CN114226734A - Copper-containing wear-resistant coating on surface of titanium alloy manufactured by additive manufacturing and preparation process thereof - Google Patents
Copper-containing wear-resistant coating on surface of titanium alloy manufactured by additive manufacturing and preparation process thereof Download PDFInfo
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Abstract
The invention relates to a copper-containing wear-resistant coating on the surface of a titanium alloy manufactured by additive manufacturing, wherein the wear-resistant coating is positioned on the surface of a titanium alloy substrate and comprises a bottom layer and a surface layer, the bottom layer is a pure copper bottom layer, the surface layer is a copper-containing surface layer uniformly distributed with wear-resistant particles, the titanium alloy substrate is mechanically combined with the pure copper bottom layer or the copper-containing surface layer, pit textures are uniformly distributed on the copper-containing surface layer, and the textures are obtained by machining the surface of the copper-containing surface layer in a mechanical extrusion or laser mode. According to the technical scheme, the idea of additive modification is adopted for 3D printing of the titanium alloy, the problem of large roughness of the 3D printing metal surface is solved without material reduction and polishing, the surface tribological performance of the 3D printing metal surface can be improved, and the 3D printing titanium alloy can be further deeply applied.
Description
Technical Field
The invention belongs to the technical field of 3D printing metal surface treatment, and particularly designs a copper-containing wear-resistant coating on the surface of a titanium alloy manufactured by additive manufacturing and a preparation process thereof.
Background
The selective laser melting forming (SLM) technology is a typical process of a metal powder additive manufacturing technology (3D printing technology), and the SLM working principle is that a three-dimensional model of a target component is designed by means of computer assistance, a derived three-dimensional model STL file is sliced and layered, layered data is then led into SLM equipment, powder is melted by laser beams according to a set track, and the steps are repeated and stacked layer by layer until the target component is printed.
Compared with additive manufacturing techniques such as laser melt deposition, electron beam melting, etc., SLM has the advantages: and (1) the laser beam has high energy density, and the thickness of the powder layer and the particle size of the powder are smaller, so that the formed part has good dimensional precision and excellent surface quality, and the compactness is close to 100%. (2) The powder bed can be used as a support and is more suitable for the direct forming of complex and fine parts. (3) The laser energy density can be changed more conveniently by controlling the process parameters, so that the size of the molten pool can be regulated and controlled, and the control on the surface roughness, the microstructure and the performance can be realized. (4) The forming efficiency can be effectively improved by simultaneously scanning a plurality of laser beams.
Nonetheless, control of the surface roughness of the shaped pieces remains one of the major challenges of SLM technology. SLM technology is based on powder bed melting, where incompletely melted powder tends to stick when the melt pool at the contour of the shaped part solidifies, so that powder particles of different sizes often stick at the contour of the shaped part, which will affect the mechanical properties of the final shaped part. Secondly, the complexity of the geometric shape of the formed part determines the diversity of the shape and the size of the molten pool, so that the roughness of different parts of the formed part is different, and the scanning track, the powder, the process parameters, the inclination angle and other process parameters have different degrees of influence on the surface roughness of the SLM formed part, thereby greatly influencing the application range and the field of the additive manufacturing parts.
In fact, for 3D printed metal parts, the surface roughness of several micrometers or even tens of micrometers seriously affects the direct application, and therefore, the surface polishing treatment by a material reduction method is mostly needed before the use. In the aspect of surface technology modification treatment by adopting a coating or a plating layer and the like, the surface of the 3D printed metal part also needs to be polished. The surface polishing treatment is carried out on the 3D printed metal part by adopting a material reduction method, so that the time cost and the processing cost are high, and the wider application of the part is restricted.
How not only to 3D print metal surface subtract material and polish the processing, can solve its roughness big problem again, can also improve its surface tribology performance simultaneously, be a very big challenge, solve this and choose the war and will produce great influence to 3D and print the application of metal in the industrial field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a copper-containing wear-resistant coating on the surface of a titanium alloy manufactured by additive manufacturing and a preparation process thereof.
