A method for preparing crystal flowers on the surface of titanium alloy

Abstract

This invention provides a method for preparing crystal flowers on the surface of titanium alloys. The preparation process involves sequentially degreasing and removing the oxide film from the surface of the titanium alloy, followed by placing it in a heat treatment furnace at a vacuum degree ≤1.0×10⁻⁶. ‑2 Under the condition of Pa, at the phase transformation temperature T of titanium alloy β ~T β Gradient cyclic heat treatment is performed at +300℃ and 500℃~800℃. After the gradient cyclic heat treatment is completed, the alloy is cooled to ≤300℃ and removed from the furnace to obtain a titanium alloy with a crystalline surface. The gradient cyclic heat treatment first involves heating to +300℃ and then cooling to ≤300℃. β ~T β Hold at +300℃ for 15-60 minutes, then cool to 500-800℃ and hold for 10-30 minutes, then raise the temperature to T. β ~T β Hold at +300℃ for 15-60 minutes, then cool to 500-800℃ and hold for 10-30 minutes. Repeat this heating-holding and cooling-holding process continuously. One heating-holding and cooling-holding cycle is defined as one cycle. Experiments show that for the same titanium alloy, the more cycles, the larger the grain size on the surface of the titanium alloy.

Description

Technical Field

[0001] This invention belongs to the field of titanium alloy surface treatment technology, and relates to a method for preparing crystal flowers on the surface of titanium alloys. Background Technology

[0002] Several technical solutions have been disclosed in the prior art for preparing crystal flowers on the surface of pure titanium sheets or pure titanium products. For example, CN202210367037.2 discloses a method for preparing pure titanium sheets with scaly crystal flowers on the surface. This method involves subjecting the pure titanium sheet raw material to a first heating and holding step and a second heating and holding step under vacuum conditions, followed by rapid air-cooling quenching, to obtain a pure titanium sheet with a scaly crystal flower appearance structure. The first heating and holding temperature is 550℃~650℃, and the time is 1h~3h, the purpose of which is to homogenize the grains; the second heating and holding temperature is T... β ~950℃(T) β =833℃~890℃), time greater than 2.5h and less than or equal to 3.5h, the purpose is to allow grain regrowth. CN201710494148.9 discloses a method for processing crystal patterns on titanium products, including the following steps: First, heat-treating the titanium product under vacuum conditions, that is, first heating the titanium product from room temperature to 1000℃~1200℃ under vacuum conditions for 1h~3h and holding it for 1h~2h, then filling it with argon gas and cooling the titanium product to 20℃~60℃ for 3h~5h; Second, polishing the heat-treated titanium product; Third, acid washing the polished titanium product to obtain the titanium product with crystal patterns. However, the applicant has not yet found relevant technical information on preparing crystal patterns on the surface of titanium alloys. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing crystal flowers on the surface of titanium alloys to meet the needs of society.

[0004] The main difference between titanium alloys and pure titanium is the presence of other metallic elements in their chemical composition. This results in variations in their corrosion resistance, heat resistance, and mechanical properties compared to pure titanium, broadening their application range and meeting diverse needs. Because titanium alloys contain other metallic elements, the phase transformation temperature T from the α phase to the β phase varies. β The specific titanium alloy is affected by the content and type of other metallic elements.

[0005] The method for preparing crystal flowers on the surface of titanium alloy according to the present invention involves sequentially degreasing and removing oxide film from the surface of the titanium alloy, followed by placing it in a heat treatment furnace at a vacuum degree ≤1.0×10⁻⁶. -2 Under the condition of Pa, at the phase transformation temperature T of titanium alloy β ~T βGradient cyclic heat treatment is performed at +300℃ and 500℃~800℃. After the gradient cyclic heat treatment is completed, the alloy is cooled to ≤300℃ and removed from the furnace to obtain a titanium alloy with a crystalline surface. The gradient cyclic heat treatment first involves heating to +300℃ and then cooling to ≤300℃. β ~T β Hold at +300℃ for 15-60 minutes, then cool to 500-800℃ and hold for 10-30 minutes, then raise the temperature to T. β ~T β Hold at +300℃ for 15-60 minutes, then cool to 500-800℃ and hold for 10-30 minutes. Repeat this heating-holding and cooling-holding process continuously. One heating-holding and cooling-holding cycle is defined as one cycle. Experiments show that for the same titanium alloy, the more cycles, the larger the grain size on the surface of the titanium alloy.

