CN113005443B - Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof - Google Patents

Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof Download PDF

Info

Publication number
CN113005443B
CN113005443B CN202110141409.5A CN202110141409A CN113005443B CN 113005443 B CN113005443 B CN 113005443B CN 202110141409 A CN202110141409 A CN 202110141409A CN 113005443 B CN113005443 B CN 113005443B
Authority
CN
China
Prior art keywords
tic
powder
substrate
preparation
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110141409.5A
Other languages
Chinese (zh)
Other versions
CN113005443A (en
Inventor
刘德福
陈涛
邓子鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202110141409.5A priority Critical patent/CN113005443B/en
Publication of CN113005443A publication Critical patent/CN113005443A/en
Application granted granted Critical
Publication of CN113005443B publication Critical patent/CN113005443B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • 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
    • A61L27/06—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
    • 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
    • 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
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L2420/06—Coatings containing a mixture of two or more compounds

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention provides a Ti5Si3A nano-structure reinforced TiC biological ceramic coating, a preparation method and application thereof. The preparation method comprises the following steps: mixing TiC powder and SiO2Preparing mixed powder consisting of the powder into uniform slurry, and coating the slurry on the surface of the pretreated substrate; drying the surface of the substrate to form a preset layer on the surface of the substrate, treating the preset layer by adopting a laser cladding process under a protective atmosphere, rapidly cooling at room temperature to obtain the Ti on the surface of the substrate5Si3The nano structure strengthens the TiC biological ceramic coating. Ti produced by the method5Si3The nano-structure reinforced TiC biological ceramic coating has higher hardness, good biocompatibility and wear resistance, can be widely used in the fields of medical treatment, industry and the like, and has better market application prospect.

