    • 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
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention is suitable for the technical field of surface modification and the technical field of biomedical materials and preparation, and provides a medical high-entropy alloy composite strengthening layer and a preparation method thereof. The high-entropy alloy composite strengthening layer is a high-entropy alloy deposition layer deposited on the surface of a metal substrate by a plasma solid-state surface metallurgy technology, and the preparation method comprises the following steps: placing a metal substrate and a high-entropy alloy source target material in plasma solid-state surface metallurgy equipment; and (3) carrying out infiltration plating deposition on the surface of the metal base material by a high-entropy alloy source target material through a solid surface metallurgy step by using plasma solid surface metallurgy equipment to form a high-entropy alloy deposition layer. According to the medical high-entropy alloy composite strengthening layer and the preparation method thereof, provided by the invention, the technical advantages of strong binding force, high surface modification efficiency, low cost, adaptability to various complex workpiece shapes and the like of a plasma solid-state surface metallurgy technology are utilized, and the wear resistance, corrosion resistance, stability and biocompatibility of a medical implant material are improved.

Description

Medical high-entropy alloy composite strengthening layer and preparation method thereof
Technical Field
The invention belongs to the technical field of surface modification and biomedical materials and preparation, and particularly relates to a medical high-entropy alloy composite strengthening layer and a preparation method thereof.
Background
At present, common bone repair metal materials for clinical application include titanium, titanium alloy, stainless steel, magnesium alloy, cobalt-chromium alloy and the like, wherein the titanium and the titanium alloy are widely applied to the manufacture of hard tissue implants because of good biocompatibility, mechanical strength and corrosion resistance. However, titanium and titanium alloy are biologically inert, so that the surface of the implant is easily wrapped by fibrous connective tissue and cannot be well combined with bone tissue, and the loosening of the implant is caused, so that the failure rate of clinical operation is high.
In addition, the bonding may also be unstable due to the large difference in thermal expansion coefficient between titanium and titanium alloys and bone. Meanwhile, the working condition of the implant in the human body is very bad, the internal environment is rich in various ions, the oxygen content is sufficient, and the implant is easy to be worn and corroded under the composite action of the friction process.
The surface modification technology can change the structure, chemical components and the like of the surface oxide film of the titanium and titanium alloy implant based on mechanical, physical, chemical and other methods, thereby further improving the biocompatibility, bioactivity, wear resistance, corrosion resistance and the like. Therefore, different surface modification techniques for titanium and titanium alloys have been proposed to meet the clinical application requirements.
In recent years, aiming at the surface modification technology of medical titanium and titanium alloy, the development is rapid, such as an anodic oxidation method, a micro-arc oxidation method, an electrophoretic deposition method, a thermal oxidation method, an ion implantation method, a vapor deposition method, a sol-gel method, a sand blasting and acid etching method and the like, so that the biological activity, the biocompatibility, the wear resistance and the corrosion resistance of the medical titanium and titanium alloy are greatly improved, but the surface modification technology of the medical titanium and titanium alloy still has some defects, mainly the bonding strength of a coating and a matrix is insufficient, and the requirement of various biological properties on a single modification method is difficult.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a medical high-entropy alloy composite strengthening layer and a preparation method thereof, wherein the high-entropy alloy has good wear resistance, corrosion resistance, stability and biocompatibility.
The technical scheme of the invention is as follows: a medical high-entropy alloy composite strengthening layer and a preparation method thereof are disclosed, wherein a high-entropy alloy deposition layer is deposited on the surface of a metal substrate in a plasma solid-state surface metallurgy mode.
Optionally, the high entropy alloy deposit comprises at least five of Ti, Ta, Zr, Mo, Nb, Hf, Fe, W, Co, Cr, Cu, Al and Ni; the metal base material is made of titanium or titanium alloy.
The invention also provides a preparation method for preparing the high-entropy alloy composite strengthening layer, which comprises the following steps:
preparing a metal substrate;
preparing a high-entropy alloy source target material containing at least five metal elements;
placing the metal substrate and the high-entropy alloy source target material in plasma solid-state surface metallurgy equipment;
and carrying out diffusion plating deposition on the high-entropy alloy source target on the surface of the metal base material through a solid surface metallurgy step by using the plasma solid surface metallurgy equipment to form a high-entropy alloy deposition layer.
Optionally, the preparation of the high-entropy alloy source target material comprises the following steps:
the material preparation step: selecting at least five of Ti, Ta, Zr, Mo, Nb, Hf, Fe, W, Co, Cr, Cu, Al and Ni with the purity of not less than 99.9%, and weighing and proportioning to obtain raw materials;
a primary smelting step: performing primary smelting on the raw materials;
vacuum arc melting: carrying out vacuum arc melting on the raw materials subjected to preliminary melting;
a target material forming step: and placing the raw material subjected to vacuum arc melting in a mold to form a set shape to obtain the high-entropy alloy source target.