The technical scheme of the invention for additive manufacturing of the copper-containing wear-resistant coating on the surface of the titanium alloy is as follows:
the wear-resistant coating is located titanium alloy basal body surface, the wear-resistant coating includes bottom and top layer, the bottom is pure copper bottom, the top layer is the copper-containing top layer that the equipartition has wear-resisting particle, the titanium alloy basal body with adopt mechanical system to combine between pure copper bottom or the copper-containing top layer, the copper-containing top layer still equipartition has pit texture, the texture is for adopting mechanical extrusion or laser's mode to obtain at the surface machining on copper-containing top layer.
The wear resistant coating surface does not comprise the pit texture region and has a roughness of no more than 0.8 microns.
The depth of the pit texture exceeds the lowest wave trough of the surface profile of the titanium alloy.
The density of the material of the pit texture area is higher than that of other non-texture areas.
Hard wear-resistant particles and antifriction components are filled in the pit texture.
The hard wear-resistant particles are nano-diamonds, and the antifriction component is graphene.
A preparation process for manufacturing a copper-containing wear-resistant coating on the surface of a titanium alloy in an additive mode comprises the following steps:
step 3, preparing a copper-containing surface layer: flatly paving the pure copper particles uniformly mixed with the wear-resistant particles on the surface of the pure copper bottom layer in the step 2, realizing the combination between the pure copper particles and the titanium alloy matrix by adopting a mechanical plane pressing or rolling mode, and controlling the plastic deformation of the copper-containing surface layer to be not less than 30%;
step 4, preparing a copper-containing surface texture: machining the surface of the copper-containing surface layer in a mechanical extrusion or laser treatment mode to obtain a pit texture, wherein the density of the pit texture is not lower than 20%;
step 5, finishing the copper-containing surface layer: and (4) rolling and finishing the pit texture copper-containing surface layer obtained in the step (4) in a mechanical mode to obtain a flat surface.
Further, in the mechanical pressing process in the step (4), the lower end part of the pressing head penetrates through the pure copper bottom layer, that is, the bottom of the obtained texture penetrates through the pure copper bottom layer.
And (4) penetrating the bottom of the pit texture obtained by laser treatment in the step (4) through the pure copper bottom layer.
And (4) in the step (4), a pressure maintaining link is arranged after the load reaches a set value in the mechanical extrusion process, and the pressure maintaining time is not less than 1 minute.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) in the aspect of processing the surface roughness problem of the 3D printing titanium alloy, the concept of 'additive manufacturing' adopted by the invention is completely different from the material reducing polishing processing in the prior art. According to the method, the surface of the 3D printing titanium alloy is treated by using the additive manufacturing copper-containing wear-resistant coating, and the copper-containing wear-resistant texture coating is prepared by using an extrusion processing mode, so that the efficiency is higher than that of material reduction processing modes such as machining polishing, laser polishing, chemical polishing and electrolytic polishing, and the problem that the surface material reduction processing is difficult to perform due to the low hardness and the poor brittleness of an SLM titanium alloy forming part is solved.
(2) According to the invention, surface texturing post-treatment is adopted, so that the bonding strength between the copper-containing metal coating and the 3D printing titanium alloy substrate is effectively increased. The texture pit depth exceeds the lowest wave trough of the titanium alloy surface profile, which means that the texture penetrates through the direct interface of the copper-containing wear-resistant coating and the 3D printing titanium alloy substrate, and the bonding strength of the coating and the workpiece surface is enhanced. In the process of preparing the texture, the mechanical extrusion mode not only utilizes extrusion deformation to prepare the texture, but also specially designs a pressure maintaining link, the pressure maintaining time of the pressure maintaining link is far longer than that of a conventional hardness test, so that the inner surfaces in the texture pits are subjected to a longer-time extrusion effect, and the mutual deformation between materials of the coating and the convex part in the matrix outline occurs in the extrusion process by utilizing the staggering between the coating and the matrix outline, so that the bonding strength between the coating and the matrix is effectively improved. Furthermore, the texture of mechanical extrusion penetrates through the pure copper bottom layer deeply and enters the titanium alloy matrix, so that the film/base bonding strength at the interface is further improved. On the other hand, the depth of the laser texture also penetrates through the pure copper bottom layer and enters the titanium alloy matrix, so that the metallurgical bonding between the coating at the section and the matrix can be realized, and the bonding strength is effectively improved.