Description

Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic coatings, and particularly relates to Ti5Si3A nano-structure reinforced TiC biological ceramic coating, a preparation method and application thereof.
Background
Titanium alloys are often used as materials for implants in the human body due to their low density, low modulus of elasticity, high strength, and high corrosion resistance. However, the lower hardness and wear resistance of titanium alloy limits its application to heavily loaded, highly worn parts (e.g., artificial articular surfaces). The surface modification technology is an effective means for improving the surface performance of the titanium alloy, but the common surface modification technology, such as the technologies of plasma spraying, chemical vapor deposition and the like, has the defects of large coating grains, cracks, micropores and the like, has poor bonding force between the coating and a substrate, and is not suitable for being used as a part of parts such as an artificial joint surface and the like.
The laser cladding technology is a surface modification technology using laser as a heat source, and is a surface strengthening technology for forming a coating with controllable thickness by melting cladding materials and a substrate thin layer by using medium/high-power laser beams. The coating prepared by laser cladding has compact and fine tissue, can realize metallurgical bonding with a substrate, is suitable for preparing a high-quality and high-performance coating required by a human implant, but the existing laser cladding metal-based composite coating has the potential problem of in vivo sensitization caused by the precipitation of metal ions, and limits the application of the coating in the field of human implants.
Therefore, it is important to design a titanium alloy-based undercoating implant suitable for the heavy-load and strong-abrasion environment in human body, and the coating needs to have excellent properties such as good abrasion resistance and biocompatibility. At present, the laser cladding technology is adopted to prepare Ti5Si3The technology of the nano-structure reinforced TiC wear-resistant biological ceramic coating is not reported.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a Ti alloy which overcomes the disadvantages and drawbacks mentioned in the background art5Si3A nano-structure reinforced TiC biological ceramic coating, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
ti5Si3The preparation method of the nano-structure reinforced TiC biological ceramic coating comprises the following steps:
(1) mixing TiC powder and SiO2Preparing mixed powder consisting of the powder into uniform slurry, and coating the slurry on the surface of the pretreated substrate;
(2) drying the surface of the substrate obtained in the step (1), forming a preset layer on the surface of the substrate, treating the preset layer by adopting a laser cladding process under a protective atmosphere, then rapidly cooling at room temperature to obtain the Ti on the surface of the substrate5Si3The nano structure strengthens the TiC biological ceramic coating.
Titanium carbide (TiC) is a typical transition groupThe metal carbide is carbide ceramic formed by mixing ionic bonds, covalent bonds and metallic bonds, and C atoms occupy octahedral gaps of a Ti close-packed lattice to form a face-centered cubic structure. TiC has the characteristics of high melting point, high strength, high hardness, good wear resistance and corrosion resistance, lower thermal expansion coefficient, good heat conductivity and electric conductivity, biocompatibility and the like, and is a potential implantable wear-resistant material. Silicon dioxide (SiO)2) Is nontoxic, can be used as a liquid phase sintering aid to influence the microstructure of ceramic particles and increase the sintering density. The technical scheme of the invention is that nano TiC ceramic powder is taken as a base material, and micron SiO is added2Powder is used as low-melting point additive material, and SiO is generated under laser irradiation2First melted to form a liquid phase, passing through the liquid phase SiO2The rapid densification of the TiC particles is realized by the flow, which is beneficial to the rapid heat transfer of the preset powder layer and the rapid melting of the TiC particles. Meanwhile, Ti can be generated through in-situ reaction in the laser cladding process5Si3The nano-structure reinforcing phase is pinned in the coating, so that the mechanical property of the TiC-based ceramic coating is further effectively improved. In addition, SiO2Provided composite anion SiO2 4-With Ti4+Has an attractive force lower than that of Ti4+And C4-The attractive force of the ionic bond between the TiC ceramic coating and the TiC ceramic coating can reduce the surface tension of the melt, so that the surface smoothness of the TiC ceramic coating is improved.
In the above preparation method, preferably, in the mixed powder, the mass fraction of the TiC powder is 70% to 90%, and the mass fraction of the SiO powder is2The mass fraction of the powder is 10-30%; the grain size of the TiC powder is 40-60 nm, and the purity is more than or equal to 99.5%; SiO 22The particle size of the powder is 3-6 mu m, and the purity is more than or equal to 99.9%. With SiO2The content is increased, the hardness and the wear resistance of the coating are increased, but the fracture toughness and the biocompatibility are reduced, and in order to ensure the comprehensive performance of the coating, TiC powder and SiO powder are required2The addition ratio of the powder is controlled within the scope of the present invention.
Preferably, in the step (2), in order to ensure the comprehensive performance of the coating, when the coating is processed by a laser cladding process, the laser power is controlled to be 300W, the scanning speed is 5mm/s, the overlapping rate is 20%, and the diameter of a light spot is 1 mm.
In the preparation method, preferably, in the step (2), the protective atmosphere is argon, and the flow of argon is controlled to be 5-15L/min.
In the preparation method, preferably, in the step (2), the thickness of the preset layer is 0.2-0.5 mm. The thickness of the preset layer needs to be controlled within the range of the invention, the excessively low thickness of the preset layer can cause the excessively high dilution rate of the coating, and the excessively high thickness of the preset layer can influence the forming quality of the coating. More preferably, the thickness of the preset layer is 0.38-0.42 mm.
Preferably, in the preparation method, in the step (1), TiC powder and SiO are weighed according to the mass ratio2And (3) uniformly mixing the powder and the slurry by adopting a ball milling mode to obtain mixed powder, adding the mixed powder into the solution under stirring, and then carrying out ultrasonic vibration treatment until the mixed powder is uniformly mixed to obtain slurry. In the process of preparing the slurry, if only stirring treatment is carried out, the surface of the preset layer obtained after drying is uneven and powder agglomeration is obvious, and the surface of the preset layer obtained after stirring and ultrasonic treatment is smooth and flat, so that the preparation of a high-quality coating by a laser cladding technology is facilitated.