[0006] In the above method for preparing grains on the surface of titanium alloys, the gradient cyclic heat treatment is performed at least twice, and in the last cycle, at T... β ~T β After the +300℃ heat preservation period, the temperature is directly reduced to ≤300℃ before the product is removed from the oven.

[0007] In the above method for preparing crystal flowers on the surface of titanium alloys, the gradient cyclic heat treatment involves a heating rate of 10–60 °C / min and a cooling rate of 10–30 °C / min.

[0008] The above-mentioned method for preparing crystal flowers on the surface of titanium alloys involves immersing the titanium alloy in a sodium dodecylbenzenesulfonate solution with a mass concentration of 5% to 50%, wiping off the oil stains on the surface of the titanium alloy, rinsing it with tap water, and then drying it.

[0009] The above-mentioned method for preparing crystal flowers on the surface of titanium alloys involves removing the oxide film from the surface of the titanium alloy by immersing the degreased titanium alloy in a hydrofluoric acid solution with a mass concentration of 8-12% for pickling. The pickling time is controlled to completely remove the oxide film on the surface of the titanium plate (usually 100s-400s). After pickling, the surface of the titanium alloy is quickly rinsed with tap water to remove any residual acid and then dried.

[0010] The method described in this invention is applicable not only to the preparation of surface flowers on titanium alloy plates, but also to the preparation of surface flowers on titanium alloy products.

[0011] The present invention has the following beneficial effects:

[0012] 1. This invention provides a feasible technical solution for preparing crystal flowers on the surface of titanium alloys. Using the method described in this invention, crystal flowers can be formed on the surface of titanium alloys (see various embodiments).

[0013] 2. The method described in this invention can control the size of the crystal flowers on the surface of titanium alloys by the number of heat treatment cycles, thus facilitating the preparation of crystal flowers of different sizes on the surface of titanium alloys as needed.

[0014] 3. The method described in this invention is simple in process and uses conventional equipment, which is conducive to large-scale production and thus beneficial to industrial application. Attached Figure Description

[0015] Figure 1 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate according to Embodiment 1 of the present invention.

[0016] Figure 2 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 2 of the present invention.

[0017] Figure 3 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 3 of the present invention.

[0018] Figure 4 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 4 of the present invention.

[0019] Figure 5 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 5 of the present invention.

[0020] Figure 6 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 6 of the present invention.

[0021] Figure 7 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 7 of the present invention.

[0022] Figure 8 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 8 of the present invention.

[0023] Figure 9 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 9 of the present invention.

[0024] Figure 10 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 10 of the present invention.

[0025] Figure 11 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 11 of the present invention.

[0026] Figure 12 This is an optical photograph of the crystal flowers prepared on the surface of a titanium alloy plate in Embodiment 12 of the present invention. Detailed Implementation

[0027] The method for preparing crystal flowers on the surface of titanium alloys according to the present invention will be further described below through embodiments and in conjunction with the accompanying drawings. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0028] In the following embodiments, heat treatment was performed using a vacuum heat treatment furnace, and all raw materials were purchased from the market.

[0029] Example 1

[0030] In this embodiment, crystal flowers were prepared on the surface of a TC4 titanium alloy (α+β titanium alloy) plate. The phase transformation temperature T of the TC4 titanium alloy... β The temperature is 995℃. The dimensions of the TC4 titanium alloy plate are 0.5mm × 50mm × 100mm. The process steps are as follows:

[0031] (1) Degreasing and oxide film removal treatment of TC4 titanium alloy plate

[0032] The TC4 titanium alloy plate was immersed in a 20% sodium dodecylbenzene sulfonate solution. After wiping off the surface oil with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TC4 titanium alloy plate was placed in a 10% hydrofluoric acid solution for pickling for 300 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0033] (2) Gradient cyclic heat treatment of TC4 titanium alloy plate

[0034] The TC4 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 9.2 × 10⁻⁶. -3 Pa, the furnace temperature is increased from room temperature to 1000℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is decreased to 800℃ at a cooling rate of 20℃ / min and held for 15min; then the temperature is increased from 800℃ to 1000℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is decreased to 300℃ at a cooling rate of 20℃ / min and removed to cool naturally at room temperature.

[0035] After the above two gradient cycle heat treatments, the grains prepared on the surface of the TC4 titanium alloy plate in this embodiment are as follows: Figure 1 As shown, from Figure 1 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 1.67 mm.

[0036] Example 2

[0037] In this embodiment, crystal flowers were prepared on the surface of a TB6 titanium alloy (near-β titanium alloy) plate. The phase transformation temperature T of the TB6 titanium alloy was... β The temperature is 798℃. The TB6 titanium alloy plate is a round plate with a diameter of 150mm and a thickness of 2mm. The process steps are as follows:

[0038] (1) Degreasing and oxide film removal treatment of TB6 titanium alloy plate

[0039] The TB6 titanium alloy plate was immersed in a 15% sodium dodecylbenzene sulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TB6 titanium alloy plate was placed in an 8% hydrofluoric acid solution for pickling for 400 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0040] (2) Gradient cyclic heat treatment of TB6 titanium alloy plate

[0041] The TB6 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 8.6 × 10⁻⁶. -3 Pa, the furnace temperature is increased from room temperature to 950℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is decreased to 500℃ at a cooling rate of 20℃ / min and held for 15min; then the temperature is increased from 500℃ to 950℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is decreased to 300℃ at a cooling rate of 20℃ / min and removed to cool naturally at room temperature.

[0042] After the above two gradient cycle heat treatments, the grains prepared on the surface of the TB6 titanium alloy plate in this embodiment are as follows: Figure 2 As shown, from Figure 2 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 0.53 mm.

[0043] Example 3

[0044] In this embodiment, crystal flowers were prepared on the surface of a TA18 titanium alloy (near-α titanium alloy) plate. The phase transformation temperature T of the TA18 titanium alloy is... β The temperature is 925℃. The TA18 titanium alloy plate is a round plate with a diameter of 60mm and a thickness of 2mm. The process steps are as follows:

[0045] (1) Degreasing and oxide film removal treatment of TA18 titanium alloy plate

[0046] The TA18 titanium alloy plate was immersed in a 15% sodium dodecylbenzenesulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TA18 titanium alloy plate was placed in a 12% hydrofluoric acid solution for pickling for 200 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0047] (2) Gradient cyclic heat treatment of TA18 titanium alloy plate

[0048] The TA18 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 5.6 × 10⁻⁶. -3 Pa, the furnace temperature is increased from room temperature to 950℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is decreased to 800℃ at a cooling rate of 20℃ / min and held for 15min; then the temperature is increased from 800℃ to 950℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is decreased to 300℃ at a cooling rate of 20℃ / min and removed to cool naturally at room temperature.

[0049] After the above two gradient cycle heat treatments, the grains prepared on the surface of the TA18 titanium alloy plate in this embodiment are as follows: Figure 3 As shown, from Figure 3 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 0.21 mm.

[0050] Example 4

[0051] In this embodiment, crystal flowers were prepared on the surface of a TC4 titanium alloy (α+β titanium alloy) plate. The phase transformation temperature T of the TC4 titanium alloy... β The temperature is 995℃. The dimensions of the TC4 titanium alloy plate are 0.5mm × 50mm × 100mm. The process steps are as follows:

[0052] (1) Degreasing and oxide film removal treatment of TC4 titanium alloy plate

[0053] The TC4 titanium alloy plate was immersed in a 15% sodium dodecylbenzene sulfonate solution. After wiping off the surface oil with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TC4 titanium alloy plate was placed in a 10% hydrofluoric acid solution for pickling for 300 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0054] (2) Gradient cyclic heat treatment of TC4 titanium alloy plate

[0055] The TC4 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 5.6 × 10⁻⁶. -3 Pa, the furnace temperature is increased from room temperature to 1200℃ at a heating rate of 10℃ / min and held for 30min, then the temperature is decreased to 800℃ at a cooling rate of 20℃ / min and held for 10min; then the temperature is increased from 800℃ to 1100℃ at a heating rate of 10℃ / min and held for 15min, then the temperature is decreased to 300℃ at a cooling rate of 20℃ / min and removed to cool naturally at room temperature.

[0056] After the above two gradient cycle heat treatments, the grains prepared on the surface of the TC4 titanium alloy plate in this embodiment are as follows: Figure 4 As shown, from Figure 4 It can be seen that the macroscopic large and small grains on the surface of the TC4 titanium plate are randomly distributed with clear morphology, and the average grain size is about 1.35 mm.

[0057] Example 5

[0058] In this embodiment, crystal flowers were prepared on the surface of a TC4 titanium alloy (α+β titanium alloy) plate. The phase transformation temperature T of the TC4 titanium alloy... β The temperature is 995℃. The dimensions of the TC4 titanium alloy plate are 0.5mm × 50mm × 100mm. The process steps are as follows:

[0059] (1) Degreasing and oxide film removal treatment of TC4 titanium alloy plate

[0060] The TC4 titanium alloy plate was immersed in a 20% sodium dodecylbenzene sulfonate solution. After wiping off the surface oil with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TC4 titanium alloy plate was placed in a 10% hydrofluoric acid solution for pickling for 300 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0061] (2) Gradient cyclic heat treatment of TC4 titanium alloy plate

[0062] The TC4 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 8.7 × 10⁻⁶. -3Pa: The furnace temperature is increased from room temperature to 1000℃ at a heating rate of 10℃ / min and held for 30 minutes. Then the temperature is decreased to 650℃ at a cooling rate of 20℃ / min and held for 15 minutes. Next, the temperature is increased from 650℃ to 1000℃ at a heating rate of 10℃ / min and held for 30 minutes. Then the temperature is decreased to 650℃ at a cooling rate of 20℃ / min and held for 15 minutes. Next, the temperature is increased from 650℃ to 1000℃ at a heating rate of 10℃ / min and held for 30 minutes. After the holding period, the power is turned off and the furnace is cooled to room temperature before being removed.

[0063] After the above three gradient cyclic heat treatments, the grains prepared on the surface of the TC4 titanium alloy plate in this embodiment are as follows: Figure 5 As shown, from Figure 5 It can be seen that the average grain size on the surface of the TC4 titanium plate is approximately 4.20 mm.

[0064] Example 6

[0065] In this embodiment, crystal flowers were prepared on the surface of a TC4 titanium alloy (α+β titanium alloy) plate. The phase transformation temperature T of the TC4 titanium alloy... β The temperature is 995℃. The dimensions of the TC4 titanium alloy plate are 0.5mm × 50mm × 100mm. The process steps are as follows:

[0066] (1) Degreasing and oxide film removal treatment of TC4 titanium alloy plate

[0067] The TC4 titanium alloy plate was immersed in a 20% sodium dodecylbenzene sulfonate solution. After wiping off the surface oil with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TC4 titanium alloy plate was placed in a 10% hydrofluoric acid solution for pickling for 300 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0068] (2) Gradient cyclic heat treatment of TC4 titanium alloy plate

[0069] The TC4 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 8.3 × 10⁻⁶. -3Pa: The furnace temperature is increased from room temperature to 1000℃ at a rate of 10℃ / min and held for 30 minutes. Then, the temperature is decreased to 750℃ at a rate of 15℃ / min and held for 15 minutes. Next, the temperature is increased from 750℃ to 1000℃ at a rate of 10℃ / min and held for 30 minutes. Then, the temperature is decreased to 750℃ at a rate of 15℃ / min and held for 15 minutes. Next, the temperature is increased from 750℃ to 1000℃ at a rate of 10℃ / min and held for 30 minutes. Then, the temperature is decreased to 750℃ at a rate of 15℃ / min and held for 15 minutes. Next, the temperature is increased from 750℃ to 1000℃ at a rate of 10℃ / min and held for 30 minutes. After the holding period, the power is turned off and the furnace is cooled to room temperature before being removed.

[0070] After the above four gradient cyclic heat treatments, the grains prepared on the surface of the TC4 titanium alloy plate in this embodiment are as follows: Figure 6 As shown, from Figure 6 It can be seen that the average grain size on the surface of the TC4 titanium plate is approximately 18.30 mm.

[0071] Example 7

[0072] In this embodiment, crystal flowers were prepared on the surface of a TA18 titanium alloy (near-α titanium alloy) plate. The phase transformation temperature T of the TA18 titanium alloy is... β The temperature is 925℃. The TA18 titanium alloy plate is a round plate with a diameter of 60mm and a thickness of 2mm. The process steps are as follows:

[0073] (1) Degreasing and oxide film removal treatment of TA18 titanium alloy plate

[0074] The TA18 titanium alloy plate was immersed in a 15% sodium dodecylbenzenesulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TA18 titanium alloy plate was placed in a 12% hydrofluoric acid solution for pickling for 200 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0075] (2) Gradient cyclic heat treatment of TA18 titanium alloy plate

[0076] The TA18 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 7.8 × 10⁻⁶. -3Pa: The furnace temperature is increased from room temperature to 950℃ at a rate of 10℃ / min and held for 30 minutes. Then the temperature is decreased to 650℃ at a rate of 20℃ / min and held for 15 minutes. Next, the temperature is increased from 650℃ to 950℃ at a rate of 15℃ / min and held for 30 minutes. Then the temperature is decreased to 650℃ at a rate of 20℃ / min and held for 15 minutes. Next, the temperature is increased from 650℃ to 950℃ at a rate of 15℃ / min and held for 30 minutes. Then the power is turned off, and the furnace is cooled to 200℃ before being removed and allowed to cool naturally at room temperature.

[0077] After the above three gradient cyclic heat treatments, the grains prepared on the surface of the TA18 titanium alloy plate in this embodiment are as follows: Figure 7 As shown, from Figure 7 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 2.03 mm.

[0078] Example 8

[0079] In this embodiment, crystal flowers were prepared on the surface of a TA18 titanium alloy (near-α titanium alloy) plate. The phase transformation temperature T of the TA18 titanium alloy is... β The temperature is 925℃. The TA18 titanium alloy plate is a round plate with a diameter of 60mm and a thickness of 2mm. The process steps are as follows:

[0080] (1) Degreasing and oxide film removal treatment of TA18 titanium alloy plate

[0081] The TA18 titanium alloy plate was immersed in a 15% sodium dodecylbenzenesulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TA18 titanium alloy plate was placed in a 12% hydrofluoric acid solution for pickling for 200 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0082] (2) Gradient cyclic heat treatment of TA18 titanium alloy plate

