CN111575643A - Method for preparing tantalum diffusion layer on surface of titanium alloy - Google Patents
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 108
- 238000009792 diffusion process Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 22
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 230000008595 infiltration Effects 0.000 claims abstract description 18
- 238000001764 infiltration Methods 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 239000013077 target material Substances 0.000 claims abstract description 13
- 238000005272 metallurgy Methods 0.000 claims abstract description 11
- 238000004544 sputter deposition Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000000053 physical method Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005275 alloying Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 231100001240 inorganic pollutant Toxicity 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 2
- 238000003491 array Methods 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 48
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005468 ion implantation Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000283899 Gazella Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 238000005121 nitriding Methods 0.000 description 1
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- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 230000035882 stress Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/354—Introduction of auxiliary energy into the plasma
- C23C14/355—Introduction of auxiliary energy into the plasma using electrons, e.g. triode sputtering
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Abstract
The invention discloses a method for preparing a tantalum diffusion layer on the surface of a titanium alloy, and belongs to the technical field of material surface modification. The method utilizes a plasma surface metallurgy technology, optimizes the target material shape, the source/workpiece electrode spacing and the metal infiltration temperature, enables the source electrode sputtering rate and the element utilization rate to reach the best, closes a source electrode and cathode power supply and a mechanical pump after tantalum infiltration is finished, and introduces a large amount of argon to rapidly cool so as to promote the internal stress to be rapidly released, and finally removes a deposition layer by adopting a conventional physical method to obtain the titanium alloy with the tantalum diffusion layer on the surface. The sample prepared by the method has the characteristics of obviously improved wear resistance and hardness, high bonding strength of the diffusion layer and the matrix, simple and convenient operation, good repeatability and low cost, and can be widely applied to the surface modification of the titanium alloy.
Description
Technical Field
The invention relates to a method for preparing a tantalum diffusion layer on the surface of a titanium alloy, and belongs to the technical field of material surface modification.
Background
Titanium alloys have been widely paid attention to their advantages of high specific strength, good heat resistance and corrosion resistance, high mechanical properties, and the like. However, poor wear resistance has always restricted the use of titanium alloys in more fields. The physical and chemical properties of the tantalum element and the titanium are relatively close, so that the tantalum element and the titanium alloy can be infiltrated into the surface layer of the titanium alloy by a surface alloying method, and an infinite solid solution is formed to play a role in solid solution strengthening, so that the wear resistance of the titanium alloy is improved.
The common titanium alloy surface alloying methods mainly include ion implantation, thermal diffusion, and double glow plasma surface metallurgy (DGPSA). The purposes of strengthening and toughening the titanium alloy and resisting wear can be realized through ion implantation, but the alloy layer is generally smaller than 1 mu m, and meanwhile, the equipment is expensive, the process is complex, and the titanium alloy is difficult to be suitable for large-area treatment. Thermal diffusion methods fall into two broad categories: 1) direct diffusion method. The method mainly comprises the steps of soaking a workpiece in a medium containing pre-infiltrated metal (comprising a solid state, a liquid state and a gas state), heating and insulating the workpiece, and enabling elements to enter a matrix by a thermal diffusion method. 2) And (4) a composite plating and infiltration method. The surface of the workpiece is coated with a solid phase coating, and then the workpiece is heated at high temperature, and the coating and the matrix metal element are diffused mutually to form an alloy layer. The heat diffusion process has the advantages of simple equipment, low cost, poor controllability, limited types of alloy elements and environmental pollution. The double glow plasma surface metallurgy (DGPSA) is a surface alloying method based on ion nitriding technology and utilizing double layer glow discharge phenomenon, and compared with ion implantation and thermal diffusion technology, it has the characteristics of controllable thickness of diffusion layer, low energy consumption and high efficiency. However, the alloy layer after the surface of the titanium alloy is infiltrated with Ta by the DGPSA process usually contains a surface deposition layer and a subsurface diffusion layer (tardy, gazelle, zhangping, etc.. double glow plasma surface metallurgy [ J ] heat treatment, 2009,24(1): 1-11.). The microhardness of titanium alloy is not more than 400 HV (easy gallium, Pengeut TC4 titanium alloy surface laser alloying coating structure and wear resistance. Metal thermal treatment, 2020,2: 48.), while Ta metal is only about 90 HV (West, Huang Yongde, Chenyuhua, et Al Ti6Al4V or Ni filler is used for laser connecting Mo and Ta thin plates, optical and laser technology, 2018,106, 487-494.). Therefore, after the titanium alloy is alloyed by Ta, the hardness and the wear resistance of the titanium alloy are improved due to the existence of the diffusion layer, but the existence of the deposition layer (pure Ta) still weakens the strengthening effect to a certain extent.
