Titanium tantalum alloy with wear-resistant film layer

Abstract

The present invention discloses a titanium tantalum alloy with an abrasion-resistant film layer, which comprises a titanium tantalum alloy matrix and an abrasion-resistant film layer provided on the surface of the titanium tantalum alloy matrix, and is prepared by a method including the following steps: First, the titanium tantalum alloy is successively polished, degreased, immersed and brightened, and ultrasonically cleaned; Second, an oxide film layer is formed on the surface of the titanium tantalum alloy by micro-arc oxidation, anodic oxidation or hard anodic oxidation treatment; Third, after sealing treatment, it is cleaned and dried. The titanium tantalum alloy of the present invention in-situ forms an oxide film layer on the surface of the titanium tantalum alloy with a flat and clean surface after treatment by the methods of micro-arc oxidation, anodic oxidation or hard anodic oxidation. The oxide film layer is more closely combined with the titanium tantalum alloy matrix, greatly improving the surface hardness of the titanium tantalum alloy, improving the wear resistance of the titanium tantalum alloy, and further increasing its service life, and has good application prospects in the fields of chemical engineering, nuclear power and biomedical materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of surface treatment of titanium-tantalum alloys, and particularly relates to a titanium-tantalum alloy with a wear-resistant and corrosion-resistant film layer. Background Art

[0002] Titanium-tantalum alloys have excellent plasticity, good biocompatibility, low elastic modulus, low density, etc., and have good high-temperature strength and high-temperature oxidation resistance, and are widely used in the fields of biomedicine, chemical engineering and nuclear.

[0003] Titanium-tantalum alloys have a lower elastic modulus, high stress absorption capacity, strong corrosion resistance, high fatigue strength, anti-thrombotic property and good biocompatibility, and are widely used in the medical field as repair and replacement materials for hard tissues such as artificial bones and artificial joints, and implant materials for the cosmetic industry and surgical reconstruction industry. However, there are also certain problems in the application process of titanium-tantalum alloys in the medical field. Due to the low elastic modulus of titanium-tantalum alloys, their wear resistance is poor, and friction and wear will occur between the alloys and bone tissues after implantation into the human body, resulting in the generation and peeling of wear debris, which not only is not conducive to bone integration, but may even lead to the occurrence of inflammation or implant failure in severe cases, causing great harm to the implant recipient.

[0004] In the chemical engineering field, with the development of the economy, the exploration of oil and natural gas has gradually shifted to areas with harsh environments and complex geological conditions, and there is an urgent need for high-strength and corrosion-resistant pipeline materials. Titanium-tantalum alloys have good high-temperature strength, high fatigue strength and high-temperature oxidation resistance, and can be applied to oil and gas well pipeline materials in high-temperature, high-pressure and highly corrosive harsh environments, effectively improving the safe service performance of the wellbore. However, defects such as low elastic modulus, poor surface wear resistance (easy to scratch), and poor galvanic corrosion resistance of titanium-tantalum alloys will cause wear, corrosion, fracture and cracking during their application in the chemical engineering field. In particular, the threaded joint parts of titanium-tantalum alloy pipes are prone to adhesion and wear, which limits the further development and application of titanium-tantalum alloys in the chemical engineering field. Therefore, it is possible to consider preparing a film layer on the surface of titanium-tantalum alloy pipes to increase surface wear resistance.

[0005] In the nuclear field, due to the good stability of titanium-tantalum alloy in high-temperature nitric acid, an oxide film composed of oxides of titanium and tantalum will form on the surface, preventing nitric acid from directly reacting with the metal, reducing the corrosion rate, and being insensitive to irradiation. It is one of the materials for key equipment in nuclear spent fuel reprocessing that China is vigorously developing at present. When used as a reprocessing device, the titanium-tantalum alloy has low hardness and poor wear resistance. The original substances in spent fuel reprocessing are all solid oxides of uranium and plutonium. During the dumping process, it is easy to scratch the surface of the nuclear fuel reprocessing equipment, damage the passivation film, and thus pitting corrosion occurs. Moreover, the reprocessing equipment is long-term in an environment of high radioactivity, high-oxidation ions, and high-concentration boiling nitric acid. As the concentration of strengthening metal ions in the later reprocessing feed liquid increases, galvanic corrosion is likely to occur on the scratched surface of the titanium-tantalum alloy, seriously affecting its service life. Therefore, it is urgent to develop a process to improve the surface hardness and wear resistance of the titanium-tantalum alloy to ensure its long-term service under high stress loads. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a titanium-tantalum alloy with a wear-resistant and corrosion-resistant film layer in view of the deficiencies of the above-mentioned prior art. The titanium-tantalum alloy forms an oxide film layer in-situ on the surface of the titanium-tantalum alloy with a flat and clean surface after being treated by micro-arc oxidation, anodic oxidation or hard anodic oxidation methods. The combination with the titanium-tantalum alloy matrix is closer, greatly improving the surface hardness of the titanium-tantalum alloy, improving the wear resistance of the titanium-tantalum alloy, and further increasing its service life, solving the problem that the application of the titanium-tantalum alloy is limited in various fields due to its low hardness, poor wear resistance and poor galvanic corrosion resistance.