Optionally, the solid state surface metallurgy step comprises the steps of:
preparing an auxiliary source barrel which can be placed in the plasma solid-state surface metallurgy equipment;
the installation step of the high-entropy alloy source electrode target material comprises the following steps: connecting the high-entropy alloy source electrode target material to the inner wall of an auxiliary source electrode barrel;
a metal base material mounting step: suspending the metal substrate in the auxiliary source electrode barrel through a conductive piece, wherein the metal substrate is not contacted with the high-entropy alloy source electrode target material;
and (3) diffusion plating deposition: and introducing inert protective gas into the plasma solid-state surface metallurgy equipment, gradually increasing the voltage and the current of the source pulse power supply, and depositing the alloy elements of the high-entropy alloy source target material on the surface of the metal base material to form a high-entropy alloy layer, wherein the component distribution of the alloy elements is gently changed along with the depth.
Optionally, before the step of diffusion coating deposition, a step of bombardment cleaning before diffusion coating is performed:
closing a furnace door of the plasma solid-state surface metallurgy device;
pumping the vacuum degree in the furnace body of the plasma solid-state surface metallurgical equipment to a set range;
and starting a source pulse power supply of the plasma solid-state surface metallurgy equipment, gradually increasing the voltage and the current of the power supply, enabling the auxiliary source barrel and the metal base material to generate glow discharge and arc striking phenomena, carrying out bombardment cleaning on the high-entropy alloy source target material and the metal base material, and finishing the bombardment cleaning after the arc striking phenomena disappear.
Optionally, before the bombardment cleaning step before diffusion plating, performing a diffusion plating pretreatment step:
polishing and cleaning the metal base material, and drying the metal base material;
cleaning dust and metal debris within a furnace body of the plasma solid state surface metallurgical equipment.
Optionally, in the step of diffusion deposition:
the inert protective gas is argon, the purity is more than or equal to 99.99%, and the flow rate is 5-40 mL/min;
adjusting the flow of argon to enable the vacuum degree to reach the working air pressure with the vacuum degree of 20-60 Pa;
the temperature of the metal base material is 800-1400 ℃;
the heat preservation time is 2-5 hours, and after the heat preservation time is finished, the flow of argon is closed.
Optionally, after the diffusion deposition step, an ion nitridation step is performed:
introducing ammonia gas into the plasma solid-state surface metallurgy equipment, wherein the purity of the ammonia gas is more than or equal to 99.99%, the flow rate of the ammonia gas is 50-200 mL/min, the glow thickness is controlled to be 3-6 mm, and the flow rate of the introduced ammonia gas is adjusted according to the observed glow thickness; the nitriding temperature is 500-550 ℃, the voltage and the current of the source pulse power supply are adjusted according to the nitriding temperature, and the voltage of the pulse power supply is controlled to be-400V-1000V; nitriding for 6-10 hours, after the heat preservation time is finished, closing the flow of ammonia gas, closing a power supply, keeping air extraction and cooling the treated material to room temperature along with the furnace;
after the ion nitriding step, performing a post heat treatment step:
and performing tube sealing treatment on the treated material, performing heat treatment by using a heat treatment furnace at the temperature of 750-1000 ℃ for 1-6 h, and quenching the treated material after the heat treatment is finished.
The invention also provides a preparation device for preparing the medical high-entropy alloy composite strengthening layer, which comprises plasma solid-state surface metallurgy equipment, wherein the plasma solid-state surface metallurgy equipment is provided with an anode cover connected to a furnace body, an auxiliary source electrode barrel is arranged in the furnace body, 20-200 high-entropy alloy source electrode target materials are arranged on the inner side of the auxiliary source electrode barrel, and the metal base material is also hung in the auxiliary source electrode barrel;
the preparation device also comprises a source electrode pulse power supply device, wherein the source electrode pulse power supply device is provided with a first path of power supply and a second path of power supply, the negative electrode of the first path of power supply is connected to the metal substrate through a workpiece cathode frame, the negative electrode of the second path of power supply is connected to the high-entropy alloy source electrode target through a working disc and an auxiliary source electrode barrel, and the positive electrode of the first path of power supply and the positive electrode of the second path of power supply are both connected to the anode cover;
the preparation device also comprises a vacuumizing device which is connected with the plasma solid-state surface metallurgy equipment and is used for vacuumizing the furnace body;
the preparation device also comprises a ventilation device which is connected with the plasma solid-state surface metallurgy equipment and is used for introducing set gas into the furnace body;
the preparation device also comprises an infrared temperature measuring device which is connected with the plasma solid-state surface metallurgy equipment and is used for measuring the temperature of the metal base material.
The medical high-entropy alloy composite strengthening layer and the preparation method thereof provided by the invention integrate the plasma solid-state metallurgy metal infiltration technology with the surface modification of a medical implant material, a medical high-entropy alloy film (coating) and the research of ion nitriding, adopt the medical implant material as a base material, and greatly improve the wear resistance, corrosion resistance, stability and biocompatibility of the medical implant material by combining the technical advantages of the plasma solid-state surface metallurgy technology, such as strong bonding force, high surface modification efficiency, low cost, adaptability to various complex workpiece shapes, and the like with the huge application potential of the ion nitriding surface modification and the medical high-entropy alloy film (coating).
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic plan view of a medical high-entropy alloy composite strengthening layer provided by an embodiment of the invention;
fig. 2 is a schematic plan view of a device for preparing a medical high-entropy alloy composite strengthening layer provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or intervening elements may also be present.