[0083] The TA18 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 9.2 × 10⁻⁶. -3Pa: The furnace temperature is increased from room temperature to 950℃ at a rate of 10℃ / min and held for 30 minutes. Then, the temperature is decreased to 650℃ at a rate of 20℃ / min and held for 15 minutes. Next, the temperature is increased from 650℃ to 950℃ at a rate of 15℃ / min and held for 30 minutes. Then, the temperature is decreased to 650℃ at a rate of 20℃ / min and held for 15 minutes. Next, the temperature is increased from 650℃ to 950℃ at a rate of 15℃ / min and held for 30 minutes. Then, the temperature is decreased to 650℃ at a rate of 20℃ / min and held for 15 minutes. Next, the temperature is increased from 650℃ to 950℃ at a rate of 15℃ / min and held for 30 minutes. Finally, the power is turned off, and the furnace is cooled to 200℃ before being removed and allowed to cool naturally at room temperature.

[0084] After the above four gradient cyclic heat treatments, the grains prepared on the surface of the TA18 titanium alloy plate in this embodiment are as follows: Figure 8 As shown, from Figure 8 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 3.05 mm.

[0085] Example 9

[0086] In this embodiment, crystal flowers were prepared on the surface of a TA18 titanium alloy (near-α titanium alloy) plate. The phase transformation temperature T of the TA18 titanium alloy is... β The temperature is 925℃. The TA18 titanium alloy plate is a round plate with a diameter of 60mm and a thickness of 2mm. The process steps are as follows:

[0087] (1) Degreasing and oxide film removal treatment of TA18 titanium alloy plate

[0088] The TA18 titanium alloy plate was immersed in a 15% sodium dodecylbenzene sulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TA18 titanium alloy plate was placed in a 10% hydrofluoric acid solution for pickling for 200 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0089] (2) Gradient cyclic heat treatment of TA18 titanium alloy plate

[0090] The TA18 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 6.2 × 10⁻⁶. -3Pa: The furnace temperature is increased from room temperature to 1150℃ at a heating rate of 10℃ / min and held for 15 minutes. Then, the temperature is decreased to 500℃ at a cooling rate of 20℃ / min and held for 10 minutes. Next, the temperature is increased from 500℃ to 1150℃ at a heating rate of 15℃ / min and held for 15 minutes. Then, the temperature is decreased to 500℃ at a cooling rate of 20℃ / min and held for 10 minutes. Next, the temperature is increased from 500℃ to 1150℃ at a heating rate of 15℃ / min and held for 15 minutes. Then, the temperature is decreased to 500℃ at a cooling rate of 20℃ / min and held for 10 minutes. Next, the temperature is increased from 500℃ to 1150℃ at a heating rate of 15℃ / min and held for 15 minutes. Finally, the power is turned off, and the furnace is cooled to 200℃ before being removed and allowed to cool naturally at room temperature.

[0091] After the above four gradient cyclic heat treatments, the grains prepared on the surface of the TA18 titanium alloy plate in this embodiment are as follows: Figure 9 As shown, from Figure 9 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 3.44 mm.

[0092] Example 10

[0093] In this embodiment, crystal flowers were prepared on the surface of a TB6 titanium alloy (near-β titanium alloy) plate. The phase transformation temperature T of the TB6 titanium alloy was... β The temperature is 798℃. The TB6 titanium alloy plate is a round plate with a diameter of 150mm and a thickness of 2mm. The process steps are as follows:

[0094] (1) Degreasing and oxide film removal treatment of TB6 titanium alloy plate

[0095] The TB6 titanium alloy plate was immersed in a 15% sodium dodecylbenzene sulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TB6 titanium alloy plate was placed in a 12% hydrofluoric acid solution for pickling for 200 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0096] (2) Gradient cyclic heat treatment of TB6 titanium alloy plate

[0097] The TB6 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 6.9 × 10⁻⁶. -3Pa, the furnace temperature is increased from room temperature to 950℃ at a heating rate of 10℃ / min and held for 30 min, then the temperature is decreased to 550℃ at a cooling rate of 20℃ / min and held for 15 min; then the temperature is increased from 550℃ to 950℃ at a heating rate of 10℃ / min and held for 30 min, then the temperature is decreased to 550℃ at a cooling rate of 20℃ / min and held for 15 min; then the temperature is increased from 550℃ to 950℃ at a heating rate of 10℃ / min and held for 30 min, then the temperature is decreased to 300℃ at a cooling rate of 20℃ / min and removed to cool naturally at room temperature.

[0098] After the above three gradient cyclic heat treatments, the grains prepared on the surface of the TB6 titanium alloy plate in this embodiment are as follows: Figure 10 As shown, from Figure 10 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 1.72 mm.

[0099] Example 11

[0100] In this embodiment, crystal flowers were prepared on the surface of a TB6 titanium alloy (near-β titanium alloy) plate. The phase transformation temperature T of the TB6 titanium alloy was... β The temperature is 798℃. The TB6 titanium alloy plate is a round plate with a diameter of 150mm and a thickness of 2mm. The process steps are as follows:

[0101] (1) Degreasing and oxide film removal treatment of TB6 titanium alloy plate

[0102] The TB6 titanium alloy plate was immersed in a 15% sodium dodecylbenzene sulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TB6 titanium alloy plate was placed in a 12% hydrofluoric acid solution for pickling for 200 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0103] (2) Gradient cyclic heat treatment of TB6 titanium alloy plate

[0104] The TB6 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 7.8 × 10⁻⁶. -3Pa: The furnace temperature is increased from room temperature to 950℃ at a rate of 10℃ / min and held for 30 min, then decreased to 550℃ at a rate of 20℃ / min and held for 15 min; then the temperature is increased from 550℃ to 950℃ at a rate of 10℃ / min and held for 30 min, then decreased to 550℃ at a rate of 20℃ / min and held for 15 min; then the temperature is increased from 550℃ to 950℃ at a rate of 10℃ / min and held for 30 min, then decreased to 550℃ at a rate of 20℃ / min and held for 15 min; then the temperature is increased from 550℃ to 950℃ at a rate of 10℃ / min and held for 30 min, then decreased to 550℃ at a rate of 20℃ / min and held for 15 min; then the temperature is increased from 550℃ to 950℃ at a rate of 10℃ / min and held for 30 min, then decreased to 300℃ at a rate of 20℃ / min and removed to allow to cool naturally at room temperature.

[0105] After the above four gradient cycle heat treatments, the grains prepared on the surface of the TB6 titanium alloy plate in this embodiment are as follows: Figure 11 As shown, from Figure 11 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 2.63 mm.

[0106] Example 12

[0107] In this embodiment, crystal flowers were prepared on the surface of a TB6 titanium alloy (near-β titanium alloy) plate. The phase transformation temperature T of the TB6 titanium alloy was... β The temperature is 798℃. The TB6 titanium alloy plate is a round plate with a diameter of 150mm and a thickness of 2mm. The process steps are as follows:

[0108] (1) Degreasing and oxide film removal treatment of TB6 titanium alloy plate

[0109] The TB6 titanium alloy plate was immersed in a 10% sodium dodecylbenzene sulfonate solution. After wiping off the oil stains on the plate surface with a velvet cloth, it was rinsed with tap water and dried at 60°C. Then, the degreased TB6 titanium alloy plate was placed in a 10% hydrofluoric acid solution for pickling for 300 seconds to completely remove the oxide film on the plate surface, exposing a silvery-white metallic luster. After pickling, the plate surface was quickly rinsed with tap water to remove any residual acid and dried at 60°C.

[0110] (2) Gradient cyclic heat treatment of TB6 titanium alloy plate

[0111] The TB6 titanium alloy plate, after oxide film removal treatment, was placed in a heat treatment furnace, and the vacuum degree inside the furnace was controlled at 8.6 × 10⁻⁶. -3Pa, the furnace temperature is increased from room temperature to 1100℃ at a heating rate of 10℃ / min and held for 15 min, then the temperature is decreased to 500℃ at a cooling rate of 20℃ / min and held for 10 min; then the temperature is increased from 500℃ to 1100℃ at a heating rate of 10℃ / min and held for 15 min, then the temperature is decreased to 500℃ at a cooling rate of 20℃ / min and held for 15 min; then the temperature is increased from 500℃ to 1100℃ at a heating rate of 10℃ / min and held for 15 min, then the temperature is decreased to 500℃ at a cooling rate of 20℃ / min and held for 15 min; then the temperature is increased from 500℃ to 1100℃ at a heating rate of 10℃ / min and held for 15 min, then the temperature is decreased to 300℃ at a cooling rate of 20℃ / min and held for 15 min; then the temperature is increased from 500℃ to 1100℃ at a heating rate of 10℃ / min and held for 15 min, then the temperature is decreased to 300℃ and removed to be allowed to cool naturally at room temperature.

[0112] After the above four gradient cycle heat treatments, the grains prepared on the surface of the TB6 titanium alloy plate in this embodiment are as follows: Figure 12 As shown, from Figure 12 It can be seen that the macroscopic large and small grains are randomly distributed with clear morphology, and the average grain size is about 2.12 mm.

Claims

1. A method for preparing crystal flowers on the surface of a titanium alloy, characterized in that... The manufacturing process involves sequentially degreasing and removing the oxide film from the surface of the titanium alloy, followed by placing it in a heat treatment furnace at a vacuum degree ≤1.0×10⁻⁶. -2 Under the condition of Pa, at the phase transformation temperature T of titanium alloy β ~ T β Gradient cyclic heat treatment is performed at +300℃ and 500℃~800℃. After the gradient cyclic heat treatment is completed, the alloy is cooled to ≤300℃ and taken out of the furnace to obtain a titanium alloy with a crystalline surface. The gradient cyclic heat treatment first involves heating to T. β ~ T β Hold at +300℃ for 15-60 minutes, then cool to 500-800℃ and hold for 10-30 minutes, then raise the temperature to T. β ~ T β Hold at +300℃ for 15-60 minutes, then cool to 500-800℃ and hold for 10-30 minutes. Repeat this heating-holding and cooling-holding process continuously. During the final cycle, at T... β ~ T β After holding at +300℃, the temperature is directly reduced to ≤300℃ before being removed from the furnace; during gradient cyclic heat treatment, the heating rate is 10 ~ 60℃ / min and the cooling rate is 10 ~ 30℃ / min.

2. The method for preparing crystal flowers on the surface of a titanium alloy according to claim 1, characterized in that... The gradient cyclic heat treatment is performed at least twice.

3. The method for preparing crystal flowers on the surface of a titanium alloy according to claim 1 or 2, characterized in that... The degreasing treatment of titanium alloy surfaces involves immersing the titanium alloy in a 5%~50% sodium dodecylbenzenesulfonate solution, wiping off the oil stains on the titanium alloy surface, rinsing with tap water, and then drying.

4. The method for preparing crystal flowers on the surface of a titanium alloy according to claim 1 or 2, characterized in that... The process of removing oxide film from the surface of titanium alloy involves immersing the degreased titanium alloy in a hydrofluoric acid solution with a mass concentration of 8-12% for pickling. The pickling time is controlled to completely remove the oxide film from the surface of the titanium alloy. After pickling, the surface of the titanium alloy is quickly rinsed with tap water to remove any residual acid and then dried.

5. The method for preparing crystal flowers on the surface of a titanium alloy according to claim 3, characterized in that... The process of removing oxide film from the surface of titanium alloy involves immersing the degreased titanium alloy in a hydrofluoric acid solution with a mass concentration of 8-12% for pickling. The pickling time is controlled to completely remove the oxide film from the surface of the titanium alloy. After pickling, the surface of the titanium alloy is quickly rinsed with tap water to remove any residual acid and then dried.

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