[0007] To solve the above technical problems, the technical solution adopted by the present invention is: a titanium-tantalum alloy with a wear-resistant and corrosion-resistant film layer, characterized in that it includes a titanium-tantalum alloy matrix and a wear-resistant and corrosion-resistant film layer provided on the surface of the titanium-tantalum alloy matrix, and is prepared by a method including the following steps:

[0008] Step 1: Grind, degrease, impregnate and brighten the titanium-tantalum alloy in sequence, and then perform ultrasonic cleaning in acetone, ethanol and deionized water in sequence to obtain a titanium-tantalum alloy with a flat and clean surface;

[0009] Step 2: Place the titanium-tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolyte for micro-arc oxidation, anodic oxidation or hard anodic oxidation treatment, and introduce compressed air into the electrolyte throughout the treatment process to form an oxide film layer on the surface of the titanium-tantalum alloy, obtaining a titanium-tantalum alloy with a film layer;

[0010] Step 3: Perform sealing treatment on the titanium-tantalum alloy with a film layer obtained in Step 2, then clean it with deionized water, and then dry it with compressed air or dry it at low temperature to obtain a titanium-tantalum alloy with a wear-resistant and corrosion-resistant film layer.

[0011] The above-mentioned titanium tantalum alloy with a wear-resistant film layer is characterized in that, in step one, the grinding is carried out with sandpaper; the mass content composition of the degreasing solution used for degreasing includes: 10% - 30% NaOH, Na 2 CO 3 20% - 45%, Na 3 PO 4 ·12H 2 O 20% - 30%, degreasing agent 5% - 20%, the degreasing temperature is 60°C - 90°C, and the time is 1 min - 5 min; the volume content composition of the impregnation solution used for impregnation includes: 25% - 40% HF solution with a mass concentration of 40%, 60% - 75% HNO 3 60% - 75%, the impregnation temperature is 70°C - 80°C, and the time is 10 s - 120 s; the volume content composition of the brightening solution used for brightening includes: 15% - 25% H 2 SO 4 solution, 75% - 85% H 2 O 2 solution, the brightening temperature is room temperature, and the time is 30 s - 60 s.

[0012] The above-mentioned titanium tantalum alloy with a wear-resistant film layer is characterized in that, in step two, the electrolyte composition used for micro-arc oxidation is: Na 2 SiO 3 10 g / L - 50 g / L, Na 3 PO 4 5 g / L - 25 g / L, Na 2 B 4 O 7 5 g / L - 15 g / L, ammonium salt 5 g / L - 15 g / L, organic acid 1 g / L - 5 g / L, pH regulator 1 g / L - 5 g / L; the ammonium salt is NH 4 VO 3 or / and NH 4 HF 2 and the organic acid is C 6 H 5 Na 3 O 7 or / and C 6 H 11 NaO 7, the pH regulator is NaOH and / or KOH; the process parameters of the micro-arc oxidation are: the power supply mode is constant current or constant voltage mode, the electrical parameters are positive voltage 300V - 600V, negative voltage 0 - 200V, frequency 200Hz - 600Hz, duty cycle 5% - 60%, temperature 15°C - 30°C, and oxidation time 10min - 60min. By adding ammonium salts and organic acids to the electrolyte used in the micro-arc oxidation and controlling their addition amounts, the present invention further promotes the uniform densification of the oxide film layer on the surface of the titanium tantalum alloy substrate, reduces the pore size, and improves its corrosion resistance.

[0013] The above-mentioned titanium tantalum alloy with a wear-resistant and corrosion-resistant film layer is characterized in that the electrolyte composition used in the anodic oxidation in step two is: H 2 SO 4 160g / L - 240g / L, H 3 PO 4 10g / L - 30g / L, C 4 H 4 Na 2 O 6 1g / L - 15g / L; the process parameters of the anodic oxidation are: current density 2A / dm 2 ~15A / dm 2 , temperature 15°C - 30°C, and oxidation time 30min - 90min. By adding C 4 H 4 Na 2 O 6 to the electrolyte used in the anodic oxidation and controlling its addition amount, the present invention further promotes the uniform fineness of the oxide film layer on the surface of the titanium tantalum alloy substrate, reduces its roughness, and improves its corrosion resistance.

[0014] The above-mentioned titanium tantalum alloy with a wear-resistant and corrosion-resistant film layer is characterized in that the electrolyte composition used in the hard anodic oxidation in step two is: H 2 SO 4 140g / L - 200g / L, organic weak acid 10g / L - 50g / L, and the organic weak acid is C 6 H 8 O 7 or / and C 4 H 6 O 5 ; the process parameters of the hard anodic oxidation are: temperature -5°C - 5°C, current density 2A / dm 2 ~8A / dm 2 , and oxidation time 40min - 120min. By adding an appropriate amount of organic weak acid to the electrolyte used in the hard anodic oxidation, the present invention further promotes the uniform fineness of the oxide film layer on the surface of the titanium tantalum alloy substrate, increases the hardness, and improves its corrosion resistance.

[0015] The above-mentioned titanium tantalum alloy with a wear-resistant film layer is characterized in that the sealing solution used in the sealing treatment in step three is a solution of nickel acetate, potassium dichromate or sodium dichromate.

[0016] The present invention has the following advantages compared with the prior art:

[0017] 1. The present invention in-situ forms an oxide film layer on the surface of a titanium tantalum alloy with a flat and clean surface after treatment by means of micro-arc oxidation, anodic oxidation or hard anodic oxidation. The oxide film layer is more tightly bonded to the titanium tantalum alloy matrix, greatly improving the surface hardness of the titanium tantalum alloy, which can reach up to more than 1500 HV, improving the wear resistance of the titanium tantalum alloy, and thus increasing its service life. It has good application prospects in the fields of nuclear power and biomedical materials.