Preferably, in the preparation method, the ball milling is carried out in a planetary ball mill, the ball milling rotating speed is 180-220 rmp/min, and the ball milling time is 2-3 h; the solution is polyvinyl alcohol aqueous solution, the concentration of the polyvinyl alcohol aqueous solution is 0.5-5% vol, and the mass ratio of the mixed powder to the polyvinyl alcohol aqueous solution is (0.4-0.5): 2-3. Considering that the pre-set layer is cracked due to too low concentration of the aqueous polyvinyl alcohol solution and the pre-set layer is warped due to too high concentration, the concentration of the aqueous polyvinyl alcohol solution is controlled within the range of the present invention. More preferably, the concentration of the polyvinyl alcohol aqueous solution is 0.5-2% vol. More preferably, the concentration of the aqueous polyvinyl alcohol solution is 1% vol.
In the above preparation method, preferably, the substrate is Ti6Al4A V titanium alloy plate.
In the preparation method, the substrate is preferably pretreated by the following specific operation steps: the substrate surface was polished with 100-mesh sandpaper to remove oxide films and oil stains, and then cleaned and dried.
As a general inventive concept, the present invention also provides Ti prepared according to the above-mentioned preparation method5Si3The nano structure strengthens the TiC biological ceramic coating.
As a general inventive concept, the present invention also provides a Ti as described above5Si3The application of the nano-structure reinforced TiC biological ceramic coating in the field of biomedicine.
Compared with the prior art, the invention has the advantages that:
(1) ti of the invention5Si3The nano-structure reinforced TiC biological ceramic coating utilizes the characteristics of a laser cladding process of fast heating and fast setting to prepare a high-quality biological ceramic coating on the surface of a titanium alloy, the surface of the coating is relatively flat, and metallurgical bonding with a substrate is realized.
(2) Ti of the invention5Si3The nanometer structure reinforced TiC bioceramic coating mainly uses TiC phase as main component, and at the same time utilizes in-situ synthesis to obtain Ti with nanometer structure5Si3And the mechanical property of the TiC ceramic coating is effectively improved in the coating by pinning, and the coating has higher hardness, good biocompatibility and wear resistance, can be widely applied to the fields of medical treatment, industry and the like, and has better market application prospect.
(3) Ti of the invention5Si3The preparation method of the nano-structure reinforced TiC biological ceramic coating has the advantages of short process flow, simple operation and low process cost, and is suitable for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a drawing of the present inventionTi prepared in example 15Si3Scanning electron micrographs of 2 ten thousand times (left) and 10 ten thousand times (right) of the nano-structure reinforced TiC biological ceramic coating are respectively amplified;
FIG. 2 is Ti prepared in example 1 of the present invention5Si3A scanning electron microscope image of the nano-structure reinforced TiC biological ceramic coating amplified by 5000 times;
FIG. 3 shows Ti prepared in examples 1 to 3 of the present invention5Si3The nano structure enhances the hardness distribution of the TiC biological ceramic coating;
FIG. 4 shows Ti prepared in examples 1 to 3 of the present invention5Si3Nano-structure reinforced TiC biological ceramic coating and Ti used thereby6Al4V, distribution of abrasion loss of the substrate;
FIG. 5 shows Ti prepared in example 2 of the present invention5Si3Scanning electron micrographs of 2 ten thousand times (left) and 10 ten thousand times (right) of the nano-structure reinforced TiC biological ceramic coating are respectively amplified;
FIG. 6 is Ti prepared in example 2 of the present invention5Si3A scanning electron microscope image of the nano-structure reinforced TiC biological ceramic coating amplified by 5000 times;
FIG. 7 shows Ti prepared in example 2 of the present invention5Si3The nano structure enhances the appearance of MG-63 cells cultured on the surface of the TiC biological ceramic coating for 1, 3 and 5 days;
FIG. 8 shows Ti prepared in example 3 of the present invention5Si3Scanning electron microscope image of nano structure reinforced TiC biological ceramic coating magnified 5000 times.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
one kind of Ti of the present invention5Si3The preparation method of the nano-structure reinforced TiC biological ceramic coating comprises the following steps:
(1) TiC powder with the mass fraction of 90% (the particle diameter is 40-60 nm, the purity is more than or equal to 99.5%) and SiO with the mass fraction of 10%2Adding the powder (the particle size is 3-6 mu m, the purity is more than or equal to 99.9%) into a planetary ball mill, and uniformly mixing to obtain mixed powder, wherein the ball milling speed is 200rmp/min, and the ball milling time is 2 hours; adding the mixed powder into a polyvinyl alcohol aqueous solution with the concentration of 1% vol, wherein the mass ratio of the mixed powder to the polyvinyl alcohol aqueous solution is 0.45: 2.8, continuously stirring, and then performing ultrasonic vibration treatment until the materials are uniformly mixed to obtain slurry; by using Ti6Al4The method comprises the following steps of taking a V titanium alloy plate as a substrate, wherein the size of the substrate is 30mm multiplied by 6mm, polishing the surface of the substrate by using 100-mesh abrasive paper to remove an oxidation film and oil stains, then cleaning and drying, and then coating slurry on the surface of the pretreated substrate;
(2) drying the surface of the substrate obtained in the step (1) to form a preset layer with the thickness of about 0.4mm on the surface of the substrate; opening an argon gas valve, adjusting the flow to 10L/min, starting laser to perform laser cladding treatment, controlling the laser power to be 300W, the scanning speed to be 5mm/s, the overlapping rate to be 20 percent, the diameter of a light spot to be 1mm, stopping the laser after the laser cladding is finished, closing the argon gas valve, rapidly cooling at room temperature, and obtaining Ti on the surface of the substrate5Si3The nano structure strengthens the TiC biological ceramic coating.
Ti prepared in this example was subjected to a scanning electron microscope5Si3The tissue morphology of the nano-structure enhanced TiC biological ceramic coating is analyzed, and the coating contains nano-spherical granular Ti5Si3Structure (see fig. 1), TiC phase being a dendritic structure (see fig. 2), and Ti5Si3The phases are pinned in the coating. The Ti was tested5Si3Hardness of nano-structure reinforced TiC biological ceramic coatingThe degree can reach 814.3HV0.2(see FIG. 3), fracture toughness of 2.33 MPa-m1/2. The frictional wear performance of the coating was tested in a Simulated Body Fluid (SBF) wear test environment using a HT-1000 type frictional wear tester, and all sample surfaces were sanded to 1000# with SiC abrasive paper before the test. The grinding ball for the abrasion test is a tungsten-cobalt alloy ball with the diameter of 6 mm. The test parameters of the abrasion test are load 10N, abrasion time 60min, rotation speed 200rpm, rotation radius 5mm and room temperature. The wear cross-sectional area of the sample was observed using a super-depth-of-field microscope with a volumetric wear loss of 23.6X 10-2mm3(see FIG. 4), the coating wears only Ti6Al41/4.1 of the V titanium alloy.