(3) The invention well utilizes the texture and the antifriction and wear-resistant components to improve the antifriction and wear-resistant performance of the copper-containing metal coating. On one hand, the copper component and the antifriction wear-resistant component in the copper-containing wear-resistant coating can effectively improve the antifriction wear-resistant performance of the coating, and on the other hand, the surface pit texture has the function of storing abrasive dust abrasive particles under the dry friction condition, so that the lubricating effect can be improved under the fluid lubricating condition, and the wear-resistant performance of the surface of a workpiece is greatly improved.
Drawings
Fig. 1 is a schematic view of the overall structure of the present invention.
Fig. 2 is a schematic representation of prismatic texture obtained by mechanical pressing.
Fig. 3 is a schematic illustration of laser pit texturing.
Detailed Description
Referring to fig. 1, a wear-resistant coating 2 containing copper on the surface of a titanium alloy manufactured by additive manufacturing is provided, the wear-resistant coating 2 is located on the surface of a titanium alloy substrate 1, the wear-resistant coating 2 includes a bottom layer 21 and a surface layer 22, the bottom layer is a pure copper bottom layer 21, the surface layer is a copper-containing surface layer 22 evenly distributed with wear-resistant particles, the titanium alloy substrate and the pure copper bottom layer or the copper-containing surface layer are combined in a mechanical manner, the copper-containing surface layer is also evenly distributed with pit textures, and the textures are obtained by processing the surface of the copper-containing surface layer in a mechanical extrusion or laser manner.
The wear resistant coating surface does not comprise the pit texture region and has a roughness of no more than 0.8 microns.
The depth of the pit texture exceeds the lowest wave trough of the surface profile of the titanium alloy, so that the structural definition of the texture effectively improves the bonding strength between the coating and the substrate.
The density of the material in the pit texture region is higher than that of other non-texture regions, and the extrusion effect of the inner surface of the texture to the matrix is realized by utilizing the deformation effect of the material in the texture processing process, so that the density and the wear resistance of the material are improved.
Hard wear-resistant particles and antifriction components are filled in the pit texture.
Further, the hard wear-resistant particles are nano-diamonds, and the antifriction component is graphene.
A preparation process for manufacturing a copper-containing wear-resistant coating on the surface of a titanium alloy in an additive mode comprises the following steps:
step 3, preparation of the copper-containing surface layer 22: flatly paving the pure copper particles uniformly mixed with the wear-resistant particles on the surface of the pure copper bottom layer 21 in the step 2, realizing the combination between the pure copper particles and the titanium alloy substrate by adopting a mechanical plane pressing or rolling mode, controlling the plastic deformation of the copper-containing surface layer to be not less than 30%, and limiting the deformation amount to enable the copper particles and the 3D printing titanium alloy substrate to generate better mechanical combination;
step 4, preparing a copper-containing surface texture: machining the surface of the copper-containing surface layer in a mechanical extrusion or laser treatment mode to obtain a pit texture, wherein the density of the pit texture is not lower than 20%;
step 5, finishing the copper-containing surface layer: and (4) rolling and finishing the pit texture copper-containing surface layer obtained in the step (4) in a mechanical mode to obtain a flat surface.
Further, during the mechanical pressing in the step (4), the lower end of the pressing head penetrates through the pure copper bottom layer 21, so that the obtained texture bottom penetrates through the pure copper bottom layer 21.
The bottom of the pit texture obtained by the laser treatment in the step (4) penetrates through the pure copper bottom layer 21.