[0018] 2. The present invention in-situ forms an oxide film layer on the surface of the titanium tantalum alloy by means of micro-arc oxidation, anodic oxidation or hard anodic oxidation, overcoming the disadvantage that the thin passivation layer on the surface of the titanium tantalum alloy is easily worn through and has poor protection effect, improving the performance of the oxide film layer, thereby improving the structural compactness and uniformity of the surface of the titanium tantalum alloy, greatly improving its corrosion resistance and stability, and making it suitable for use in the chemical industry and nuclear power fields.

[0019] 3. The present invention only needs to immerse the titanium tantalum alloy in the electrolyte for oxidation treatment by means of micro-arc oxidation, anodic oxidation or hard anodic oxidation, realizing the overall treatment of large-sized and shaped titanium tantalum alloys and in-situ generating a surface oxide film layer. The process is simple, economical and convenient.

[0020] 4. The oxide film layer prepared by micro-arc oxidation of the present invention is thicker and has higher hardness, better wear resistance and corrosion resistance. The oxide film layer prepared by anodic oxidation or hard anodic oxidation is thinner, with improved hardness and good wear resistance, and its corrosion resistance is lower than that of the micro-arc oxidation film layer, but it has better biocompatibility. Therefore, the present invention controls different oxide film layer preparation methods to adjust the performance of the oxide film layer to meet different application needs, expanding the application scope of the present invention.

[0021] 5. During the process of micro-arc oxidation, anodic oxidation or hard anodic oxidation treatment of the present invention, compressed air is introduced into the electrolyte for stirring, effectively reducing the concentration gradient and temperature gradient at the phase interface between the titanium tantalum alloy and the electrolyte solution, making the current distribution more uniform, and being beneficial to improving the uniformity of the oxide film layer.

[0022] 6. The present invention in-situ forms an oxide film layer on the surface of the titanium tantalum alloy as a wear-resistant film layer by means of micro-arc oxidation, anodic oxidation or hard anodic oxidation, with a short reaction cycle and a wide application range.

[0023] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Description of the Drawings

[0024] Figure 1 It is a morphology diagram of the micro-arc oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 1 of the present invention.

[0025] Figure 2 It is a morphology diagram of the micro-arc oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 2 of the present invention.

[0026] Figure 3 It is a morphology diagram of the micro-arc oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 3 of the present invention.

[0027] Figure 4 It is a morphology diagram of the anodic oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 4 of the present invention.

[0028] Figure 5 It is a morphology diagram of the anodic oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 5 of the present invention.

[0029] Figure 6 It is a morphology diagram of the anodic oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 6 of the present invention.

[0030] Figure 7 It is a morphology diagram of the hard anodic oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 7 of the present invention.

[0031] Figure 8 It is a morphology diagram of the hard anodic oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 8 of the present invention.

[0032] Figure 9 It is a morphology diagram of the hard anodic oxidation film layer on the surface of the titanium-tantalum alloy in Embodiment 9 of the present invention. Detailed Embodiments

[0033] Embodiment 1

[0034] The titanium-tantalum alloy with a wear-resistant film layer in this embodiment includes a titanium-tantalum alloy substrate and a wear-resistant film layer provided on the surface of the titanium-tantalum alloy substrate, and is prepared by a method including the following steps:

[0035] Step 1: Grind the titanium-tantalum alloy with 240# - 2000# sandpaper, and then place it in a degreasing solution at 60°C - 90°C for 1 minute for degreasing. The mass content composition of the degreasing solution includes: 30% NaOH, 20% Na 2 CO 3 20%, Na 3 PO 4 ·12H 2O 30%, degreasing agent 20%. After degreasing, the titanium-tantalum alloy is cleaned with deionized water and then immersed in the immersion solution at 70°C - 80°C for 10 s. The volume content composition of the immersion solution includes: HF solution with a mass concentration of 40% at 40%, HNO 3 60%. After immersion, the titanium-tantalum alloy is cleaned with deionized water and then immersed in the brightening solution at room temperature for 60 s. The volume content composition of the brightening solution includes: H 2 SO 4 solution 25%, H 2 O 2 solution 75% at 75%. After brightening, the titanium-tantalum alloy is ultrasonically cleaned in acetone, ethanol, and deionized water in sequence to obtain a titanium-tantalum alloy with a flat and clean surface;

[0036] Step 2: Place the titanium-tantalum alloy with a flat and clean surface obtained in Step 1 in the electrolyte and perform micro-arc oxidation treatment using a double-pulse power supply. During the whole process of the treatment, compressed air is introduced into the electrolyte to form a micro-arc oxidation film layer on the surface of the titanium-tantalum alloy, obtaining a titanium-tantalum alloy with a film layer. The electrolyte composition used for micro-arc oxidation is: Na 2 SiO 3 10 g / L, Na 3 PO 4 25 g / L, Na 2 B 4 O 7 15 g / L, NH 4 VO 3 5 g / L, NH 4 HF 2 10 g / L, C 6 H 5 Na 3 O 7 1 g / L, NaOH 1 g / L. The process parameters of the micro-arc oxidation are: the power supply mode is the constant voltage mode, the electrical parameters are the positive voltage 600 V, the negative voltage 200 V, the frequency 600 Hz, the duty cycle 40%, the temperature 15°C, and the oxidation time 60 min;

[0037] Step 3: Immerse the titanium-tantalum alloy with a film layer obtained in Step 2 in a nickel acetate solution at 90°C ± 5°C for 30 min for sealing treatment, then clean it with deionized water, and then dry it with compressed air to obtain a titanium-tantalum alloy with an abrasion-resistant film layer.