Disclosure of Invention
The invention aims to provide a method for preparing a tantalum diffusion layer on the surface of a titanium alloy, wherein the prepared Ta diffusion layer and a substrate form a solid solution, so that the Ta diffusion layer has high bonding strength, and the surface hardness and the wear resistance of the Ta diffusion layer are improved to a certain extent.
In the invention, the preparation of the tantalum diffusion layer comprises three steps of Ta infiltration, cooling and stripping of a deposited layer. The purpose of the first two steps is: the sputtering rate and the element utilization rate are optimized (the Ta infiltration is carried out by selecting a filament target and a proper working distance), so that the growth speed of the infiltrated layer is higher; the higher heat preservation temperature is also beneficial to the growth of a diffusion layer, but mainly aims to realize larger temperature difference with the room temperature, and then utilizes the inherent thermal expansion coefficient difference between the Ta deposition layer and the titanium alloy matrix and the higher cooling speed to ensure that the volume shrinkage of the Ta deposition layer and the titanium alloy matrix is not coordinated in the cooling process, and certain thermal stress is accumulated at the most unstable phase interface with the most defects. The process of stripping the deposition layer is to actually apply external force to further release the internal stress between the deposition layer and the titanium alloy matrix, so as to achieve the purpose of cracking or falling off the deposition layer, and prepare the titanium alloy with the Ta diffusion layer on the surface.
The invention provides a method for preparing a tantalum diffusion layer on the surface of a titanium alloy, which comprises the following steps:
(1) polishing the titanium alloy workpiece, and respectively ultrasonically cleaning the titanium alloy workpiece by using acetone, alcohol and deionized water to remove organic and inorganic pollutants to obtain a clean surface;
(2) placing a pretreated titanium alloy workpiece on a sample table of a plasma surface metallurgy device, adding a titanium alloy gasket made of the same material between the sample table and the titanium alloy workpiece, selecting a Ta target as a target material, flatly placing the titanium alloy workpiece on the sample table, vertically suspending the target material right above the titanium alloy workpiece, wherein the distance from the lower surface of the target material to the upper surface of the workpiece is 15-20 mm, and opening a vacuum pump to vacuumize to below 5 Pa;
(3) introducing high-purity argon, and carrying out sputtering cleaning on the surface of the titanium alloy workpiece, wherein the technological parameters are as follows: the working air pressure is 20 +/-5 Pa, the cathode voltage is 200-500V, and the cleaning time is 10-30 min;
(4) carrying out Ta infiltration on the titanium alloy workpiece, wherein the technological parameters are as follows: working air pressure is 35 +/-5 Pa, cathode and source electrode voltages are 500-620V and 750-870V respectively, the temperature of the titanium alloy workpiece is 900-1000 ℃, and heat preservation is carried out for 10-120 min;
(5) after the Ta infiltration is finished, closing a source electrode and a cathode power supply, closing a vacuum pump, and introducing a large amount of argon to rapidly cool the vacuum chamber to room temperature for 1.5-2.5 h;
(6) and after the furnace body is completely cooled, taking out the titanium alloy workpiece with the surface permeated with Ta, and completely stripping the deposited layer by adopting a conventional physical method to finally obtain the titanium alloy with the surface only containing the Ta diffusion layer.
In the above technical solution, further additional technical features are as follows:
the Ta target adopts a filament target with high sputtering rate, and the purity is more than 99.5%;
the temperature of the titanium alloy workpiece is 900-1000 ℃ during Ta infiltration;
the distance between the source electrode and the workpiece is 15-20 mm.
The cooling mode is as follows: closing the source electrode and the cathode power supply after the Ta infiltration is finished, closing the vacuum pump, and introducing a large amount of argon to rapidly cool the vacuum chamber to room temperature for 1.5-2.5 h;
the conventional physical methods for peeling off the deposited layer include, but are not limited to, ultrasonic cleaning, alcohol cotton wiping, plastic tweezers peeling, and the like, and combinations thereof;
the above additional technical parameters need to act together to completely peel off the deposited layer, so as to obtain the titanium alloy with the surface only containing the tantalum diffusion layer.
The thickness of the Ta diffusion layer of the titanium alloy workpiece with the Ta diffusion layer on the surface prepared by the method can reach about 2-20 mu m, and the surface is smooth and bright and has metallic luster. The micro-morphology comprises nanometer step arrays with different orientations, all groups of steps are connected with each other, and a small number of small platforms are inserted in the middle. The step array and the small platform are in micrometer scale. The titanium alloy with the Ta diffusion layer on the surface has improved microhardness and wear resistance, which are mainly due to the solid solution strengthening effect of Ta diffusion on the surface of the titanium alloy.