And a pressure maintaining link is arranged after the loading reaches a set value in the extrusion process, the pure copper particles in the pit texture are further subjected to plastic deformation, and the average plastic deformation amount in the horizontal direction is not lower than 30%. This deformation definition can result in a better mechanical bond between the copper particles of the inner surface in the textured pits and the 3D printed titanium alloy substrate.
The process of the present invention is further illustrated by the following preferred examples, but the scope of the invention is not limited thereto.
Example 1
The copper-containing wear-resistant coating 2 on the surface of the titanium alloy is manufactured in an additive mode, the wear-resistant coating is located on the surface of the titanium alloy base body 1, the wear-resistant coating comprises a bottom layer 21 and a surface layer 22, the bottom layer is a pure copper bottom layer 21, the surface layer is a copper-containing surface layer 22 with wear-resistant particles uniformly distributed, the titanium alloy base body 1 and the pure copper bottom layer 21 or the copper-containing surface layer 22 are combined in a mechanical mode, pit textures are uniformly distributed on the copper-containing surface layer, and the textures are obtained by machining the surface of the copper-containing surface layer in a mechanical extrusion mode.
The SLM titanium alloy form has a surface roughness of 20 to 60 microns.
The particle size of the copper powder is 20-100 micrometers, the average size of the nano-diamond is 100nm, and the graphene is graphene ethanol slurry.
The mixed powder of the wear-resistant coating comprises the following components in percentage by mass: 0.1-5% of graphene powder, 1-10% of nano diamond and the balance of copper powder.
The mixed powder is prepared by uniformly mixing in an ethanol solution and then drying.
The preparation method of the copper-containing wear-resistant coating on the surface of the titanium alloy by additive manufacturing comprises the following steps:
And 2, placing the titanium alloy workpiece obtained by the SLM selective laser melting process on a press workbench, covering a layer of copper powder on the surface of the titanium alloy workpiece to form a pure copper bottom layer 21, setting the granularity of the copper powder on the basis of 3-10 times of the roughness value of the surface of the 3D printed titanium alloy, doping small-granularity powder and large-granularity powder according to needs to realize more approximate density of the copper-containing wear-resistant coating, and lightly scraping by using a scraper to ensure that the height of the copper powder bottom layer does not exceed the highest surface contour of the 3D printed titanium alloy workpiece, so that the bottom of the copper-containing surface layer can also have the opportunity to be in direct contact with the 3D printed titanium alloy substrate, and the bonding strength of the titanium alloy workpiece is improved.
And 3, covering pure copper particles uniformly mixed with wear-resistant particles on the pure copper bottom layer 21, wherein the wear-resistant particles are nano diamonds or micro diamonds, and lightly scraping by using a scraper to obtain a 30-micron copper-containing surface layer 22. And (2) pressing the copper-containing surface by using a press, setting the pressure to be 30-50MPa lower than the yield strength of the 3D printing titanium alloy, ensuring that deformation mainly occurs on the wear-resistant coating, so that the plastic deformation of the copper-containing surface layer is not less than 30%, changing the thickness of the copper-containing surface layer from the original 30 micrometers to not more than 20 micrometers after pressing, and mechanically combining the titanium alloy substrate 1 and the coating 2 through plastic deformation by using a mechanical extrusion mode.
And 4, mechanically extruding by using a diamond pressure head of a microhardness tester according to the graph shown in FIG. 2, preparing a prismatic pit texture with the density of 20-50% on the surface of the copper-containing surface layer 22 obtained in the previous step, wherein the prismatic texture is 221 shown in FIG. 2, the pit depth is 65 micrometers, so as to ensure that the bottom of the pit texture penetrates through the pure copper bottom layer, the diamond pressure head of the microhardness tester is in a quadrangular pyramid shape, performing a search test in the early stage, summarizing the relation between the pressing depth of the pressure head and the diagonal length of the section of the pressure head on the horizontal plane, accurately determining the pressing depth, keeping static pressure of each pit pressure head for 2-5 min during preparing the texture, and combining the titanium alloy substrate and the coating by using an extrusion mode again, so as to increase the bonding strength of the coating. The problem of surface roughness of the SLM titanium alloy workpiece is solved by preparing the copper-containing coating, the bonding strength of the copper-containing coating and a titanium alloy matrix is enhanced through the texture, and the texture also has the antifriction and wear-resistant effects of collecting abrasive particles, so that the surface performance of the workpiece is further enhanced. In order to improve the friction-reducing and wear-resisting performance, mixed powder containing hard wear-resisting particles and friction-reducing components is filled in the pit texture, and the mixed powder is filled in a part of the texture or the whole texture according to requirements.