[0038] Figure 1 This is the morphology diagram of the micro-arc oxidation film layer on the surface of the titanium-tantalum alloy in this embodiment. From Figure 1 it can be seen that obvious volcanic-shaped micropores can be seen in the micro-arc oxidation film layer.

[0039] After detection, the thickness of the micro-arc oxidation film layer on the surface of the titanium-tantalum alloy in this example is about 53 μm, and the Vickers hardness is about 896 HV. From the friction and wear test, it can be known that the friction coefficient of the titanium-tantalum alloy with a wear-resistant film layer in this example is 0.4 - 0.7, and no obvious peeling phenomenon is observed on the wear-resistant film layer after the test.

[0040] Example 2

[0041] The titanium-tantalum alloy with a wear-resistant film layer in this example includes a titanium-tantalum alloy substrate and a wear-resistant film layer provided on the surface of the titanium-tantalum alloy substrate, and is prepared by a method including the following steps:

[0042] Step 1: Polish the titanium-tantalum alloy with sandpaper of 240# - 2000#, then place it in a degreasing solution and degrease it at 60°C - 90°C for 3 minutes. The mass content composition of the degreasing solution includes: 10% NaOH, 40% Na 2 CO 3 40%, 30% Na 3 PO 4 ·12H 2 O, 20% defoamer. After degreasing the titanium-tantalum alloy, wash it with deionized water and then place it in an impregnating solution and impregnate it at 70°C - 80°C for 60 seconds. The volume content composition of the impregnating solution includes: 25% HF solution with a mass concentration of 40%, 75% HNO 3 . After impregnating the titanium-tantalum alloy, wash it with deionized water and then place it in a brightening solution and soak it at room temperature for 30 seconds. The volume content composition of the brightening solution includes: 20% solution of H 2 SO 4 with a mass concentration of 98%, 80% solution of H 2 O 2 with a mass concentration of 30%. After brightening, ultrasonically clean the titanium-tantalum alloy in acetone, ethanol, and deionized water in sequence to obtain a titanium-tantalum alloy with a flat and clean surface;

[0043] Step 2: Place the titanium-tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolyte and perform micro-arc oxidation treatment using a bipolar pulse power supply, and introduce compressed air into the electrolyte throughout the treatment process to form a micro-arc oxidation film layer on the surface of the titanium-tantalum alloy, obtaining a titanium-tantalum alloy with a film layer. The electrolyte composition used for the micro-arc oxidation is: Na 2 SiO 3 40 g / L, Na 3 PO 4 15 g / L, Na 2 B 4 O 7 10 g / L, NH 4 VO 3 5 g / L, C6 H 11 NaO 7 5 g / L, NaOH 3 g / L; The process parameters of the micro-arc oxidation are as follows: the power supply mode is a constant voltage mode, the electrical parameters are a positive voltage of 450 V, a negative voltage of 100 V, a frequency of 400 Hz, a duty cycle of 60%, a temperature of 25 °C, and an oxidation time of 30 min;

[0044] Step 3: Immerse the titanium tantalum alloy with the film layer obtained in Step 2 in a potassium dichromate solution at 85 °C ± 5 °C for 20 min for sealing treatment, then clean it with deionized water, and then dry it at a low temperature to obtain a titanium tantalum alloy with a wear-resistant film layer.

[0045] Figure 2 This is the morphology diagram of the micro-arc oxidation film layer on the surface of the titanium tantalum alloy in this embodiment. From Figure 2 it can be seen that obvious volcanic-shaped micropores can be seen in the micro-arc oxidation film layer, and the micro-arc oxidation film layer is more uniform and dense.

[0046] After testing, the thickness of the micro-arc oxidation film layer on the surface of the titanium tantalum alloy in this embodiment is about 36 μm, and the Vickers hardness is about 1530 HV; through the friction and wear test, it can be known that the friction coefficient of the titanium tantalum alloy with a wear-resistant film layer in this embodiment is 0.2 - 0.42. After the test, it is observed that there is no obvious peeling phenomenon on the wear-resistant film layer, and the corrosion resistance in boiling nitric acid is improved by one order of magnitude.

[0047] Example 3

[0048] The titanium tantalum alloy with a wear-resistant film layer in this embodiment includes a titanium tantalum alloy substrate and a wear-resistant film layer provided on the surface of the titanium tantalum alloy substrate, and is prepared by a method including the following steps:

[0049] Step 1: Grind the titanium tantalum alloy with sandpaper of 240# - 2000#, then place it in a degreasing solution at 60 °C - 90 °C for 5 min for degreasing. The mass content composition of the degreasing solution includes: 30% NaOH, Na 2 CO 3 45%, Na 3 PO 4 ·12H 2 O 20%, and 5% of a degreasing agent. After degreasing, the titanium tantalum alloy is cleaned with deionized water and then placed in an impregnating solution at 70 °C - 80 °C for 120 s. The volume content composition of the impregnating solution includes: 30% of an HF solution with a mass concentration of 40%, and 70% of an HNO 3 After impregnation, the titanium tantalum alloy is cleaned with deionized water and then placed in a brightening solution at room temperature for 30 s. The volume content composition of the brightening solution includes: 98% of an H 2 SO 4Solution 15%, H with a mass concentration of 30% 2 O 2 Solution 85%. After brightening, the titanium tantalum alloy is ultrasonically cleaned in acetone, ethanol, and deionized water in sequence to obtain a titanium tantalum alloy with a flat and clean surface;