It should be noted that the terms of orientation such as left, right, up and down in the embodiments of the present invention are only relative to each other or are referred to the normal use state of the product, and should not be considered as limiting.
As shown in fig. 1, the medical high-entropy alloy composite strengthening layer provided by the embodiment of the invention comprises a metal substrate 100 and a high-entropy alloy deposition layer 112 deposited on the surface of the metal substrate 100 by a plasma solid-state surface metallurgy manner, wherein the high-entropy alloy deposition layer 112 comprises at least five metal elements. By depositing the high-entropy alloy deposition layer 112 on the surface of the metal substrate 100 in a plasma solid-state surface metallurgy manner, a novel biomedical gradient high-entropy alloy composite strengthening layer in metallurgical bonding can be obtained. The novel biomedical gradient high-entropy alloy composite strengthening layer can keep good mechanical property, has good corrosion resistance, friction and abrasion resistance and biocompatibility in a biological environment, and solves the problems of insufficient bonding strength between a coating and a matrix and the like in the prior art.
Specifically, the high-entropy alloy deposition layer 112 includes at least five of Ti, Ta, Zr, Mo, Nb, Hf, Fe, W, Co, Cr, Cu, Al, and Ni, and in the present embodiment, the high-entropy alloy deposition layer 112 includes Al, Fe, Co, Cr, Cu, and Ti. In a specific application, the high-entropy alloy deposition layer 112 may be 5 to 25 μm, for example, 10 to 20 μm, and in this embodiment, the high-entropy alloy deposition layer 112 may be a medical high-entropy alloy composite strengthening layer with a thickness of 15 μm. The diffusion layer 111 (transition layer) is formed at the joint (combination) of the metal substrate 100 and the high-entropy alloy deposition layer 112, the elements of the high-entropy alloy deposition layer 112 are diffused into the diffusion layer 111, the thickness of the diffusion layer 111 can be 10 μm to 30 μm, preferably 15 μm to 25 μm, and in this embodiment, the thickness of the diffusion layer 111 is 20 μm. The diffusion layer 111 and the high-entropy alloy deposition layer 112 have the same elements, the element composition in the diffusion layer 111 changes slowly (becomes less) with the depth, and the deposition layer 112 and the diffusion layer 111 and the metal base material 100 are in a metallurgical bonding state.
Specifically, the material of the metal base material 100 may be titanium or a titanium alloy.
The embodiment of the invention also provides a preparation method, which can be used for preparing the medical high-entropy alloy composite strengthening layer and comprises the following steps:
preparing a metal substrate 100;
preparing a high-entropy alloy source target material containing at least five metal elements;
placing the metal substrate 100 and the high-entropy alloy source target material in plasma solid-state surface metallurgy equipment;
the high-entropy alloy source target material is subjected to infiltration plating deposition on the surface of the metal substrate 100 through a solid surface metallurgy step by the plasma solid surface metallurgy device to form a high-entropy alloy deposition layer 112, so that the high-entropy alloy layer is obtained, and a novel biomedical gradient high-entropy alloy composite strengthening layer in metallurgical bonding can be obtained. The novel biomedical gradient high-entropy alloy composite strengthening layer can keep good mechanical property, has good corrosion resistance, friction and abrasion resistance and biocompatibility in a biological environment, and solves the problems of insufficient bonding strength between a coating and a matrix and the like in the prior art.
Specifically, the preparation of the high-entropy alloy source target material comprises the following steps: the method comprises the steps of material preparation, preliminary melting, vacuum arc melting and target material forming.
Wherein, the batching step includes: selecting at least five of Ti, Ta, Zr, Mo, Nb, Hf, Fe, W, Co, Cr, Cu, Al and Ni with the purity of not less than 99.9%, and weighing and proportioning to obtain raw materials; in the embodiment, Al, Fe, Co, Cr, Cu and Ti are selected as raw materials, the materials are mixed according to the components of Al0.75, Fe, Co, Cr, Cu and Ti0.5, the mixture is mixed by 25 g in each part, and the mixture is smelted into the high-entropy alloy source target material by 30 parts in total. The high-entropy alloy source target material can be rod-shaped.
Wherein, the preliminary smelting step comprises: and performing primary smelting on the raw materials, wherein the primary smelting can be performed for multiple times. In the specific application, the vacuum magnetic suspension smelting furnace can be adopted for preliminary smelting, the whole vacuum magnetic suspension smelting furnace is checked before operation, cooling water and a power supply are started after all the parts are normal, a furnace cover is opened, and impurities in the furnace are cleaned by alcohol. Then the raw materials are put in and the furnace cover is closed. Starting the vacuum system, and pumping the vacuum degree to 3.0 multiplied by 10-3Introducing argon to 0.05-0.08 Pa above Pa, repeatedly vacuumizing and washing gas, and filling argon for 2-3 times. Then, a small amount of argon gas is filled into the furnace chamber, so that an inert atmosphere is formed in the furnace chamber. Confirming the working of power supply and cooling waterAfter that, the smelting operation is started. It usually requires 3 to 5 repeated heats to ensure that the sample is melted uniformly, depending on the fluidity of the liquid metal during melting. After cooling to normal temperature, opening an air release valve, and opening the furnace to take materials when the temperature in the furnace is changed to normal temperature and normal pressure to obtain a sample; after the crucible is cooled, the furnace chamber is cleaned by alcohol, the furnace cover is closed, the lock catch is locked, the furnace is vacuumized, and the water and electricity are cut off.