And 5, rolling the flat surface by using a press machine, and obtaining the copper-containing wear-resistant coating on the surface of the titanium alloy manufactured by the additive manufacturing on the surface of the titanium alloy substrate.
It should be noted that, in the determination of the plastic deformation amount of the material, the characteristic may be performed by an average line strain in a specific direction, or the determination may be performed by a structure observation experiment after the surface of the texture area is corroded, and the like.
Example 2
The copper-containing wear-resistant coating 2 on the surface of the titanium alloy is manufactured in an additive mode, the wear-resistant coating is located on the surface of the titanium alloy base body 1, the wear-resistant coating comprises a bottom layer 21 and a surface layer 22, the bottom layer is a pure copper bottom layer 21, the surface layer is a copper-containing surface layer 22 with wear-resistant particles uniformly distributed, the titanium alloy base body 1 and the pure copper bottom layer 21 or the copper-containing surface layer 22 are combined in a mechanical mode, pit textures are uniformly distributed on the copper-containing surface layer, and the textures are obtained by machining the surface of the copper-containing surface layer in a mechanical extrusion mode.
The SLM titanium alloy form has a surface roughness of 30 to 90 microns.
The particle size of the copper powder is 100-500 micrometers, the average size of the nano-diamond is 200nm, and the graphene is graphene ethanol slurry.
The wear-resistant coating comprises the following components in percentage by mass: 5-10% of graphene powder, 10-30% of nano diamond and the balance of copper powder.
The mixed powder is prepared by uniformly mixing in an ethanol solution and then drying.
The preparation method of the copper-containing wear-resistant coating on the surface of the titanium alloy by additive manufacturing comprises the following steps:
And 2, placing the SLM titanium alloy workpiece on a press workbench, covering a layer of copper powder on the surface of the SLM titanium alloy workpiece to form a pure copper bottom layer 21, and lightly scraping the pure copper bottom layer with a scraper to ensure that the height of the copper powder bottom layer does not exceed the highest surface profile of the 3D printed titanium alloy workpiece.
And 3, covering pure copper particles mixed with wear-resistant particles on the pure copper bottom layer 21, and lightly scraping by using a scraper to obtain a 30-micron copper-containing surface layer 22. And (3) pressing the copper-containing surface by using a plane pressing head of a press machine to enable the plastic deformation of the copper-containing surface layer to be not less than 30%, and combining the titanium alloy substrate 1 and the coating 2 in a mechanical extrusion mode. The sample of corresponding size and appearance can be printed as required in actual processing, can adopt the matching anchor clamps cooperation press head to carry out extrusion processing to the arc surface.
And 4, preparing a texture with the density of 20-50% on the copper-containing surface 22 by using picosecond laser processing equipment, wherein the laser wavelength is 1064nm, the pulse frequency is 400kHz, the scanning speed is 300mm/s, the output power is 18W, the light spot diameter is 50 microns, the pit depth is 100 microns, and the texture penetrates through the pure copper bottom layer 21 to reach the substrate 1. The laser pit texture is shown in figure 3 as 222. The laser processing texture realizes the metallurgical bonding of the copper-containing layer and the titanium alloy matrix at the edge section of the pit, and greatly enhances the bonding strength of the coating and the matrix. The problem of surface roughness of the SLM titanium alloy workpiece is solved by preparing the copper-containing coating, the bonding strength of the copper-containing coating and a titanium alloy matrix is enhanced through the texture, and the texture also has the anti-attrition effect of collecting abrasive particles, so that the surface performance of the workpiece is further enhanced. In order to improve the friction-reducing and wear-resisting performance, mixed powder containing hard wear-resisting particles and friction-reducing components is filled into the pit texture.