[0050] Step 2: Place the titanium tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolyte and perform micro-arc oxidation treatment using a dual-pulse power supply. During the whole process of the treatment, compressed air is introduced into the electrolyte to form a micro-arc oxidation film layer on the surface of the titanium tantalum alloy, obtaining a titanium tantalum alloy with a film layer. The electrolyte composition used for the micro-arc oxidation is: Na 2 SiO 3 50 g / L, Na 3 PO 4 5 g / L, Na 2 B 4 O 7 5 g / L, NH 4 HF 2 10 g / L, C 6 H 5 Na 3 O 7 5 g / L, NaOH 5 g / L. The process parameters of the micro-arc oxidation are: the power supply mode is the constant voltage mode, the electrical parameters are a positive voltage of 300 V, a negative voltage of 0 V, a frequency of 200 Hz, a duty cycle of 5%, a temperature of 30 °C, and an oxidation time of 10 min;

[0051] Step 3: Immerse the titanium tantalum alloy with a film layer obtained in Step 2 in a sodium dichromate solution at 90 °C ± 5 °C for 20 min for sealing treatment, then clean it with deionized water, and then dry it with compressed air to obtain a titanium tantalum alloy with an abrasion-resistant film layer.

[0052] Figure 3 This is the morphology diagram of the micro-arc oxidation film layer on the surface of the titanium tantalum alloy in this example. It can be seen from Figure 3 that obvious volcanic micropores can be seen in the micro-arc oxidation film layer.

[0053] After testing, the thickness of the micro-arc oxidation film layer on the surface of the titanium tantalum alloy in this example is about 24 μm, and the Vickers hardness is about 758 HV. From the friction and wear test, it can be known that the friction coefficient of the titanium tantalum alloy with an abrasion-resistant film layer in this example is 0.5 - 0.7. After the test, no obvious peeling phenomenon is observed on the abrasion-resistant film layer, and the corrosion resistance in boiling nitric acid is improved by an order of magnitude.

[0054] Example 4

[0055] The titanium tantalum alloy with a wear-resistant film layer in this embodiment includes a titanium tantalum alloy substrate and a wear-resistant film layer provided on the surface of the titanium tantalum alloy substrate, and is prepared by a method including the following steps:

[0056] Step 1: Grind the titanium tantalum alloy with sandpaper of 240# - 2000#, then place it in a degreasing solution and degrease it at 60°C - 90°C for 3 minutes. The mass content composition of the degreasing solution includes: 10% NaOH, 40% Na 2 CO 3 40%, 30% Na 3 PO 4 ·12H 2 O, 20% defoamer. After degreasing, wash the titanium tantalum alloy with deionized water and then immerse it in an impregnating solution at 70°C - 80°C for 60 seconds. The volume content composition of the impregnating solution includes: 25% HF solution with a mass concentration of 40%, 75% HNO 3 75%. After impregnation, wash the titanium tantalum alloy with deionized water and then soak it in a brightening solution at room temperature for 30 seconds. The volume content composition of the brightening solution includes: 20% H 2 SO 4 solution with a mass concentration of 98%, 80% H 2 O 2 solution with a mass concentration of 30%. After brightening, ultrasonically clean the titanium tantalum alloy in acetone, ethanol, and deionized water in sequence to obtain a titanium tantalum alloy with a flat and clean surface;

[0057] Step 2: Place the titanium tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolytic solution and perform anodic oxidation treatment using a high-frequency switching power supply. Use the titanium tantalum alloy as the anode and a lead plate as the cathode, and introduce compressed air into the electrolytic solution throughout the treatment process to form an anodic oxidation film layer on the surface of the titanium tantalum alloy, obtaining a titanium tantalum alloy with a film layer; The composition of the electrolytic solution used for anodic oxidation is: H 2 SO 4 160 g / L, H 3 PO 4 30 g / L, C 4 H 4 Na 2 O 6 1 g / L; The process parameters of the anodic oxidation are: current density 6 A / dm 2 , temperature 25°C, oxidation time 30 minutes;

[0058] Step 3: Immerse the titanium tantalum alloy with a film layer obtained in Step 2 in a nickel acetate solution at 90°C ± 5°C for 30 minutes for sealing treatment, then wash it clean with deionized water, and then dry it with compressed air to obtain a titanium tantalum alloy with a wear-resistant film layer.

[0059] Figure 4 This is the morphology diagram of the anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment. It can be seen from Figure 4 that the anodic oxidation film layer is relatively flat and uniform, with a small amount of uneven pits formed.

[0060] After testing, the thickness of the anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment is about 27.5 μm, and the Vickers hardness is about 692 HV; after the friction and wear test, no obvious peeling phenomenon is observed on the wear-resistant film layer.

[0061] Example 5

[0062] The titanium tantalum alloy with a wear-resistant film layer in this embodiment includes a titanium tantalum alloy substrate and a wear-resistant film layer provided on the surface of the titanium tantalum alloy substrate, and is prepared by a method including the following steps:

[0063] Step 1: Grind the titanium tantalum alloy with sandpaper of 240# - 2000#, then place it in a degreasing solution and degrease it at 60°C - 90°C for 1 minute. The mass content composition of the degreasing solution includes: 30% NaOH, 20% Na 2 CO 3 20%, 30% Na 3 PO 4 ·12H 2 O, and 20% degreasing agent. After degreasing, wash the titanium tantalum alloy with deionized water and then immerse it in an impregnating solution at 70°C - 80°C for 10 seconds. The volume content composition of the impregnating solution includes: 40% HF solution with a mass concentration of 40%, and 60% HNO 3 60%. After impregnation, wash the titanium tantalum alloy with deionized water and then soak it in a brightening solution at room temperature for 60 seconds. The volume content composition of the brightening solution includes: 25% H 2 SO 4 solution, and 75% H 2 O 2 solution. After brightening, ultrasonically clean the titanium tantalum alloy in acetone, ethanol, and deionized water in sequence to obtain a titanium tantalum alloy with a flat and clean surface;