Wherein, vacuum arc melting includes: and (4) carrying out vacuum arc melting on the raw materials subjected to preliminary melting, and repeatedly melting for multiple times. In the specific application, the vacuumizing step is carried out before vacuum arc melting: before operation, the vacuum arc melting equipment is checked, after all is normal, the power supply is switched on, the sample chamber is cleaned and the sample is filled, the vacuum system is started to vacuumize (the mechanical pump is started to vacuumize to below 5Pa, the mechanical pump valve is closed, the front valve is opened, the molecular pump is started, and the vacuum degree is pumped to 3.0 x 10-3And (4) closing the knob after Pa is higher than Pa, closing the molecular pump, closing the front-stage valve), introducing argon to 0.05-0.08 Pa, repeatedly vacuumizing and washing gas, and filling argon for 2-3 times. During vacuum arc melting: turning on illumination, adjusting the distance between the tip of the tungsten electrode rod and the sample to be 2-5 mm (about), turning off the illumination, turning on an electric welding machine, and turning on a high-frequency power supply; starting an arc welding rectifier power supply, clicking an arc starting button to start an arc, quickly lifting an electric gun, adjusting the current and whether to start magnetic current stirring according to the sample melting condition, reducing the current after melting, and extinguishing the arc. And turning the sample, then smelting for the 2 nd time, and repeating the smelting for 3 to 4 times to ensure that the sample is smelted more uniformly.
Wherein, the target material forming step: and placing the raw material subjected to vacuum arc melting in a mold to form a set shape to obtain the high-entropy alloy source target. In the specific application, a suction casting mold with the mold cavity size diameter of 5-12 mm and the length of 5-15 mm is adopted, and after the last melting, the sample cast ingot is turned into a suction casting mold groove while the sample cast ingot is hot, and the sample cast ingot is melted. Heating the edge of the high-entropy alloy source electrode target material for a circle, heating the edge until the edge is melted at the center, melting the edge until the surface is punctured, increasing the current, instantly opening a suction casting valve, closing an electric arc melting power supply, cooling a sample, a cavity and an electrode, then discharging gas, dismounting a die, and taking out the melted rod-shaped source electrode target material to obtain the high-entropy alloy source electrode target material. Then, cleaning the sample chamber, cleaning the mould, lowering the lifting platform, vacuumizing, turning off the mechanical pump and turning off the power supply.
Specifically, the solid-state surface metallurgy step comprises the following steps: the method comprises the steps of preparing an auxiliary source electrode barrel, installing a high-entropy alloy source electrode target material, installing a metal substrate 100 and performing diffusion plating and deposition. Before the diffusion plating deposition step, a bombardment cleaning step before diffusion plating is carried out. Before the bombardment cleaning step before the diffusion plating, a diffusion plating pretreatment step is carried out.
Wherein, the preparation step of the auxiliary source electrode barrel comprises the following steps: preparing an auxiliary source barrel which can be placed in the plasma solid-state surface metallurgy equipment. In the concrete application, the auxiliary source electrode barrel can adopt a workpiece-imitating shape structure, and in the concrete application, the barrel-shaped size is as follows: phi (80-120) × (120-180) mm (diameter × length); the square size is (80-200) × (60-200) × (50-150) mm (length × width × height), and it is helpful for adjusting a certain number of cathode cover plates. The assisted source bucket design also involves the geometry, size, weight, number of sources and placement in the assisted source. And considering the influence factors of the sputtering rate and sputtering amount of the source material, the absorptivity of the surface of the workpiece, the diffusion coefficient, the diffusion speed and the like, and the size, the shape and the like of the source material can be set and selected according to the actual situation.
The method comprises the following steps of: and connecting the high-entropy alloy source electrode target material to the inner wall of the auxiliary source electrode barrel.
Wherein the metal base material 100 mounting step: and suspending the metal substrate 100 in the auxiliary source barrel through a conductive piece, wherein the metal substrate 100 is not in contact with the high-entropy alloy source target. In this example, the metal base material 100 (base material) is made of two types of columnar and plate-like titanium or titanium alloy, and the dimensions of the column are: phi (10-25) × (60-70) mm (diameter × length); the plate size was: (60-70) × (20-25) × (2-3) mm (length × width × thickness). In this embodiment, the metal base material 100 is made of pure titanium.