In the preparation method, the structure of the plasma surface metallurgy device is as follows:
the vacuum chamber of the device is of a cylindrical structure, the upper end of the vacuum chamber is provided with an anode, the sample table is connected with a cathode at the lower end, and the target is connected with the source and positioned between the anode and the cathode; when the device works, the target material is aligned with the anode and the cathode, the titanium alloy workpiece is placed on the sample table, a gasket is additionally arranged between the titanium alloy workpiece and the sample table, and the height of the target material is adjusted to realize the adjustment of the working distance between the target material and the titanium alloy workpiece; the upper end of the furnace body is provided with an argon inlet, and the lower end is provided with an air outlet which is connected with a vacuum pumping device.
The invention has the beneficial effects that:
(1) compared with a thermal diffusion process, the method has the advantages of small environmental pollution and high efficiency.
(2) Compared with the ion implantation technology, the element penetration depth range is larger, the equipment is relatively cheap, and the process is simple.
(3) The method can be realized by adjusting the technological parameters and cooling mode of the metal infiltration without developing new equipment and combining with a conventional physical method.
Drawings
Fig. 1 is a schematic structural view of a plasma alloying apparatus used in the present invention.
FIG. 2 shows the surface, cross-sectional profile and Ta element distribution of the samples in example 1.
FIG. 3 shows the thickness of the diffusion layer of the samples of examples 1, 2 and 3.
FIG. 4 is a graph showing the change in microhardness of the samples of examples 1, 2 and 3.
In the figure: 1-vacuum chamber 2-anode 3-source 4-cathode 5-argon gas inlet 6-vacuum pump 7-target 8-sample table 9-gasket 10-titanium alloy workpiece.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
the preparation method of the thin Ta diffusion layer on the surface of the Ti-6Al-4V titanium alloy provided by the embodiment includes the following steps:
(1) polishing the titanium alloy workpiece, and respectively ultrasonically cleaning the titanium alloy workpiece by using acetone, alcohol and deionized water to remove organic and inorganic pollutants to obtain a clean surface;
(2) placing a pretreated titanium alloy workpiece 10 on a sample table 8 of a plasma surface metallurgy device, additionally arranging a titanium alloy gasket 9 which is 20 mm thick and is made of the same material between the sample table 8 and the titanium alloy workpiece, selecting a Ta target as a source target 7, vertically suspending the target 7 right above the titanium alloy workpiece 10 at a distance of 18 mm, and opening a vacuum pump 6 to vacuumize to below 5 Pa;
(3) introducing high-purity argon through an argon inlet 5, and carrying out sputtering cleaning on the surface of the titanium alloy workpiece 10, wherein the technological parameters are as follows: working air pressure is 20 Pa, cathode voltage is 300V, and cleaning time is 20 min;
(4) carrying out Ta infiltration on the titanium alloy workpiece, wherein the technological parameters are as follows: working pressure is 40 Pa, voltage of a cathode 4 and voltage of a source electrode 3 are respectively 500V and 750V, temperature of a titanium alloy workpiece 10 is 900 ℃, and heat preservation time is 30 min;
(5) after the Ta infiltration, the vacuum chamber 1 is cooled in the following way: turning off the power supplies of the source electrode 3 and the cathode 4, turning off the vacuum pump 6, and introducing a large amount of argon to rapidly cool the vacuum chamber 1 to room temperature for 1.8 h;
(6) and after the vacuum chamber 1 is completely cooled, taking out the titanium alloy workpiece 10 with the surface permeated with Ta, carrying out ultrasonic cleaning in an absolute ethyl alcohol solution, and completely stripping a deposition layer to finally obtain the Ti-6Al-4V titanium alloy with the surface containing a thin Ta diffusion layer.