Example 2:
one kind of Ti of the present invention5Si3The preparation method of the nano-structure reinforced TiC biological ceramic coating comprises the following steps:
(1) TiC powder with the mass fraction of 80% (the particle diameter is 40-60 nm, the purity is more than or equal to 99.5%) and SiO with the mass fraction of 20%2Adding the powder (the particle size is 3-6 mu m, the purity is more than or equal to 99.9%) into a planetary ball mill, and uniformly mixing to obtain mixed powder, wherein the ball milling speed is 200rmp/min, and the ball milling time is 2 hours; adding the mixed powder into a polyvinyl alcohol aqueous solution with the concentration of 1% vol, wherein the mass ratio of the mixed powder to the polyvinyl alcohol aqueous solution is 0.45: 2.8, continuously stirring, and then performing ultrasonic vibration treatment until the materials are uniformly mixed to obtain slurry; by using Ti6Al4The method comprises the following steps of taking a V titanium alloy plate as a substrate, wherein the size of the substrate is 30mm multiplied by 6mm, polishing the surface of the substrate by using 100-mesh abrasive paper to remove an oxidation film and oil stains, then cleaning and drying, and then coating slurry on the surface of the pretreated substrate;
(2) drying the surface of the substrate obtained in the step (1) to form a preset layer with the thickness of about 0.4mm on the surface of the substrate; opening an argon gas valve, adjusting the flow to 10L/min, starting laser to perform laser cladding treatment, controlling the laser power to be 300W, the scanning speed to be 5mm/s, the overlapping rate to be 20 percent, the diameter of a light spot to be 1mm, stopping the laser after the laser cladding is finished, closing the argon gas valve, rapidly cooling at room temperature, and obtaining Ti on the surface of the substrate5Si3The nano structure strengthens the TiC biological ceramic coating.
Ti prepared in this example was subjected to a scanning electron microscope5Si3The tissue morphology of the nano-structure enhanced TiC biological ceramic coating is analyzed, and the coating contains nano-lamellar Ti5Si3Structure (see fig. 5), TiC phase being a cell structure (see fig. 6), and Ti5Si3The phases are pinned in the coating. The Ti was tested5Si3The hardness of the TiC biological ceramic coating reinforced by the nano structure can reach 935.7HV0.2(see FIG. 3), fracture toughness of 2.22 MPa-m1/2. The frictional wear performance of the coating was tested in a Simulated Body Fluid (SBF) wear test environment using a HT-1000 type frictional wear tester, and all sample surfaces were sanded to 1000# with SiC abrasive paper before the test. The grinding ball for the abrasion test is a tungsten-cobalt alloy ball with the diameter of 6 mm. The test parameters of the abrasion test are load 10N, abrasion time 60min, rotation speed 200rpm, rotation radius 5mm and room temperature. The wear cross-sectional area of the sample was observed using a microscope with an ultra depth of field, and the volume wear was 17.3X 10-2mm3(see FIG. 4), the coating wears only Ti6Al41/5.6 of the V titanium alloy.
The MG63 cells on the surface of the TiC ceramic coating prepared in this example can normally adhere and proliferate, as shown in fig. 7, the cells on the surface of the coating gradually increase with the increase of the culture time, and the cells almost cover the surface of the coating by day 5, which indicates that the cells have good biocompatibility and have the potential to be used as a human body implant material.
Example 3:
one kind of Ti of the present invention5Si3The preparation method of the nano-structure reinforced TiC biological ceramic coating comprises the following steps:
(1) 70 percent of TiC powder (the particle diameter is 40-60 nm, the purity is more than or equal to 99.5 percent) and 30 percent of SiO by mass fraction2Adding the powder (the particle size is 3-6 mu m, the purity is more than or equal to 99.9%) into a planetary ball mill, and uniformly mixing to obtain mixed powder, wherein the ball milling speed is 200rmp/min, and the ball milling time is 2 hours; adding the mixed powder into a polyvinyl alcohol aqueous solution with the concentration of 1% vol,the mass ratio of the mixed powder to the polyvinyl alcohol aqueous solution is 0.45: 2.8, continuously stirring, and then performing ultrasonic vibration treatment until the materials are uniformly mixed to obtain slurry; by using Ti6Al4The method comprises the following steps of taking a V titanium alloy plate as a substrate, wherein the size of the substrate is 30mm multiplied by 6mm, polishing the surface of the substrate by using 100-mesh abrasive paper to remove an oxidation film and oil stains, then cleaning and drying, and then coating slurry on the surface of the pretreated substrate;
(2) drying the surface of the substrate obtained in the step (1) to form a preset layer with the thickness of about 0.4mm on the surface of the substrate; opening an argon gas valve, adjusting the flow to 10L/min, starting laser to perform laser cladding treatment, controlling the laser power to be 300W, the scanning speed to be 5mm/s, the overlapping rate to be 20 percent, the diameter of a light spot to be 1mm, stopping the laser after the laser cladding is finished, closing the argon gas valve, rapidly cooling at room temperature, and obtaining Ti on the surface of the substrate5Si3The nano structure strengthens the TiC biological ceramic coating.
Ti prepared in this example was subjected to a scanning electron microscope5Si3The tissue morphology of the nano-structure enhanced TiC bioceramic coating is analyzed, and the coating contains nano-lamellar Ti consistent with that in example 25Si3Structure, TiC phase is a cellular dendrite structure (see FIG. 8), and Ti5Si3The phases are pinned in the coating. The Ti was tested5Si3The hardness of the TiC biological ceramic coating reinforced by the nano structure can reach 1045.0HV0.2(see FIG. 3), fracture toughness of 2.13 MPa-m1/2. The frictional wear performance of the coating was tested in a Simulated Body Fluid (SBF) wear test environment using a HT-1000 type frictional wear tester, and all sample surfaces were sanded to 1000# with SiC abrasive paper before the test. The grinding ball for the abrasion test is a tungsten-cobalt alloy ball with the diameter of 6 mm. The test parameters of the abrasion test are load 10N, abrasion time 60min, rotation speed 200rpm, rotation radius 5mm and room temperature. The wear cross-sectional area of the sample was observed using a super-depth-of-field microscope with a volumetric wear loss of 15.1X 10-2mm3(see FIG. 4), the coating wears only Ti6Al41/6.4 of the V titanium alloy.