Specifically, the diffusion plating pretreatment step comprises: polishing and cleaning the metal base material 100, and drying the metal base material 100, wherein in the specific application, 400#, 600# and 800# abrasive paper are respectively adopted to polish the surface of the base material to be smooth, then an ultrasonic cleaning machine is adopted to respectively add alcohol and acetone to clean for 10-30 min, and finally the base material is dried for later use; cleaning dust and metal debris in a furnace body, uniformly inserting a rod-shaped source target (phi 5-12 mm and length 5-15 mm) formed by suction casting into the wall of an auxiliary source barrel, hanging a substrate in the auxiliary source barrel by using a conductive metal rod and a hook, and not contacting the target, ensuring that the inter-polar distance between the substrate and the rod-shaped source target is 10-50 mm, placing the auxiliary source barrel on a working disc connected with a source pulse power supply, and simultaneously supporting the auxiliary source barrel by using 3 metal cushion blocks with the height of 5-10 mm; and cleaning dust and metal scraps in the furnace body of the plasma solid-state surface metallurgical equipment, namely performing bombardment cleaning before diffusion plating.
Specifically, the bombardment cleaning step before the diffusion plating is carried out:
closing a furnace door of the plasma solid-state surface metallurgy device;
pumping the vacuum degree in the furnace body of the plasma solid-state surface metallurgy equipment to a set range (below 2000Pa in the embodiment);
and starting a source pulse power supply of the plasma solid-state surface metallurgy equipment, gradually increasing the voltage and the current of the power supply, enabling the auxiliary source barrel and the metal substrate 100 to generate glow discharge and arc striking phenomena, and performing bombardment cleaning on the high-entropy alloy source target (target) and the metal substrate 100 (base body).
In the specific application, the furnace door is closed, the mechanical pump is started to pump vacuum, the source pulse power supply is started when the pressure is below 2000Pa, the voltage and the current of the power supply are gradually increased, the auxiliary source barrel and the base material generate glow discharge and arc striking phenomena at the moment, the rod-shaped metal source material and the base material are bombarded and cleaned, after the arc striking phenomena disappear, the bombard cleaning is finished, and then the diffusion plating deposition step is carried out.
The diffusion plating deposition step comprises the following steps: and introducing inert protective gas, which can be argon, into the plasma solid-state surface metallurgy equipment, gradually increasing the voltage and the current of the source pulse power supply, so that the alloy elements of the high-entropy alloy source target material are deposited on the surface of the metal substrate 100 to form a high-entropy alloy, and the component distribution of the alloy elements is gently changed along with the depth. In the specific application, high-purity argon with a certain flow is gradually introduced, the purity of the argon is more than or equal to 99.99%, the flow is 5-40 mL/min, the voltage and the current of a source pulse power supply are gradually increased, at the moment, the metal substrate 100 (substrate) starts to be rapidly heated, and meanwhile, an infrared thermometer device is utilized to test the temperature of the substrate; adjusting the flow of argon gas to make the vacuum degree reach the working pressure (the vacuum degree is 20-60 Pa); the working temperature is 800-1400 ℃, and the voltage and the current of the source pulse power supply are adjusted according to the working temperature (the voltage of the source pulse power supply is controlled to be-600V-1000V); the heat preservation time is 2-5 hours; and after the heat preservation time is finished, closing the flow of argon.
Specifically, after the diffusion plating deposition step, an ion nitriding step is performed:
introducing ammonia gas into the plasma solid-state surface metallurgical equipment, wherein the purity of the ammonia gas is more than or equal to 99.99%, the flow rate is 50-200 mL/min, the glow thickness is controlled to be 3-6 mm, the introduced ammonia gas flow rate is adjusted according to the observed glow thickness, and the larger the ammonia gas flow rate is, the higher the air pressure is, and the thinner the glow thickness is; the nitriding temperature is 500-550 ℃, the voltage and the current of the source pulse power supply are adjusted according to the nitriding temperature, and the voltage of the pulse power supply is controlled to be-400V-1000V; and nitriding for 6-10 hours, after the heat preservation time is finished, closing the flow of ammonia gas, closing a power supply, keeping a mechanical pump to pump air, and cooling the high-entropy alloy to room temperature along with the furnace. In the embodiment, a plasma solid-state metallurgy metal infiltration technology is integrated with surface modification of a medical implant material, a medical high-entropy alloy film (coating) and ion nitriding research, the medical implant material is used as a base material, and the technical advantages of strong bonding force, high surface modification efficiency, low cost, adaptability to various complex workpiece shapes and the like of the plasma solid-state surface metallurgy technology are combined with the huge application potential of the ion nitriding surface modification and the medical high-entropy alloy film (coating), so that the wear resistance, corrosion resistance, stability and biocompatibility of the medical implant material are greatly improved, and the bonding strength is high.
Specifically, after the ion nitriding step, a post heat treatment step is performed:
the high-entropy alloy is subjected to tube sealing treatment, a quartz tube sealing machine can be used for sealing a base material, then a heat treatment furnace is used for heat treatment, the heat treatment temperature is 750-1000 ℃, the time is 1-6 hours, and after the heat treatment is finished, the high-entropy alloy is quenched in an ice-water mixture or liquid nitrogen.