Example 2:
the preparation method of the medium-thickness Ta diffusion layer on the surface of the Ti-6Al-4V titanium alloy provided by the embodiment comprises the following steps:
(1) polishing the titanium alloy workpiece, and respectively ultrasonically cleaning the titanium alloy workpiece by using acetone, alcohol and deionized water to remove organic and inorganic pollutants to obtain a clean surface;
(2) placing a pretreated titanium alloy workpiece 10 on a sample table 8 of a plasma surface metallurgy device, additionally arranging a titanium alloy gasket 9 which is 20 mm thick and is made of the same material between the sample table 8 and the titanium alloy workpiece, selecting a Ta target as a source target 7, vertically suspending the target 7 right above the titanium alloy workpiece 10 at a distance of 18 mm, and opening a vacuum pump 6 to vacuumize to below 5 Pa;
(3) introducing high-purity argon through an argon inlet 5, and carrying out sputtering cleaning on the surface of the titanium alloy workpiece 10, wherein the technological parameters are as follows: working air pressure is 20 Pa, cathode voltage is 300V, and cleaning time is 20 min;
(4) carrying out Ta infiltration on the titanium alloy workpiece, wherein the technological parameters are as follows: working pressure is 40 Pa, voltage of a cathode 4 and voltage of a source electrode 3 are respectively 500V and 750V, temperature of a titanium alloy workpiece 10 is 900 ℃, and heat preservation time is 60 min;
(5) after the Ta infiltration, the vacuum chamber 1 is cooled in the following way: turning off the power supplies of the source electrode 3 and the cathode 4, turning off the vacuum pump 6, and introducing a large amount of argon to rapidly cool the vacuum chamber 1 to room temperature for 2 hours;
(6) and after the vacuum chamber 1 is completely cooled, taking out the titanium alloy workpiece 10 with the surface permeated with Ta, carrying out ultrasonic cleaning in an absolute ethyl alcohol solution, and completely stripping a deposition layer to finally obtain the Ti-6Al-4V titanium alloy with the surface containing the medium-thickness Ta diffusion layer.
Example 3:
the preparation method of the thick Ta diffusion layer on the surface of the Ti-6Al-4V titanium alloy provided by the embodiment comprises the following steps:
(1) polishing the titanium alloy workpiece, and respectively ultrasonically cleaning the titanium alloy workpiece by using acetone, alcohol and deionized water to remove organic and inorganic pollutants to obtain a clean surface;
(2) placing a pretreated titanium alloy workpiece 10 on a sample table 8 of a plasma surface metallurgy device, additionally arranging a titanium alloy gasket 9 which is 20 mm thick and is made of the same material between the sample table 8 and the titanium alloy workpiece, selecting a Ta target as a source target 7, vertically suspending the target 7 right above the titanium alloy workpiece 10 at a distance of 18 mm, and opening a vacuum pump 6 to vacuumize to below 5 Pa;
(3) introducing high-purity argon through an argon inlet 5, and carrying out sputtering cleaning on the surface of the titanium alloy workpiece 10, wherein the technological parameters are as follows: working air pressure is 20 Pa, cathode voltage is 300V, and cleaning time is 20 min;
(4) carrying out Ta infiltration on the titanium alloy workpiece, wherein the technological parameters are as follows: working pressure is 40 Pa, voltage of a cathode 4 and voltage of a source electrode 3 are respectively 500V and 750V, temperature of a titanium alloy workpiece 10 is 900 ℃, and heat preservation time is 60 min;
(5) after the Ta infiltration, the vacuum chamber 1 is cooled in the following way: turning off the power supplies of the source electrode 3 and the cathode 4, turning off the vacuum pump 6, and introducing a large amount of argon to rapidly cool the vacuum chamber 1 to room temperature for 2.2 h;
(6) and after the vacuum chamber 1 is completely cooled, taking out the titanium alloy workpiece 10 with the surface permeated with Ta, carrying out ultrasonic cleaning in an absolute ethyl alcohol solution, and completely stripping a deposition layer to finally obtain the Ti-6Al-4V titanium alloy with the thicker Ta diffusion layer on the surface.
The titanium alloy products obtained in the above examples were tested for microhardness and wear resistance, and the data are shown in table 1; by using Si3N4The ceramic ball and the sample are dry-ground for 20 min at room temperature under the loading force of 5N, the length of a grinding trace is 5mm, and the wear resistance of the ceramic ball and the sample is also obviously improved through calculation.
TABLE 1
Examples 1, 2 and 3 Ta diffusion layers with different thicknesses were prepared on the surface of Ti-6Al-4V alloy. The basic characterization and performance tests performed on the samples obtained in example 1 found that: the surface appearance of the Ta diffusion layer is a step array with different orientations and sizes, the minimum size of a single step is in a nanometer level, Ta elements are diffused inwards along the depth direction (figure 2), and the thickness of the Ta diffusion layer obtained in the embodiments 1, 2 and 3 is respectively 2.39 +/-0.24 mu m, 7.8 +/-1.69 mu m and 15.47 +/-3.3 mu m (figure 3); the microhardness test conditions of each group of examples are that the loading force is 1.96N, the loading time is 10 s, more than 3 regions are randomly selected for each group of samples to test (according to GB/T4340), the result is shown in figure 4, the microhardness of the titanium alloy containing the Ta diffusion layer is improved compared with that of a Ti-6Al-4V matrix, the hardness of the matrix is 395.9 HV0.2, and the maximum hardness of the examples is 598.88 HV0.2 (example 3).