[0064] Step 2: Place the titanium tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolyte and perform anodic oxidation treatment using a high-frequency switching power supply. Use the titanium tantalum alloy as the anode and a lead plate as the cathode, and introduce compressed air into the electrolyte throughout the treatment process to form an anodic oxidation film layer on the surface of the titanium tantalum alloy, obtaining a titanium tantalum alloy with a film layer; the electrolyte used for the anodic oxidation has the following composition: H 2 SO 4 180 g / L, H 3 PO 4 20 g / L, C4 H 4 Na 2 O 6 15 g / L; The process parameters of the anodic oxidation are: current density 2 A / dm 2 , temperature 30 °C, oxidation time 90 min;

[0065] Step 3: Immerse the titanium tantalum alloy with the film layer obtained in Step 2 in a potassium dichromate solution at 85 °C ± 5 °C for 15 min for sealing treatment, then clean it with deionized water, and then dry it with compressed air to obtain a titanium tantalum alloy with a wear-resistant film layer.

[0066] Figure 5 is the morphology diagram of the anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment. From Figure 5 it can be seen that the anodic oxidation film layer is relatively flat and uniform, and no uneven pits are generated.

[0067] After testing, the thickness of the anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment is about 31.5 μm, and the Vickers hardness is about 733 HV; after the friction and wear test, no obvious peeling phenomenon is observed on the wear-resistant film layer.

[0068] Example 6

[0069] The titanium tantalum alloy with a wear-resistant film layer in this embodiment includes a titanium tantalum alloy matrix and a wear-resistant film layer provided on the surface of the titanium tantalum alloy matrix, and is prepared by a method including the following steps:

[0070] Step 1: Grind the titanium tantalum alloy with 240# - 2000# sandpaper, and then place it in a degreasing solution at 60 °C - 90 °C for 5 min for degreasing. The mass content composition of the degreasing solution includes: 30% NaOH, Na 2 CO 3 45%, Na 3 PO 4 ·12H 2 O 20%, degreasing agent 5%. After degreasing, the titanium tantalum alloy is cleaned with deionized water and then placed in an impregnation solution at 70 °C - 80 °C for 120 s. The volume content composition of the impregnation solution includes: 30% HF solution with a mass concentration of 40%, 70% HNO 3 70%. After impregnation, the titanium tantalum alloy is cleaned with deionized water and then placed in a brightening solution at room temperature for 30 s. The volume content composition of the brightening solution includes: 15% H 2 SO 4 solution with a mass concentration of 98%, 30% H 2 O 2The solution is 85%. The titanium-tantalum alloy after brightening is ultrasonically cleaned in acetone, ethanol, and deionized water in sequence to obtain a titanium-tantalum alloy with a flat and clean surface.

[0071] Step 2: Place the titanium-tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolyte and perform anodic oxidation treatment using a high-frequency switching power supply. Use the titanium-tantalum alloy as the anode and a lead plate as the cathode, and introduce compressed air into the electrolyte throughout the treatment process to form an anodic oxidation film layer on the surface of the titanium-tantalum alloy, obtaining a titanium-tantalum alloy with a film layer. The composition of the electrolyte used for the anodic oxidation is as follows: H 2 SO 4 240 g / L, H 3 PO 4 10 g / L, C 4 H 4 Na 2 O 6 1 g / L; The process parameters of the anodic oxidation are: current density 15 A / dm 2 , temperature 15 °C, oxidation time 30 min.

[0072] Step 3: Immerse the titanium-tantalum alloy with a film layer obtained in Step 2 in a solution of sodium dichromate at 85 °C ± 5 °C for 15 min for sealing treatment, then clean it with deionized water, and then dry it with compressed air to obtain a titanium-tantalum alloy with an abrasion-resistant film layer.

[0073] Figure 6 This is the morphology diagram of the anodic oxidation film layer on the surface of the titanium-tantalum alloy in this example. It can be seen from Figure 6 that the anodic oxidation film layer is relatively flat and uniform, with a small number of uneven pits generated.

[0074] After testing, the thickness of the anodic oxidation film layer on the surface of the titanium-tantalum alloy in this example is about 21 μm, and the Vickers hardness is about 683 HV; after the friction and wear test, it is observed that there is no obvious peeling phenomenon on the abrasion-resistant film layer, and the corrosion resistance in boiling nitric acid is increased by about two times.