The high-entropy alloy has the characteristics of high biological safety, high strength, high corrosion resistance, high wear resistance, easiness in forming simple phases and the like, is one of medical metal materials with the most research potential in recent years, and in the field of biological medicine, the high-entropy alloy has the hardness similar to that of bones, high specific strength and good corrosion resistance and wear resistance, and the characteristics are matched with the typical characteristics of the biological medical metal materials, so that the high-entropy alloy has good application potential in the field of medical health. The high-entropy alloy coating (film) not only can greatly reduce the production cost of the high-entropy alloy, but also can greatly improve the surface performance of a base material, is an important channel for developing the practical application of the high-entropy alloy, and has important strategic research value. The plasma solid surface metallurgy technology can overcome the defects of preparing high-entropy alloy coatings (films) by the traditional method, and the method can prepare the high-entropy alloy coatings (films) on the surfaces of various workpieces with complex shapes, has controllable components, forms metallurgical bonding with a base material, ensures enough bonding strength, has the thickness of dozens of micrometers, and has high surface modification efficiency.
The method adopts a plasma solid surface metallurgy technology to carry out multicomponent (5 or more alloy elements) co-permeation treatment on the surface of titanium or titanium alloy so as to obtain a novel gradient high-entropy alloy layer (high-entropy alloy deposition layer 112) which is in metallurgical bonding, and the alloy layer can keep good mechanical property and has good corrosion resistance, friction and abrasion resistance and biocompatibility under the biological environment.
The composite reinforced high-entropy alloy obtained by the preparation method is detected, and the detection result is as follows:
(1) a high-entropy alloy deposit layer 112 having a thickness of 15 μm was formed on the surface of the metal base 100 of pure titanium as a medical high-entropy alloy composite reinforcing layer, and a diffusion layer 111 (transition layer) having a thickness of 20 μm was formed on the metal base 100. The atomic percentage of each element in the medical high-entropy alloy composite strengthening layer (high-entropy alloy deposition layer 112) is respectively as follows: copper (Cu): 19%, cobalt (Co): 17%, chromium (Cr): 16%, titanium (Ti): 10%, iron (Fe): 20%, aluminum (Al): 13 percent of nitrogen (N) and 5 percent of nitrogen (N), and the surface high-entropy alloy is formed; and the element composition in the diffusion layer 111 changes slowly with the depth, and is metallurgically bonded with the pure titanium substrate.
(2) Hardness and frictional wear tests show that: the microhardness of the surface of the pure titanium substrate is 150HV, the microhardness of the surface of the medical high-entropy alloy composite strengthening layer is 1052HV, and the hardness is improved by 7 times; the specific wear rate of the pure titanium matrix was 18.3 (x 10)- 3mm3N-1m-1) The specific wear rate of the medical high-entropy alloy composite strengthening layer sample is 2.6 (multiplied by 10)-3mm3N-1m-1) 1/7 for the matrix only.
(3) Biocompatibility experiments show that: in vitro blood coagulation test, pure titanium and medical high-entropy alloy composite strengthening layer prothrombin time (APTT) and Prothrombin Time (PT) are respectively 26.3s, 10.9s, 26.1s and 10.8 s. Hemolysis rate experiments show that the Hemolysis Rates (HR) of the pure titanium and the medical high-entropy alloy composite strengthening layer are 0.13 percent and 0.38 percent respectively. Are all less than 5 percent, and meet the requirements of medical clinic. The cytotoxicity experiment shows that the relative proliferation rates of the L929 cells on the pure titanium and medical high-entropy alloy composite strengthening layer are 100% and 104% respectively. The cytotoxicity ratings were all 0.
The detection result shows that: by adopting the plasma solid-state surface metallurgy technology (plasma solid-state surface metallurgy mode), a medical high-entropy alloy composite strengthening layer (high-entropy alloy deposition layer 112) is successfully prepared on the surface of pure titanium, so that the hardness and the wear resistance of a workpiece are greatly improved by about 7 times. The prothrombin time (APTT) and the Prothrombin Time (PT) of the pure titanium and the medical high-entropy alloy composite strengthening layer are similar, which indicates that the composite strengthening layer has similar anticoagulant property; compared with pure titanium, the medical high-entropy alloy composite strengthening layer has relatively high hemolysis rate and cell proliferation rate, which shows that the hemolysis performance is relatively slightly poor, the cytotoxicity is relatively low, and the medical high-entropy alloy composite strengthening layer has better cell compatibility. According to the detection result, the pure titanium matrix and the medical high-entropy alloy composite strengthening layer are compared, and the following conclusion can be obtained: the medical high-entropy alloy composite strengthening layer obviously improves the wear resistance, hardness, stability and biocompatibility of the medical implant pure titanium material, and has good application prospect.
As shown in fig. 1 and fig. 2, an embodiment of the present invention further provides a manufacturing apparatus, which can be used for preparing the high-entropy alloy, and can adopt the manufacturing method, including a plasma solid-state surface metallurgy apparatus, where the plasma solid-state surface metallurgy apparatus has an anode cover 211, the anode cover 211 is connected to a furnace body 218, an auxiliary source barrel 223 is disposed in the furnace body 218, a plurality of high-entropy alloy source targets 214 are disposed inside the auxiliary source barrel 223, and the metal base material 100 is suspended in the auxiliary source barrel 223. The sidewalls of auxiliary source barrel 233 may be pre-formed with a plurality of through holes for high entropy alloy source target 214 to pass through.