Claims (7)
1. A method for preparing a tantalum diffusion layer on the surface of a titanium alloy is characterized by comprising the following steps: by utilizing a plasma surface metallurgy technology and optimizing alloying parameters, large internal stress is accumulated between the tantalum diffusion layer and the deposition layer, the internal stress is promoted to be released by a rapid cooling mode, and finally the deposition layer is removed by a physical method to obtain the titanium alloy with the tantalum diffusion layer on the surface.
2. The method for preparing the tantalum diffusion layer on the surface of the titanium alloy according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) polishing the titanium alloy workpiece, and respectively ultrasonically cleaning the titanium alloy workpiece by using acetone, alcohol and deionized water to remove organic and inorganic pollutants to obtain a clean surface;
(2) placing a pretreated titanium alloy workpiece on a sample table of a plasma surface metallurgy device, additionally arranging a titanium alloy gasket made of the same material between the sample table and the titanium alloy workpiece, selecting a Ta target as a target material, flatly placing the titanium alloy workpiece on the sample table, vertically suspending the target material right above the titanium alloy workpiece, setting the distance between the target material and the workpiece to be 15-20 mm, and opening a vacuum pump to pump the titanium alloy workpiece to be vacuum below 5 Pa;
(3) introducing high-purity argon, and carrying out sputtering cleaning on the surface of the titanium alloy workpiece, wherein the technological parameters are as follows: the working air pressure is 20 +/-5 Pa, the cathode voltage is 200-500V, and the cleaning time is 10-30 min;
(4) carrying out Ta infiltration on the titanium alloy workpiece, wherein the technological parameters are as follows: working air pressure is 35 +/-5 Pa, cathode and source electrode voltages are 500-620V and 750-870V respectively, the temperature of the titanium alloy workpiece is 900-1000 ℃, and heat preservation is carried out for 10-120 min;
(5) after the Ta infiltration is finished, closing a source electrode and a cathode power supply, closing a vacuum pump, and introducing a large amount of argon to rapidly cool the vacuum chamber to room temperature;
(6) and after the furnace body is completely cooled, taking out the titanium alloy workpiece with the surface permeated with Ta, and completely stripping the deposited layer by adopting a physical method to finally obtain the titanium alloy with the surface only containing the Ta diffusion layer.
3. The method for preparing the tantalum diffusion layer on the surface of the titanium alloy according to claim 2, wherein the method comprises the following steps: the Ta target adopts a filament target with high sputtering rate, and the purity is more than 99.5%.
4. The method for preparing the tantalum diffusion layer on the surface of the titanium alloy according to claim 2, wherein the method comprises the following steps: and (5) in the cooling process of the step (5), the duration is 1.5-2.5 h.
5. The method for preparing the tantalum diffusion layer on the surface of the titanium alloy according to claim 2, wherein the method comprises the following steps: the physical method for stripping the deposited layer comprises any one method of ultrasonic cleaning, alcohol cotton wiping and light wiping, plastic tweezers stripping or the combination of the methods.
6. The method for preparing the tantalum diffusion layer on the surface of the titanium alloy according to claim 2, wherein the method comprises the following steps: the structure of the plasma surface metallurgical device is as follows: the vacuum chamber of the device is of a cylindrical structure, the upper end of the vacuum chamber is provided with an anode, the sample table is connected with a cathode at the lower end, and the target is connected with the source and positioned between the anode and the cathode; when the device works, the target material is aligned with the anode and the cathode, the titanium alloy workpiece is placed on the sample table, a gasket is additionally arranged between the titanium alloy workpiece and the sample table, and the height of the target material is adjusted to realize the adjustment of the working distance between the target material and the titanium alloy workpiece; the upper end of the furnace body is provided with an argon inlet, and the lower end is provided with an air outlet which is connected with a vacuum pumping device.
7. A titanium alloy surface tantalum diffusion layer prepared by the method of any one of claims 1 to 6, wherein: the thickness of the Ta diffusion layer is 2-20 mu m, the surface is flat, smooth and bright, and the Ta diffusion layer has metallic luster; the microscopic morphology comprises nanometer step arrays with different orientations, all groups of steps are connected with each other, and a small number of small platforms are inserted in the middle; the step array and the small platform are in micrometer scale.
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