[0075] Example 7

[0076] The titanium-tantalum alloy with an abrasion-resistant film layer in this example includes a titanium-tantalum alloy substrate and an abrasion-resistant film layer provided on the surface of the titanium-tantalum alloy substrate, and is prepared by a method including the following steps:

[0077] Step 1: Polish the titanium-tantalum alloy with sandpaper of 240# - 2000#, then place it in a degreasing solution and perform degreasing at 60 °C - 90 °C for 3 min. The mass content composition of the degreasing solution includes: NaOH 10%, Na 2 CO 3 40%, Na 3 PO4 12H 2 O 30%, degreasing agent 20%, the degreased titanium-tantalum alloy is washed with deionized water and then immersed in the immersion solution at 70℃~80℃ for 60s. The volume content of the immersion solution includes: 40% by mass concentration HF solution 25%, 68% by mass concentration HNO 3 75%, the impregnated titanium-tantalum alloy was washed with deionized water and then immersed in a light emitting liquid at room temperature for 30 seconds. The volume content of the light emitting liquid included: H 2 SO 4 Solution 20%, mass concentration 30% H 2 O 2 The solution is 80%, and the titanium-tantalum alloy after light emission is ultrasonically cleaned in acetone, ethanol and deionized water in turn to obtain a titanium-tantalum alloy with a smooth and clean surface;

[0078] Step 2: placing the titanium-tantalum alloy with a smooth and clean surface obtained in step 1 in an electrolyte and performing hard anodizing treatment using a chiller combined with a high-frequency switching power supply, with the titanium-tantalum alloy as the anode and the lead plate as the cathode, and introducing compressed air into the electrolyte throughout the treatment process to form a hard anodized film layer on the surface of the titanium-tantalum alloy, thereby obtaining a titanium-tantalum alloy with a film layer; the electrolyte composition used for the hard anodizing is: H 2 SO 4 140g / L, C 4 H 6 O 5 25g / L; the process parameters of the hard anodizing are: temperature 5°C, current density 8A / dm 2 , oxidation time 40min;

[0079] Step 3: Place the titanium-tantalum alloy with a film layer obtained in step 2 in a nickel acetate solution at 90°C±5°C for 30 minutes for sealing treatment, then clean it with deionized water, and then blow dry it with compressed air to obtain a titanium-tantalum alloy with a wear-resistant film layer.

[0080] Figure 7 The morphology of the hard anodized film layer on the surface of the titanium-tantalum alloy in this embodiment is shown in FIG. Figure 7 It can be seen that the hard anodized film layer is relatively uniform and flat, with more uneven pits and a large number of cracks generated.

[0081] According to the test, the thickness of the hard anodized film layer on the surface of the titanium-tantalum alloy in this embodiment is about 45 μm, and the Vickers hardness is about 748 HV; after the friction and wear test, it was observed that the wear-resistant film layer had no obvious peeling phenomenon.

[0082] Example 8

[0083] The titanium tantalum alloy with a wear-resistant film layer in this embodiment includes a titanium tantalum alloy substrate and a wear-resistant film layer provided on the surface of the titanium tantalum alloy substrate, and is prepared by a method including the following steps:

[0084] Step 1: Polish the titanium tantalum alloy with sandpaper of 240# - 2000#, then place it in a degreasing solution and degrease it at 60°C - 90°C for 5 minutes. The mass content composition of the degreasing solution includes: 30% NaOH, 45% Na 2 CO 3 45%, 20% Na 3 PO 4 ·12H 2 O, 5% defoamer. After degreasing the titanium tantalum alloy, wash it with deionized water and then place it in an impregnating solution and impregnate it at 70°C - 80°C for 120 s. The volume content composition of the impregnating solution includes: 30% HF solution with a mass concentration of 40%, 70% HNO 3 70%. After impregnating the titanium tantalum alloy, wash it with deionized water and then place it in a brightening solution and soak it at room temperature for 30 s. The volume content composition of the brightening solution includes: 15% H 2 SO 4 solution, 85% H 2 O 2 solution. After brightening, ultrasonically clean the titanium tantalum alloy in acetone, ethanol, and deionized water in sequence to obtain a titanium tantalum alloy with a flat and clean surface;

[0085] Step 2: Place the titanium tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolyte and perform hard anodic oxidation treatment by combining an ice water machine with a high-frequency switching power supply. Use the titanium tantalum alloy as the anode and a lead plate as the cathode, and introduce compressed air into the electrolyte throughout the treatment process to form a hard anodic oxidation film layer on the surface of the titanium tantalum alloy, obtaining a titanium tantalum alloy with a film layer. The electrolyte composition used for the hard anodic oxidation is: 180 g / L H 2 SO 4 , 20 g / L C 4 H 6 O 5 , 30 g / L C 6 H 8 O 7 30 g / L. The process parameters of the hard anodic oxidation are: temperature 0°C, current density 4 A / dm 2 , oxidation time 120 min;

[0086] Step 3: Place the titanium tantalum alloy with a film layer obtained in Step 2 in a solution of sodium dichromate at 85°C ± 5°C and soak it for 15 minutes for sealing treatment, then wash it clean with deionized water, and then dry it with compressed air to obtain a titanium tantalum alloy with a wear-resistant film layer.

[0087] Figure 8 This is the morphology diagram of the hard anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment. From Figure 8 it can be seen that the hard anodic oxidation film layer is relatively uniform and flat, and uneven pits are formed on the surface.

[0088] After testing, the thickness of the hard anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment is about 89 μm, and the Vickers hardness is about 1083 HV; after the friction and wear test, no obvious peeling phenomenon is observed on the wear-resistant film layer.