And 5, rolling the flat surface by using a press machine, and obtaining the copper-containing wear-resistant coating on the surface of the titanium alloy manufactured by the additive manufacturing on the surface of the titanium alloy substrate.
According to the technical scheme, the additive concept is adopted, the problems of surface roughness and tribology performance of the 3D printing titanium alloy part are effectively solved, and the deep application of the 3D printing titanium alloy part in the wider industrial field is effectively promoted.
Claims (10)
1. The copper-containing wear-resistant coating on the surface of the titanium alloy is manufactured in an additive mode and is characterized in that the wear-resistant coating is located on the surface of a titanium alloy substrate and comprises a bottom layer and a surface layer, the bottom layer is a pure copper bottom layer, the surface layer is a copper-containing surface layer with wear-resistant particles uniformly distributed, the titanium alloy substrate is combined with the pure copper bottom layer or the copper-containing surface layer in a mechanical mode, pit textures are uniformly distributed on the copper-containing surface layer, and the textures are obtained by machining the surface of the copper-containing surface layer in a mechanical extrusion or laser mode.
2. The copper-containing wear-resistant coating for the additive manufactured titanium alloy surface of claim 1, wherein the wear-resistant coating surface does not comprise the pit texture region having a roughness of no more than 0.8 microns.
3. The copper-containing wear resistant coating of an additive manufactured titanium alloy surface of claim 1, wherein the depth of the pit texture exceeds the lowest valleys of the titanium alloy surface profile.
4. The copper-containing wear-resistant coating for the additive manufactured titanium alloy surface of claim 1, wherein the textured regions of pits are denser than the other untextured regions.
5. The copper-containing wear resistant coating for the additive manufactured titanium alloy surface of claim 1, wherein the pit texture is filled with hard wear resistant particles and a friction reducing component.
6. The additive manufactured titanium alloy surface copper-containing wear resistant coating according to claim 5, wherein the hard wear resistant particles are nanodiamonds and the friction reducing component is graphene.
7. The preparation process of the copper-containing wear-resistant coating on the surface of the titanium alloy by additive manufacturing is characterized by comprising the following steps of:
(1) preparing a 3D printing titanium alloy workpiece: preparing a 3D printing titanium alloy workpiece by adopting a metal 3D printer;
(2) directly preparing a pure copper bottom layer on the surface of a titanium alloy workpiece: directly spreading pure copper particles on the surface of the titanium alloy workpiece obtained in the previous step;
(3) preparation of the copper-containing surface layer: spreading pure copper particles uniformly mixed with wear-resistant particles on the surface of the pure copper bottom layer in the previous step, and realizing the combination between the pure copper particles and the titanium alloy matrix by adopting a mechanical plane pressing or rolling mode;
(4) preparing a copper-containing surface texture: processing the surface of the copper-containing surface layer by adopting a mechanical extrusion or laser treatment mode to obtain a pit texture;
(5) finishing the copper-containing surface layer: and (4) rolling and finishing the pit texture copper-containing surface layer obtained in the previous step in a mechanical mode to obtain a flat surface.
8. The process for preparing the copper-containing wear-resistant coating on the surface of the titanium alloy in the additive manufacturing manner according to claim 7, wherein the texture obtained by the mechanical extrusion in the step (4) penetrates through the pure copper bottom layer.
9. The process for preparing the copper-containing wear-resistant coating on the surface of the titanium alloy in the additive manufacturing manner according to claim 7, wherein the bottoms of the pit textures obtained by the laser treatment in the step (4) penetrate through the pure copper bottom layer.
10. The process for preparing the copper-containing wear-resistant coating on the surface of the titanium alloy in the additive manufacturing manner according to claim 8, wherein a pressure maintaining link is arranged after the load reaches a set value in the extrusion process.
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