Claims (8)

1. Ti5Si3The preparation method of the nano-structure reinforced TiC biological ceramic coating is characterized by comprising the following steps:
(1) mixing TiC powder and SiO2Preparing mixed powder consisting of the powder into uniform slurry, and coating the slurry on the surface of the pretreated substrate;
(2) drying the surface of the substrate obtained in the step (1), forming a preset layer on the surface of the substrate, treating the preset layer by adopting a laser cladding process under a protective atmosphere, then rapidly cooling at room temperature to obtain the Ti on the surface of the substrate5Si3The nano structure strengthens the TiC biological ceramic coating.
2. The preparation method of claim 1, wherein the mixed powder comprises 70-90% by mass of TiC powder and SiO powder2The mass fraction of the powder is 10% -30%; the grain size of the TiC powder is 40-60 nm, and the purity is more than or equal to 99.5%; SiO 22The particle size of the powder is 3-6 mu m, and the purity is more than or equal to 99.9%.
3. The preparation method according to claim 1 or 2, wherein in the step (2), when the laser cladding process is adopted for treatment, the laser power is controlled to be 300W, the scanning speed is 5mm/s, the overlapping rate is 20%, and the spot diameter is 1 mm.
4. The preparation method according to claim 1 or 2, wherein in the step (2), the protective atmosphere is argon, and the flow rate of the argon is controlled to be 5-15L/min.
5. The method according to claim 1 or 2, wherein in the step (2), the thickness of the pre-layer is 0.2 to 0.5 mm.
6. The production method according to claim 1 or 2, wherein in the step (1), TiC powder and SiO are weighed in a mass ratio2Mixing the powder and the powder by ball millingAnd uniformly mixing to obtain mixed powder, adding the mixed powder into the solution under stirring, and then performing ultrasonic vibration treatment until the mixed powder is uniformly mixed to obtain slurry.
7. The preparation method of claim 6, wherein the ball milling is carried out in a planetary ball mill, the ball milling rotation speed is 180-220 rmp/min, and the ball milling time is 2-3 h; the solution is polyvinyl alcohol aqueous solution, the concentration of the polyvinyl alcohol aqueous solution is 0.5-5% vol, and the mass ratio of the mixed powder to the polyvinyl alcohol aqueous solution is (0.4-0.5): 2-3.
8. The production method according to claim 1 or 2, wherein the substrate is Ti6Al4A V titanium alloy plate.
CN202110141409.5A 2021-01-29 2021-01-29 Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof Active CN113005443B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110141409.5A CN113005443B (en) 2021-01-29 2021-01-29 Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110141409.5A CN113005443B (en) 2021-01-29 2021-01-29 Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113005443A CN113005443A (en) 2021-06-22
CN113005443B true CN113005443B (en) 2022-02-01