Specifically, the preparation device further comprises a source pulse power supply device, the source pulse power supply device is provided with a first power supply 221 and a second power supply 222, a negative electrode of the first power supply 221 is connected to the metal base material 100 through a workpiece cathode frame 212 and a metal hook 213, a negative electrode of the second power supply 222 is connected to the high-entropy alloy source target 214 through a working disc 217 and an auxiliary source barrel 223, and a positive electrode of the first power supply 221 and a positive electrode of the second power supply 222 are both connected to the anode cover 211. The auxiliary source barrel 223 is seated on the work plate 217, and a metal pad 216 may be disposed between the auxiliary source barrel 223 and the work plate 217.
Specifically, the preparation device further comprises a vacuum pumping device connected to the plasma solid-state surface metallurgy equipment and used for pumping vacuum to the furnace body 218; the furnace body 218 or the anode cover 211 may be provided with a vacuum interface 220, and a vacuum device may be connected to the vacuum interface 220.
Specifically, the preparation device further comprises an aeration device which is connected to the plasma solid-state surface metallurgy equipment and is used for introducing set gas into the furnace body 218; the furnace body 218 or the anode cover 211 may be provided with a ventilation interface 224, and a ventilation device may be connected at the ventilation interface 224.
Specifically, the preparation device further comprises an infrared temperature measuring device which is connected to the plasma solid-state surface metallurgy device and used for measuring the temperature of the metal base material 100. The furnace body 218 or the anode cover 211 may be provided with a temperature measuring device interface 219, and the infrared temperature measuring device may be connected to the temperature measuring device interface 219.
The embodiment of the invention provides a medical high-entropy alloy composite strengthening layer and a preparation method thereof, which adopts a leading-level plasma solid surface metallurgy technology to fuse biomedicine, materials, machinery, electrons, an electric field, a magnetic field and plasma together, is a technical fusion in the multidisciplinary cross field, is a leading-edge technology of the surface modification research of the biomedical materials in the world at present, solves the problems of infiltration and surface alloying of high-melting-point metals which cannot be solved in the world at present, can process in a large area and realize the controllability of surface alloy components, and is an advanced surface engineering technology; the method has the advantages of saving alloy elements, greatly improving the surface performance, having no pollution and the like, can meet the requirement of mass production, has wide prospect, and is a high and new technology for sustainable development; moreover, the formed gradient high-entropy alloy layer has the component distribution of alloy elements which is gently changed along with the depth, is a gradient alloy material, is metallurgically bonded with the base material, has good bonding force, does not generate the stripping phenomenon, has good wear resistance, corrosion resistance, stability and biocompatibility, and can be well applied to the field of biological implantation materials.
The medical high-entropy alloy composite strengthening layer and the preparation method thereof provided by the embodiment of the invention integrate the plasma solid-state metallurgy metal infiltration technology with the surface modification of a medical implant material, a medical high-entropy alloy film (coating) and the research of ion nitriding, adopt the medical implant material as a base material, and greatly improve the wear resistance, corrosion resistance, stability and biocompatibility of the medical implant material by combining the technical advantages of the plasma solid-state surface metallurgy technology, such as strong bonding force, high surface modification efficiency, low cost, adaptability to various complex workpiece shapes and the like, with the ion nitriding surface modification and the huge application potential of the medical high-entropy alloy film (coating).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The medical high-entropy alloy composite strengthening layer is characterized in that a high-entropy alloy deposition layer is deposited on the surface of a metal substrate through a plasma solid-state surface metallurgy technology.
2. The medical high-entropy alloy composite strengthening layer of claim 1, wherein the high-entropy alloy deposition layer comprises at least five of Ti, Ta, Zr, Mo, Nb, Hf, Fe, W, Co, Cr, Cu, Al and Ni; the metal base material is made of titanium or titanium alloy.
3. A method for preparing the medical high-entropy alloy composite reinforced layer as claimed in claim 1 or 2, characterized by comprising the following steps:
preparing a metal substrate;
preparing a high-entropy alloy source target material containing at least five metal elements;
placing the metal substrate and the high-entropy alloy source target material in plasma solid-state surface metallurgy equipment;
and carrying out diffusion plating deposition on the high-entropy alloy source target on the surface of the metal base material through a solid surface metallurgy step by using the plasma solid surface metallurgy equipment to form a high-entropy alloy deposition layer.
4. The preparation method according to claim 3, wherein preparing the high-entropy alloy source target material comprises the following steps:
the material preparation step: selecting at least five of Ti, Ta, Zr, Mo, Nb, Hf, Fe, W, Co, Cr, Cu, Al and Ni with the purity of not less than 99.9%, and weighing and proportioning to obtain raw materials;
a primary smelting step: performing primary smelting on the raw materials;
vacuum arc melting: carrying out vacuum arc melting on the raw materials subjected to preliminary melting;
a target material forming step: and placing the raw material subjected to vacuum arc melting in a mold to form a set shape to obtain the high-entropy alloy source target.