[0089] Example 9

[0090] The titanium tantalum alloy with a wear-resistant film layer in this embodiment includes a titanium tantalum alloy substrate and a wear-resistant film layer provided on the surface of the titanium tantalum alloy substrate, and is prepared by a method including the following steps:

[0091] Step 1: Grind the titanium tantalum alloy with 240# - 2000# sandpaper, and then place it in a degreasing solution at 60°C - 90°C for 3 minutes for degreasing. The mass content composition of the degreasing solution includes: 10% NaOH, 40% Na 2 CO 3 40%, 30% Na 3 PO 4 ·12H 2 O, and 20% degreasing agent. After degreasing, wash the titanium tantalum alloy with deionized water and then place it in an impregnating solution at 70°C - 80°C for 60 seconds. The volume content composition of the impregnating solution includes: 25% HF solution with a mass concentration of 40%, 75% HNO 3 After impregnation, wash the titanium tantalum alloy with deionized water and then place it in a brightening solution at room temperature for 30 seconds. The volume content composition of the brightening solution includes: 20% H 2 SO 4 solution, 80% H 2 O 2 solution. After brightening, ultrasonically clean the titanium tantalum alloy in acetone, ethanol, and deionized water in sequence to obtain a titanium tantalum alloy with a flat and clean surface;

[0092] Step 2: Place the titanium tantalum alloy with a flat and clean surface obtained in Step 1 in an electrolyte and perform hard anodic oxidation treatment using an ice water machine combined with a high-frequency switching power supply. Use the titanium tantalum alloy as the anode and a lead plate as the cathode, and introduce compressed air into the electrolyte throughout the treatment process to form a hard anodic oxidation film layer on the surface of the titanium tantalum alloy to obtain a titanium tantalum alloy with a film layer. The electrolyte composition used for the hard anodic oxidation is: H 2 SO 4 200 g / L, C 6H 8 O 7 10 g / L; The process parameters of the hard anodic oxidation are: temperature -5°C, current density 2 A / dm 2 , oxidation time 60 min;

[0093] Step 3: Immerse the titanium tantalum alloy with the film layer obtained in Step 2 in a potassium dichromate solution at 85°C ± 5°C for 15 min for sealing treatment, then clean it with deionized water, and then dry it with compressed air to obtain a titanium tantalum alloy with an abrasion-resistant film layer.

[0094] Figure 9 is the morphology diagram of the hard anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment. From Figure 9 it can be seen that the hard anodic oxidation film layer is relatively uniform and flat, the number of uneven pits on the surface is reduced compared with Example 8, and a small amount of cracks are generated.

[0095] After testing, the thickness of the hard anodic oxidation film layer on the surface of the titanium tantalum alloy in this embodiment is about 68 μm, and the Vickers hardness is about 945 HV; after the friction and wear test, no obvious peeling phenomenon is observed on the abrasion-resistant film layer.

[0096] The above is only a preferred embodiment of the present invention, and does not impose any limitation on the present invention. Any simple modification, change, and equivalent change made to the above embodiments according to the technical essence of the invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A titanium tantalum alloy with an abrasion-resistant film layer, characterized in that, it comprises a titanium tantalum alloy substrate and an abrasion-resistant film layer provided on the surface of the titanium tantalum alloy substrate, and is prepared by a method comprising the following steps: Step 1: Grind, degrease, immerse and brighten the titanium tantalum alloy in sequence, and then ultrasonically clean it in acetone, ethanol and deionized water in sequence to obtain a titanium tantalum alloy with a flat and clean surface; Step 2: Place the titanium-tantalum alloy with a flat and clean surface obtained in Step 1 into an electrolyte for micro-arc oxidation treatment. During the whole process of the treatment, compressed air is introduced into the electrolyte to form an oxide film layer on the surface of the titanium-tantalum alloy, obtaining a titanium-tantalum alloy with a film layer. The electrolyte composition used for the micro-arc oxidation is as follows: Na 2 SiO 3 10 g / L to 50 g / L, Na 3 PO 4 5 g / L to 25 g / L, Na 2 B 4 O 7 5 g / L to 15 g / L, ammonium salt 5 g / L to 15 g / L, organic sodium salt 1 g / L to 5 g / L, pH regulator 1 g / L to 5 g / L; the ammonium salt is NH 4 VO 3 or / and NH 4 HF 2 , the organic sodium salt is C 6 H 5 Na 3 O 7 or / and C 6 H 11 NaO 7 , the pH regulator is NaOH or / and KOH; the process parameters of the micro-arc oxidation are as follows: the power supply mode is constant current or constant voltage mode, the electrical parameters are forward voltage 300 V to 600 V, reverse voltage 0 to 200 V, frequency 200 Hz to 600 Hz, duty cycle 5% to 60%, temperature 15 °C to 30 °C, oxidation time 10 min to 60 min; Step 3: Perform a sealing treatment on the titanium tantalum alloy with a film layer obtained in Step 2, then clean it with deionized water, and then dry it with compressed air or dry it at a low temperature to obtain a titanium tantalum alloy with an abrasion-resistant film layer.

2. The titanium tantalum alloy with an abrasion-resistant film layer according to claim 1, characterized in that, The grinding in Step 1 is carried out with sandpaper; the degreasing solution used for degreasing consists of the following components by mass content: 10% - 30% NaOH, 2 CO 3 20% - 45%, Na 3 PO 4 ·12H 2 O 20% - 30%, 5% - 20% degreasing agent. The degreasing temperature is 60°C - 90°C, and the time is 1 min - 5 min; the pickling solution used for pickling consists of the following components by volume content: 25% - 40% HF solution with a mass concentration of 40%, 60% - 75% HNO 3 . The pickling temperature is 70°C - 80°C, and the time is 10 s - 120 s; the brightening solution used for brightening consists of the following components by volume content: 15% - 25% H 2 SO 4 solution, 75% - 85% H 2 O 2 solution with a mass concentration of 30%. The brightening temperature is room temperature, and the time is 30 s - 60 s.

3. The titanium tantalum alloy with an abrasion-resistant film layer according to claim 1, characterized in that, the sealing liquid used in the sealing treatment in Step 3 is a solution of nickel acetate, potassium dichromate or sodium dichromate.

Images