Family

ID=76385214

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110141409.5A Active CN113005443B (en) 2021-01-29 2021-01-29 Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113005443B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113445045A (en) * 2021-06-24 2021-09-28 中南大学 Method for preparing artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding
CN114807723B (en) * 2022-04-13 2023-01-17 北京科技大学 Metal ceramic composite coating and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB894593A (en) * 1957-11-22 1962-04-26 Siemens Planiawerke Ag Improvements in or relating to shaped bodies composed of porous material, such as graphite or carbon, and having a gas tight and liquid tight surface
CN1789202A (en) * 2004-12-15 2006-06-21 中国科学院金属研究所 Ti3AlC2/Ti5Si3 compound material and its preparation method
CN104018155A (en) * 2014-06-06 2014-09-03 江苏大学 Method for preparing Ti-Si-C coating on surface of titanium metal
CN106893879A (en) * 2017-02-27 2017-06-27 盐城工学院 A kind of titanium matrix composite and preparation method thereof
CN107488853A (en) * 2017-08-15 2017-12-19 成都新柯力化工科技有限公司 A kind of laser heat treatment technology for improving titanium alloy wearability
CN108517518A (en) * 2018-03-28 2018-09-11 中南林业科技大学 A kind of preparation method for the composite coating improving titanium alloy high-temperature antioxygenic property