5. The method of claim 4, wherein the solid state surface metallurgy step comprises the steps of:
preparing an auxiliary source barrel which can be placed in the plasma solid-state surface metallurgy equipment;
the installation step of the high-entropy alloy source electrode target material comprises the following steps: connecting the high-entropy alloy source electrode target material to the inner wall of an auxiliary source electrode barrel;
a metal base material mounting step: suspending the metal substrate in the auxiliary source electrode barrel through a conductive piece, wherein the metal substrate is not contacted with the high-entropy alloy source electrode target material;
and (3) diffusion plating deposition: and introducing inert protective gas into the plasma solid-state surface metallurgy equipment, gradually increasing the voltage and the current of the source pulse power supply, and depositing the alloy elements of the high-entropy alloy source target material on the surface of the metal base material to form a high-entropy alloy layer, wherein the component distribution of the alloy elements is gently changed along with the depth.
6. The method of claim 5, wherein prior to the step of diffusion depositing, a pre-diffusion bombardment cleaning step is performed:
closing a furnace door of the plasma solid state surface metallurgical equipment;
pumping the vacuum degree in the furnace body of the plasma solid-state surface metallurgical equipment to a set range;
and starting a source pulse power supply of the plasma solid-state surface metallurgy equipment, gradually increasing the voltage and the current of the power supply, enabling the auxiliary source barrel and the metal base material to generate glow discharge and arc striking phenomena, carrying out bombardment cleaning on the high-entropy alloy source target material and the metal base material, and finishing the bombardment cleaning after the arc striking phenomena disappear.
7. The method according to claim 6, wherein a pre-diffusion treatment step is performed before the pre-diffusion bombardment cleaning step:
polishing and cleaning the metal base material, and drying the metal base material;
cleaning dust and metal debris within a furnace body of the plasma solid state surface metallurgical equipment.
8. The production method according to claim 5, wherein in the diffusion deposition step:
the inert protective gas is argon, the purity is more than or equal to 99.99%, and the flow rate is 5-40 mL/min;
adjusting the flow of argon to enable the vacuum degree to reach the working air pressure with the vacuum degree of 20-60 Pa;
the temperature of the metal base material is 800-1400 ℃;
the heat preservation time is 2-5 hours, and after the heat preservation time is finished, the flow of argon is closed.
9. The method of claim 8, wherein the step of diffusion deposition is followed by a step of ion nitridation:
introducing ammonia gas into the plasma solid-state surface metallurgy equipment, wherein the purity of the ammonia gas is more than or equal to 99.99%, the flow rate of the ammonia gas is 50-200 mL/min, the glow thickness is controlled to be 3-6 mm, and the flow rate of the introduced ammonia gas is adjusted according to the observed glow thickness; the nitriding temperature is 500-550 ℃, the voltage and the current of the source pulse power supply are adjusted according to the nitriding temperature, and the voltage of the pulse power supply is controlled to be-400V-1000V; nitriding for 6-10 hours, after the heat preservation time is finished, closing the flow of ammonia gas, closing a power supply, keeping air extraction and cooling the treated material to room temperature along with the furnace;
after the ion nitriding step, performing a post heat treatment step:
and (3) performing tube sealing treatment on the treated material, then performing heat treatment by using a heat treatment furnace, wherein the heat treatment temperature is 750-1000 ℃, the time is 1-6 h, and quenching the treated material after the heat treatment is finished.
10. The preparation device for preparing the medical high-entropy alloy composite strengthening layer as claimed in claim 1 or 2, is characterized by comprising plasma solid-state surface metallurgy equipment, wherein the plasma solid-state surface metallurgy equipment is provided with an anode cover connected to a furnace body, an auxiliary source barrel is arranged in the furnace body, 20-200 high-entropy alloy source target materials are arranged on the inner side of the auxiliary source barrel, and the metal substrate is suspended in the auxiliary source barrel;
the preparation device also comprises a source electrode pulse power supply device, wherein the source electrode pulse power supply device is provided with a first path of power supply and a second path of power supply, the negative electrode of the first path of power supply is connected to the metal substrate through a workpiece cathode frame, the negative electrode of the second path of power supply is connected to the high-entropy alloy source electrode target through a working disc and an auxiliary source electrode barrel, and the positive electrode of the first path of power supply and the positive electrode of the second path of power supply are both connected to the anode cover;
the preparation device also comprises a vacuumizing device which is connected with the plasma solid-state surface metallurgy equipment and is used for vacuumizing the furnace body;
the preparation device also comprises a ventilation device which is connected with the plasma solid-state surface metallurgy equipment and is used for introducing set gas into the furnace body;
the preparation device also comprises an infrared temperature measuring device which is connected with the plasma solid-state surface metallurgy equipment and is used for measuring the temperature of the metal base material.
CN202210119130.1A 2022-02-08 2022-02-08 Medical high-entropy alloy composite strengthening layer and preparation method thereof Pending CN114525478A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116479251A (en) * 2023-06-25 2023-07-25 北京中辰至刚科技有限公司 Preparation method of high-entropy alloy cast ingot

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116479251A (en) * 2023-06-25 2023-07-25 北京中辰至刚科技有限公司 Preparation method of high-entropy alloy cast ingot
CN116479251B (en) * 2023-06-25 2023-09-01 北京中辰至刚科技有限公司 Preparation method of high-entropy alloy cast ingot

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