CN113445045A - Method for preparing artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding - Google Patents
Method for preparing artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding Download PDFInfo
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- CN113445045A CN113445045A CN202110705455.3A CN202110705455A CN113445045A CN 113445045 A CN113445045 A CN 113445045A CN 202110705455 A CN202110705455 A CN 202110705455A CN 113445045 A CN113445045 A CN 113445045A
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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
- 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
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
- C22C32/0057—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides based on B4C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
Abstract
The invention discloses a method for preparing an artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding, which comprises the following steps: placing a titanium alloy matrix on a constant-temperature heating platform, coating ceramic slurry on the surface of the titanium alloy matrix, drying to obtain the titanium alloy matrix containing a coating layer, fixing the titanium alloy matrix on an ultrasonic vibration device, and carrying out laser cladding treatment under a protective atmosphere with the assistance of ultrasonic vibration to obtain the artificial articular surface ceramic coating. The invention introduces ultrasonic vibration in the laser cladding process, utilizes the acoustic flow effect of ultrasonic waves to strengthen the stirring of a laser cladding molten pool and enhance the fluidity of the molten pool, and simultaneously, the cavitation effect of the ultrasonic waves breaks growing dendrites, thereby playing the role of refining grains, reducing the number of air holes, and obtaining a coating with smooth surface and better mechanical property and tribological property.
Description
Technical Field
The invention belongs to the field of material surface engineering, and particularly relates to a method for preparing an artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding.
Background
Currently, the artificial joint materials for clinical application mainly comprise stainless steel, cobalt-based alloy and titanium-based alloy. The mechanical property and biocompatibility of medical stainless steel and cobalt-based alloy have certain defects, and the implant is easy to lose efficacy. The titanium alloy has excellent biocompatibility, excellent biomechanical property, good corrosion resistance and excellent forming and processing properties, and becomes a preferred material for artificial joints. However, the titanium alloy surface has poor tribological properties, which results in wear resistance that does not meet the long life requirements of the prosthetic joint. In order to maintain the excellent mechanical property of the titanium alloy artificial joint and improve the surface tribological property of the titanium alloy artificial joint, a reliable surface modification method needs to be found.
Laser cladding technology is commonly used for surface modification and strengthening processing of materials as a rapid manufacturing technology. The laser cladding mode can be divided into a preset powder laying mode and a coaxial powder feeding mode. The process principle of the preset powder spreading type is as follows: under the irradiation of high-energy laser beams, the powder material precoated on the surface of the matrix is quickly melted, meanwhile, the surface of the matrix is slightly melted to form a molten pool, and the molten pool is quickly solidified after the laser beams leave, so that the interface forms firm metallurgical bonding, thereby ensuring the bonding strength of the coating and the matrix and meeting the implantation requirements. However, due to the characteristics of fast melting and fast setting of laser cladding and the difference between the temperature gradient and the thermal expansion coefficient of the coating and the base material, the coating is prone to generating cracks, air holes and other defects, and the problem of poor coating performance is also one of the problems which are being researched and solved by domestic and foreign scholars.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing an artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding. The ceramic coating is prepared by applying ultrasonic vibration, assisting the laser cladding process and utilizing the effects of ultrasonic cavitation acoustic flow and the like so as to achieve the purposes of refining crystal grains and improving the surface forming quality of the coating, and further improve the mechanical property and the tribological property of the titanium alloy artificial joint surface.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a method for preparing an artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding, which comprises the following steps:
placing a titanium alloy matrix on a constant-temperature heating platform, coating ceramic slurry on the surface of the titanium alloy matrix, drying to obtain the titanium alloy matrix containing a coating layer, fixing the titanium alloy matrix on an ultrasonic vibration device, and carrying out laser cladding treatment under a protective atmosphere with the assistance of ultrasonic vibration to obtain the artificial articular surface ceramic coating.
The invention introduces ultrasonic vibration in the laser cladding process, utilizes the acoustic flow effect of ultrasonic waves to strengthen the stirring of a laser cladding molten pool and enhance the fluidity of the molten pool, and simultaneously, the cavitation effect of the ultrasonic waves breaks growing dendrites, thereby playing the role of refining grains, reducing the number of air holes, and obtaining a coating with smooth surface and better mechanical property and tribological property.
Preferably, the titanium alloy matrix comprises Ti6Al 4V.
In the actual operation process, the titanium alloy substrate is cut into a step shape by a titanium alloy plate by utilizing a wire, and the step-shaped titanium alloy substrate can be better, more stably and firmly fixed on the ultrasonic vibration device. Meanwhile, the surface of the titanium alloy substrate is pretreated and dried for standby. The pretreatment process comprises the following steps: and (2) polishing the surface of the titanium alloy matrix by using 80-mesh coarse abrasive paper, removing oxide skin and oil stains on the surface, respectively placing the polished matrix in deionized water and absolute ethyl alcohol, cleaning for 10min by using an ultrasonic cleaning machine, and blow-drying for later use.
Preferably, the temperature of the constant-temperature heating platform is 70-80 ℃.
The inventor finds that the slurry can be evenly and flatly coated on the surface of the titanium alloy substrate by placing the titanium alloy substrate on a constant-temperature heating platform at 70-80 ℃ for preheating, and coating the slurry at 70-80 ℃, and if the temperature is too high, cracks are generated on the surface of the finally preset coating, so that the performance of the finished coating is greatly influenced; if the temperature is too low, drying is slow, and the surface of the pre-coating is uneven due to the agglomeration of the slurry.
In the preferred scheme, after the ceramic slurry is coated on the surface of the titanium alloy substrate, the temperature is kept for 20-40min at 70-80 ℃.
Preferably, the ceramic slurry is prepared by mixing Ti powder and B4Ball milling of C powderObtaining mixed powder, adding the mixed powder into a polyvinyl alcohol aqueous solution, and mixing to obtain the titanium-doped titanium dioxide powder, wherein in the mixed powder, the mass fraction of Ti powder is 60-80%, and B powder is4The mass fraction of the C powder is 20-40%.
More preferably, the Ti powder has a particle size of 3-8 μm and a purity of more than 99.9%, B4The average grain diameter of the C powder is 50-200nm, and the purity is more than 99.9%.
Further preferably, the rotation speed of the ball milling is 150-.
Further preferably, the mass fraction of the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol is 2-3 wt.%.
More preferably, the solid-liquid mass volume ratio of the mixed powder to the polyvinyl alcohol aqueous solution is 0.3-0.5g:1.5-2 ml.
Further preferably, the mixing mode is stirring for 20-30 min.
Preferably, the drying is carried out in a vacuum drying oven, the drying temperature is 40-50 ℃, and the drying time is 24-36 h.
The ceramic slurry prepared by the method can be evenly and flatly coated on the surface of the titanium alloy substrate by adopting the method of the invention.
In the practical operation process, the ultrasonic vibration device is firstly fixed on a moving platform of laser cladding equipment, and then the titanium alloy matrix containing the coating layer is fixed on a clamp of the ultrasonic vibration device.
In a preferred embodiment, the output power of the ultrasonic vibration is 200-600W. Preferably 200-400W.
In the invention, the output power of ultrasound needs to be effectively controlled, and the peeling of the preset coating and the deterioration of the surface quality can be caused by the overlarge output power of ultrasound, so that the effect of improving the performance can not be achieved; too little power is not significant.
In the preferred scheme, the specific process of performing laser cladding treatment under the protection atmosphere with the assistance of ultrasonic vibration comprises the following steps: firstly opening an ultrasonic vibration device, applying ultrasonic vibration to the titanium alloy matrix from the bottom, then introducing shielding gas for 10-20s, carrying out laser cladding treatment after the laser cladding device is filled with the shielding gas, and then closing the ultrasonic vibration after cladding is finished for 10-20 s.
In a preferred scheme, the laser cladding process parameters are as follows: the laser power is 400-500W, the laser scanning speed is 3-7mm/s, the laser spot diameter is 1-2mm, the lap joint rate is 20-40%, and the flow of the protective gas is 10-15L/min.
Further preferably, the protective atmosphere is argon.
The performance detection steps of the coating are as follows: after the cladded sample is subjected to warp cutting, inlaying, grinding and polishing, analyzing the tissue morphology of the cladding layer by adopting a Scanning Electron Microscope (SEM); testing the microhardness of the cladding layer by adopting a Vickers microhardness tester; 6mm of Si was used in a frictional wear tester3N4Performing a friction and wear experiment on a grinding ball in an SBF simulated body fluid, wherein the ball milling radius is 3mm, the rotating speed is 200rpm, and the wear time is 90 min; and measuring the wear section area of the wear sample by using a super-depth-of-field microscope, and calculating to obtain the wear volume.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, by introducing ultrasonic vibration, designing a scheme for applying the ultrasonic vibration, assisting the laser cladding process and utilizing the cavitation acoustic flow and other effects of the ultrasonic, the surface of the coating is more flat, and the shape of the uneven coating is obviously improved.
2. The invention designs the scheme of applying ultrasonic vibration by introducing ultrasonic vibration, assists the laser cladding process, and reduces the number of air holes in the coating by utilizing the effects of ultrasonic cavitation acoustic flow and the like, thereby prolonging the service life of the coating.
3. The invention improves the hardness and the wear resistance of the coating by introducing ultrasonic vibration, designing a scheme for applying the ultrasonic vibration, assisting the laser cladding process and utilizing the cavitation acoustic flow and other effects of the ultrasonic.
The technical scheme of the invention is further detailed by the following figures and examples
Drawings
Fig. 1 is a schematic structural diagram of an ultrasonic vibration-assisted laser cladding apparatus of the present invention.
The device comprises a laser 1, an optical fiber 2, a laser head 3, a high-temperature-resistant glass sheet 4, a sample 5, a clamp 6, an amplitude transformer 7, a support 8, a sleeve 9, an ultrasonic transducer 10, an argon tank 11, a motion platform 12, an ultrasonic generator 13 and a computer 14.
FIG. 2(a) is a photograph of a pre-set coating sample and (b) is a photograph of a finished coating sample; the shape and size of the sample can be seen in fig. 2.
FIG. 3 is a schematic view of a pre-coated sample; in fig. 3, 1 is a bolt fixing groove, 2 is a titanium alloy substrate, and 3 is a preset coating;
FIG. 4 is a cross-sectional profile of an ultra-depth of field three-dimensional microscope observation of the ceramic coatings prepared by ultrasonic vibration assisted laser cladding and the ceramic coatings prepared without ultrasonic vibration application of examples 1-3; as can be seen from fig. 4, the surface becomes more even with the application of the ultrasonic vibration of the coating; meanwhile, the number of air holes is obviously reduced;
FIG. 5 is SEM electron microscope observed cross-sectional profiles of ceramic coatings prepared by ultrasonic vibration assisted laser cladding and ceramic coatings prepared without ultrasonic vibration application of examples 1-3; it can be seen from fig. 5 that the dendrites of the coating applied with the ultrasonic vibration are broken up, and the grains are refined;
FIG. 6 is SEM electron microscope observations of the surface wear profiles of the coatings of examples 1-3 prepared by ultrasonic vibration assisted laser cladding and ceramic coatings prepared without ultrasonic vibration; it can be seen from FIG. 6 that the coating surface wear pattern is manifested as micro-furrowing and flaking;
FIG. 7 is a graph of the average Vickers hardness values of cross-sections of ceramic coatings prepared by ultrasonic vibration assisted laser cladding and ceramic coatings prepared without ultrasonic vibration applied in examples 1-3; it can be seen from fig. 7 that the coating to which the ultrasonic vibration is applied has a higher hardness;
FIG. 8 is a graph of the amount of wear of ceramic coatings prepared by ultrasonic vibration assisted laser cladding and ceramic coatings prepared without the application of ultrasonic vibration for examples 1-3; it can be seen from fig. 8 that the wear resistance of the coating layer to which ultrasonic vibration is applied is significantly improved;
FIG. 9 shows the surface morphology of the coating of comparative example 1, and it can be seen from FIG. 9 that the pre-coat is peeled off, and the coating is not coated on the surface of the substrate, revealing a very distinct metallic luster.
FIG. 10 shows the surface morphology of the pre-coat of comparative example 2, and it can be seen from FIG. 10 that the pre-coat has uneven surface and agglomerated particles are present.
FIG. 11 shows the surface morphology of the pre-coating of comparative example 3, and it can be seen from FIG. 11 that cracks appear on the surface of the pre-coating, which affect the quality and performance of the finished coating.
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:
the method for preparing the artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding comprises the following steps: the method specifically comprises the following steps:
(1) firstly, cutting a Ti6Al4V plate into a designed size by using a wire, polishing the surface of a substrate by using 80-mesh abrasive paper, removing oxide skin on the surface, then respectively placing the polished substrate into deionized water and absolute ethyl alcohol, cleaning for 10min by using an ultrasonic cleaning machine, and blow-drying for later use;
(2) mixing Ti powder (purity is more than or equal to 99.9% and average grain diameter is 5 μm) with B4C powder (purity is more than or equal to 99.9%, average particle size is 50nm) according to massThe content ratio is 70%: adding 30 percent of the mixture into a horizontal planetary ball mill for ball milling and mixing (the rotating speed is 200r/min, the ball milling time is 5 hours), and preparing into mixed powder. Weighing 0.4g of the mixed powder by using an electronic analytical balance, adding the weighed mixed powder into 2mL of a polyvinyl alcohol aqueous solution with the concentration of 2 wt.%, and stirring for 15min to prepare slurry;
(3) placing the sample block prepared in the step (1) on a constant-temperature heating platform at 70 ℃, then uniformly presetting the slurry in the step (2) on the surface of a sample block substrate, heating for 30min, and then placing the sample block substrate in a vacuum dryer at 40 ℃ for drying for 12 h;
(4) fixing the sample prepared in the step (3) on an ultrasonic vibration device through a bolt;
(5) then, carrying out laser cladding treatment in a continuous lapping mode, wherein the specific process parameters are as follows: the ultrasonic vibration frequency is 20kHz, the ultrasonic vibration output power is 200W, the laser power is 450W, the laser scanning speed is 3mm/s, the spot diameter is 1mm, the lap joint rate is 40%, and the flow of protective gas argon is 10L/min.
The adopted device for preparing the ceramic coating by ultrasonic vibration assisted laser cladding has a structural schematic diagram as shown in figure 1, and comprises an ultrasonic vibration device, a laser 1, a motion platform 12, a computer 14, an ultrasonic generator 13 and an argon tank 11; the ultrasonic vibration device comprises an ultrasonic transducer 10, an amplitude transformer 7 is connected above the ultrasonic transducer 10, a clamp 6 is connected above the amplitude transformer 7, a test sample 5 is fixed on the clamp 6, the amplitude transformer 7 is fixed on a support 8 through bolts, the support 8 is fixed on a sleeve 9 through bolts, the sleeve 9 is fixed on a motion platform 12 through bolts, a high-temperature-resistant glass sheet 4 is placed above the sleeve 9, the ultrasonic transducer 10 is connected with an ultrasonic generator 13, a computer 14 is connected with the motion platform 12 to control the motion platform 12 to move, the laser 1 is connected with a laser head 3 through an optical fiber 2, a circular light spot is focused on the surface of the test sample 5, an argon tank 11 is connected with the sleeve 9, and argon is introduced into the sleeve 9.
After the clad sample is subjected to warp cutting, inlaying, grinding and polishing, the structure morphology of the clad layer is analyzed by a Scanning Electron Microscope (SEM), as shown in FIG. 5 (b); using a Vickers microhardness testerThe microhardness of the cladding layer was measured and the results are shown in fig. 7; 6mm of Si was used in a frictional wear tester3N4Performing a friction wear experiment on a grinding ball in an SBF simulated body fluid, wherein the ball milling radius is 3mm, the rotating speed is 200rpm, the wear time is 90min, and the wear morphology result is shown in fig. 6 (b); the wear cross-sectional area of the wear specimen was measured using a super field depth microscope and the wear volume was calculated as shown in table 1.
TABLE 1 test results of the properties of the cladding layer
The average microhardness of the ceramic coating prepared by ultrasonic vibration assisted laser cladding of this example was about 836.4HV0.2The average microhardness of the coating without ultrasonic vibration is about 758HV0.2. Therefore, the ceramic coating prepared by the ultrasonic vibration assisted laser cladding has higher hardness, the hardness is improved by 10.34%, and the wear resistance is improved by 37.81% compared with the coating without ultrasonic vibration.
Example 2:
the method for preparing the artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding comprises the following steps: the method specifically comprises the following steps:
(1) firstly, cutting a Ti6Al4V plate into a designed size by utilizing linear cutting, polishing the surface of a substrate by using 80-mesh abrasive paper, removing oxide skin on the surface, then respectively placing the polished substrate into deionized water and absolute ethyl alcohol, cleaning for 10min by using an ultrasonic cleaning machine, and drying for later use;
(2) mixing Ti powder (purity is more than or equal to 99.9% and average grain diameter is 5 μm) with B4C powder (purity is more than or equal to 99.9%, and average particle size is 50nm) is 70% by mass: adding 30 percent of the mixture into a horizontal planetary ball mill for ball milling and mixing (the rotating speed is 200r/min, the ball milling time is 5 hours), and preparing into mixed powder. Weighing 0.4g of the mixed powder by using an electronic analytical balance, adding the weighed mixed powder into 2mL of a polyvinyl alcohol aqueous solution with the concentration of 2 wt.%, and stirring for 15min to prepare slurry;
(3) placing the sample block prepared in the step (1) on a constant-temperature heating platform at 70 ℃, then uniformly presetting the slurry in the step (2) on the surface of a sample block substrate, heating for 30min, and then placing the sample block substrate in a vacuum dryer at 40 ℃ for drying for 12 h;
(4) fixing the sample prepared in the step (3) on an ultrasonic vibration device through a bolt;
(5) then, carrying out laser cladding treatment in a continuous lapping mode, wherein the specific process parameters are as follows: the ultrasonic vibration frequency is 20kHz, the ultrasonic vibration output power is 400W, the laser power is 450W, the laser scanning speed is 3mm/s, the spot diameter is 1mm, the lap joint rate is 40%, and the flow of protective gas argon is 10L/min.
The device for preparing the ceramic coating by using the ultrasonic vibration assisted laser cladding is the same as that used in the embodiment 1.
After the clad sample is subjected to warp cutting, inlaying, grinding and polishing, the structure morphology of the clad layer is analyzed by a Scanning Electron Microscope (SEM), as shown in FIG. 5 (c); the microhardness of the cladding layer was measured using a vickers microhardness tester, and the results are shown in fig. 7; 6mm of Si was used in a frictional wear tester3N4Performing a friction wear experiment on a grinding ball in an SBF simulated body fluid, wherein the ball milling radius is 3mm, the rotating speed is 200rpm, the wear time is 90min, and the wear morphology result is shown in fig. 6 (c); the wear cross-sectional area of the wear specimen was measured using a super field depth microscope and the wear volume was calculated as shown in table 2.
TABLE 2 test results of the properties of the cladding layer
The average microhardness of the ceramic coating prepared by ultrasonic vibration assisted laser cladding of this example was about 896.1HV0.2The average microhardness of the coating without ultrasonic vibration is about 758HV0.2. Therefore, the ceramic coating prepared by the ultrasonic vibration assisted laser cladding has higher hardness, the hardness is improved by 18.22%, and the wear resistance is improved by 127.33% compared with the coating without ultrasonic vibration.
Example 3:
the method for preparing the artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding comprises the following steps: the method specifically comprises the following steps:
(1) firstly, cutting a Ti6Al4V plate into a designed size by utilizing linear cutting, polishing the surface of a substrate by using 80-mesh abrasive paper, removing oxide skin on the surface, then respectively placing the polished substrate into deionized water and absolute ethyl alcohol, cleaning for 10min by using an ultrasonic cleaning machine, and drying for later use;
(2) mixing Ti powder (purity is more than or equal to 99.9% and average grain diameter is 5 μm) with B4C powder (purity is more than or equal to 99.9%, and average particle size is 50nm) is 70% by mass: adding 30 percent of the mixture into a horizontal planetary ball mill for ball milling and mixing (the rotating speed is 200r/min, the ball milling time is 5 hours), and preparing into mixed powder. Weighing 0.4g of the mixed powder by using an electronic analytical balance, adding the weighed mixed powder into 2mL of a polyvinyl alcohol aqueous solution with the concentration of 2 wt.%, and stirring for 15min to prepare slurry;
(3) placing the sample block prepared in the step (1) on a constant-temperature heating platform at 70 ℃, then uniformly presetting the slurry in the step (2) on the surface of a sample block substrate, heating for 30min, and then placing the sample block substrate in a vacuum dryer at 40 ℃ for drying for 12 h;
(4) fixing the sample prepared in the step (3) on an ultrasonic vibration device through a bolt;
(5) then, carrying out laser cladding treatment in a continuous lapping mode, wherein the specific process parameters are as follows: the ultrasonic vibration frequency is 20kHz, the ultrasonic vibration output power is 600W, the laser power is 450W, the laser scanning speed is 3mm/s, the spot diameter is 1mm, the lap joint rate is 40%, and the flow of protective gas argon is 10L/min.
The device for preparing the ceramic coating by using the ultrasonic vibration assisted laser cladding is the same as that used in the embodiment 1.
After the clad sample is subjected to warp cutting, inlaying, grinding and polishing, the structure morphology of the clad layer is analyzed by a Scanning Electron Microscope (SEM), as shown in FIG. 5 (d); the microhardness of the cladding layer was measured using a vickers microhardness tester, and the results are shown in fig. 7; 6mm of Si was used in a frictional wear tester3N4Performing a friction wear experiment on a grinding ball in an SBF simulated body fluid, wherein the ball milling radius is 3mm, the rotating speed is 200rpm, the wear time is 90min, and the wear morphology result is shown in fig. 6 (d); the wear cross-sectional area of the wear specimen was measured using a super field depth microscope and the wear volume was calculated as shown in table 3.
TABLE 3 test results of the properties of the cladding layer
The average microhardness of the ceramic coating prepared by ultrasonic vibration assisted laser cladding of this example was about 785.9HV0.2The average microhardness of the coating without ultrasonic vibration is about 758HV0.2. Therefore, the ceramic coating prepared by the ultrasonic vibration assisted laser cladding has higher hardness, the hardness is improved by 3.68%, and the wear resistance is improved by 30.44% compared with the coating without ultrasonic vibration.
Comparative example 1
The other conditions were the same as in example 1 except that: the ultrasonic vibration output power is 800W; the obtained product has poor surface quality, the preset coating is peeled off in the ultrasonic vibration process and cannot be cladded on the substrate, and the surface of the coating is shown in figure 9.
Comparative example 2
The other conditions were the same as in example 1 except that: when the coating is pre-coated, the substrate is not heated; the resulting pre-coat surface was not flat and was shown in fig. 10.
Comparative example 3
The other conditions were the same as in example 1 except that: when the coating is pre-coated, the heating temperature of the substrate is 90 ℃; cracks appear on the surface of the obtained pre-coating, which affects the quality and performance of the finished coating, and the surface of the pre-coating is shown in fig. 11.
In conclusion, the technical scheme of the invention can ensure that the prepared ceramic coating has better coating surface quality, higher hardness and higher wear resistance compared with the coating without ultrasonic vibration.
Claims (10)
1. A method for preparing an artificial articular surface ceramic coating by ultrasonic vibration-assisted laser cladding is characterized by comprising the following steps: the method comprises the following steps: placing a titanium alloy matrix on a constant-temperature heating platform, coating ceramic slurry on the surface of the titanium alloy matrix, drying to obtain the titanium alloy matrix containing a coating layer, fixing the titanium alloy matrix on an ultrasonic vibration device, and carrying out laser cladding treatment under a protective atmosphere with the assistance of ultrasonic vibration to obtain the artificial articular surface ceramic coating.
2. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the titanium alloy matrix comprises Ti6Al 4V.
3. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the temperature of the constant-temperature heating platform is 70-80 ℃; and coating the ceramic slurry on the surface of the titanium alloy substrate, and keeping the temperature at 70-80 ℃ for 20-40 min.
4. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the ceramic slurry is prepared by mixing Ti powder and B4Ball-milling the powder C to obtain mixed powder, adding the mixed powder into a polyvinyl alcohol aqueous solution, and mixing to obtain the powder, wherein in the mixed powder, the mass fraction of Ti powder is 60-80%, and B powder is4The mass fraction of the C powder is 20-40%.
5. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the particle size of the Ti powder is 3-8 μm, the purity is more than 99.9 percent, B4The average grain diameter of the C powder is 50-200nm, and the purity is more than 99.9%; the rotation speed of the ball milling is 150-.
6. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the solid-liquid mass-volume ratio of the mixed powder to the polyvinyl alcohol aqueous solution is 0.3-0.5g:1.5-2ml, and the mass fraction of polyvinyl alcohol in the polyvinyl alcohol aqueous solution is 2-3 wt.%;
the mixing mode is stirring for 20-30 min;
the drying is carried out in a vacuum drying oven, the drying temperature is 40-50 ℃, and the drying time is 24-36 h.
7. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the output power of the ultrasonic vibration is 200-600W.
8. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the specific process of carrying out laser cladding treatment under the protective atmosphere with the assistance of ultrasonic vibration comprises the following steps: firstly opening an ultrasonic vibration device, applying ultrasonic vibration to the titanium alloy matrix from the bottom, then introducing shielding gas for 10-20s, carrying out laser cladding treatment after the laser cladding device is filled with the shielding gas, and then closing the ultrasonic vibration after cladding is finished for 10-20 s.
9. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the laser cladding process parameters are as follows: the laser power is 400-500W, the laser scanning speed is 3-7mm/s, the laser spot diameter is 1-2mm, the lap joint rate is 20-40%, and the flow of the protective gas is 10-15L/min.
10. The method for preparing the artificial articular surface ceramic coating by the ultrasonic vibration assisted laser cladding according to the claim 1, which is characterized in that: the protective atmosphere is argon.
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| CN114277242A (en) * | 2021-12-29 | 2022-04-05 | 浙江工业大学 | Periodic surface structure forming method based on ultrasonic vibration assisted laser remelting |
| CN114318331A (en) * | 2021-12-29 | 2022-04-12 | 浙江工业大学 | Ultrasonic semi-solid roll forging composite laser cladding forming method and device |
| CN115281897A (en) * | 2022-07-29 | 2022-11-04 | 大连理工大学 | Metal-ceramic hip joint prosthesis lining and manufacturing method thereof |
| CN117089837A (en) * | 2023-10-19 | 2023-11-21 | 烟台核电智能技术研究院有限公司 | Preparation method of ultrasonic strong vibration reinforced titanium-based composite wear-resistant coating |
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