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB894593A (en) * 1957-11-22 1962-04-26 Siemens Planiawerke Ag Improvements in or relating to shaped bodies composed of porous material, such as graphite or carbon, and having a gas tight and liquid tight surface
CN1789202A (en) * 2004-12-15 2006-06-21 中国科学院金属研究所 Ti3AlC2/Ti5Si3 compound material and its preparation method
CN104018155A (en) * 2014-06-06 2014-09-03 江苏大学 Method for preparing Ti-Si-C coating on surface of titanium metal
CN106893879A (en) * 2017-02-27 2017-06-27 盐城工学院 A kind of titanium matrix composite and preparation method thereof
CN107488853A (en) * 2017-08-15 2017-12-19 成都新柯力化工科技有限公司 A kind of laser heat treatment technology for improving titanium alloy wearability
CN108517518A (en) * 2018-03-28 2018-09-11 中南林业科技大学 A kind of preparation method for the composite coating improving titanium alloy high-temperature antioxygenic property

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Unraveling the mechanical and tribological properties o a novel Ti5Si3/TiC nanocomposite coating synthesized by a double glow discharge plasma technique";Jiang Xu等;《Ceramics International》;20130530;第39卷;第9480页结论 *
"原位生成TiC/Ti5Si3纳米复合材料的显微结构研究";李建林等;《无机材料学报》;20000430;第15卷(第2期);第336-340页 *

Also Published As

Publication number Publication date
CN113005443A (en) 2021-06-22

Similar Documents

Publication Publication Date Title
CN113005443B (en) Ti5Si3Nano-structure reinforced TiC biological ceramic coating and preparation method and application thereof
CN111005019B (en) Method for preparing TiC/TiB wear-resistant coating in situ through laser cladding
CN110938816B (en) Laser cladding SiC nanoparticle reinforced Ti (C, N) ceramic coating and application thereof
CN113652642B (en) Gradient ceramic high-entropy alloy coating and preparation method thereof
Motallebzadeh et al. Mechanical properties of TiTaHfNbZr high-entropy alloy coatings deposited on NiTi shape memory alloy substrates
Wu et al. An advanced self-lubricating ceramic composite with the addition of core-shell structured h-BN@ Ni powders
CN108103494A (en) A kind of new high-entropy alloy coating and preparation method thereof
CN105506613A (en) Preparation method for high-entropy alloy coating
CN113445045A (en) Method for preparing artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding
CN105483432B (en) A kind of titanium alloy wearing layer and preparation method thereof
CN107779814A (en) A kind of preparation method of the gradient of nano-particle containing Ag wear-resistant coating
Cheng et al. Tribology property of laser cladding crack free Ni/WC composite coating
Zhao et al. Synergistic effects of Mo and in-situ TiC on the microstructure and wear resistance of AlCoCrFeNi high entropy alloy fabricated by laser cladding
TWI790132B (en) Wc-base hard alloy and its application
CN107557782A (en) Titanium alloy surface laser in-situ synthesizes TiBx‑TiN/Ti3Al composite coatings and preparation method
Zhou et al. Effect of laser power on anisotropic microstructure and mechanical behavior of biomedical Ti-35Nb-15Zr (at%) alloy fabricated by laser powder bed fusion
Yang et al. Microstructure and wear resistance of Ti–Cu–N composite coating prepared via laser cladding/laser nitriding technology on Ti–6Al–4V alloy
Wäsche et al. In situ formation of tribologically effective oxide interfaces in SiC‐based ceramics during dry oscillating sliding
CN110241419A (en) A kind of surface has titanium alloy material and the application of resistance to high temperature oxidation and wear-resistant coating
CN110408924A (en) It is a kind of for the titanium-based mixed-powder and manufacturing method of laser cladding coating and application
CN109732496A (en) Iron-binding agent fused alumina zirconia grinding wheel and preparation method thereof for railway track reconditioning
CN112795919B (en) Composite coating material for improving friction performance of TC4 alloy and preparation method thereof
CN115287588A (en) TiN gradient nano hard coating and preparation method thereof
CN109881028A (en) A kind of resistant amorphous alloy system and its application
CN115433932B (en) Pure titanium surface gradient micro-nano TiZn 3 -TiZn X Composite coating and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant