A one-step method for shaping and deoxidizing titanium powder

Abstract

This invention discloses a one-step method for shaping and deoxidizing titanium powder. The method includes (1) mixing and ball milling a ball milling ball, hydrogenated dehydrogenated titanium powder, and a metal reducing agent under an inert atmosphere. In this method, the hydrogenated dehydrogenated titanium powder, the metal reducing agent, and the ball milling ball undergo intense impact and collision. This causes atomic diffusion within the powder particles, and the reducing agent reacts in situ with the oxide film on the surface of the hydrogenated dehydrogenated titanium powder. The hydrogenated dehydrogenated titanium powder is reduced to titanium by the metal reducing agent, thereby reducing the oxygen content of the titanium powder.

Description

Technical Field

[0001] This invention belongs to the field of titanium alloy material preparation technology, and specifically relates to a one-step method for shaping and deoxidizing titanium powder. Background Technology

[0002] Titanium alloys, due to their superior mechanical properties and corrosion resistance, have wide applications in aerospace, medical devices, and the 3C industry. Titanium powder, as a key raw material for titanium alloy preparation, directly affects the performance of the final product through its oxygen content and morphology. Currently, titanium powder deoxidation technologies mainly include calcium reduction, sodium reduction, and magnesium reduction methods. However, most of these technologies rely on high-temperature processes, and low-temperature deoxidation technologies have not yet been reported. Furthermore, existing technologies have not yet achieved simultaneous deoxidation and shaping of titanium powder, limiting the further development of titanium powder in high-performance applications. Summary of the Invention

[0003] Therefore, the purpose of this invention is to provide a one-step method for shaping and deoxidizing titanium powder. This method combines ball milling and mechanical alloying to achieve deoxidation and morphology optimization of the titanium powder. The method of this invention has advantages such as low-temperature deoxidation, low energy consumption, low cost, and high efficiency. The prepared titanium powder is suitable for the preparation of titanium alloy materials.

[0004] The technical solution of the present invention is as follows:

[0005] A one-step method for shaping and deoxidizing titanium powder, the method comprising:

[0006] (1) Under an inert atmosphere, the ball milling ball, hydrogenated dehydrogenated titanium powder and metal reducing agent are mixed and ball milled.

[0007] According to an embodiment of the present invention, step (1) further includes separating the grinding balls.

[0008] According to an embodiment of the present invention, in step (1), titanium powder with low oxygen content and a metal reducing agent are obtained. Preferably, the oxygen content of the titanium powder is less than 1000 ppm.

[0009] According to an embodiment of the present invention, the method further includes:

[0010] (2) Place the titanium powder with low oxygen content obtained in step (1) and the metal reducing agent in the air to oxidize the reducing agent and obtain a mixed powder.

[0011] According to an embodiment of the present invention, the method further includes:

[0012] (3) The mixed powder obtained in step (2) is acid washed. After the acid washing is completed, the solution is separated from the powder.

[0013] According to an embodiment of the present invention, the method further includes:

[0014] (4) The powder obtained in step (3) is washed and dried to obtain titanium powder with low oxygen content.

[0015] According to an embodiment of the present invention, in step (1), the hydrogenated dehydrogenated titanium powder is non-spherical or non-ellipsoidal, for example, with an irregular shape with sharp corners. Preferably, the particle size of the hydrogenated dehydrogenated titanium powder is 5-150 μm.

[0016] According to an embodiment of the present invention, in step (1), the metal reducing agent may be calcium and / or magnesium. Preferably, the morphology of the metal reducing agent may be granules or powder. Preferably, the metal reducing agent may be calcium granules and / or magnesium powder. Preferably, the particle size of the metal reducing agent is 0.1-3 mm.

[0017] According to an embodiment of the present invention, in step (1), the mass ratio of hydrogenated dehydrogenated titanium powder, metal reducing agent and ball milling ball is 1:(0.03-0.3):(1-10), preferably 1:(0.05-0.2):(1-6).

[0018] According to an embodiment of the present invention, in step (1), the temperature during ball milling is 15-50 degrees Celsius; the ball milling time is 2-8 hours; and the ball milling speed is 200-600 revolutions per minute.

[0019] According to an embodiment of the present invention, in step (1), the grinding balls of the ball mill can be separated by screening.

[0020] According to an embodiment of the present invention, in step (1), the grinding ball is made of agate or titanium alloy.

[0021] According to an embodiment of the present invention, in step (2), the time for which the titanium powder with low oxygen content and the metal reducing agent obtained in step (1) are placed in the air is not particularly limited, as long as the metal reducing agent is completely oxidized. For example, the time for placement in the air is 1-3 days.

[0022] Preferably, the metal reducing agent is oxidized in air to a metal oxide, for example, to calcium oxide and / or magnesium oxide.

[0023] According to an embodiment of the present invention, in step (3), the mixed powder obtained in step (2) is mixed with an acid for acid washing. The acid is, for example, hydrochloric acid. The concentration and content of the acid are not particularly limited, as long as the pH value of the system after mixing the mixed powder and the acid is not higher than 5.

[0024] According to an embodiment of the present invention, in step (3), after the acid washing is completed, the obtained mixture can be separated from the powder by sedimentation or centrifugation.

[0025] According to an embodiment of the present invention, in step (4), water washing is used. Specifically, water washing is used until the pH value of the mixture is 7.

[0026] According to an embodiment of the present invention, in step (4), the drying time and temperature are not particularly limited, and the moisture in the titanium powder can be dried.

[0027] According to an embodiment of the present invention, in step (4), the titanium powder is nearly spherical or ellipsoidal.

[0028] According to an embodiment of the present invention, in step (4), the oxygen content in the titanium powder is less than 1000 ppm.

[0029] As an exemplary embodiment of the present invention, the method specifically includes the following steps:

[0030] 1) Mix the ball milling balls, hydrogenated dehydrogenated titanium powder and metal reducing agent, ball mill, separate the ball milling balls, and obtain titanium powder with low oxygen content and residual metal reducing agent;

[0031] 2) Place the titanium powder with low oxygen content obtained in step 1) and the residual metal reducing agent in a tray and expose it to air for 1-2 days until the metal reducing agent is oxidized in the air to generate metal oxides (e.g., calcium oxide and / or magnesium oxide) to obtain a mixed powder.

[0032] 3) Pour the mixed powder obtained in step 2) into a dilute hydrochloric acid solution for acid washing. While stirring the solution, pour the mixed powder in batches. After acid washing, separate the solution from the powder by sedimentation or centrifugation. Wash the obtained powder with water until the pH of the mixed solution is neutral.

[0033] 4) The titanium powder washed in step 3) is placed into a vacuum dryer for drying for 12-72 hours to obtain titanium powder with low oxygen content.

[0034] The beneficial effects of this invention are:

[0035] (1) The method of the present invention involves grinding hydrogenated dehydrogenated titanium powder with a metal reducing agent and a ball milling ball (the three are subjected to intense impact and collision). Atoms diffuse in the powder particles, and the metal reducing agent undergoes an in-situ reduction reaction with the oxide film on the surface of the hydrogenated dehydrogenated titanium powder. The hydrogenated dehydrogenated titanium powder is reduced to titanium by the metal reducing agent, thereby reducing the oxygen content of the titanium powder.

[0036] (2) In the ball milling process, the hydrogenated dehydrogenated titanium powder of the present invention undergoes centrifugal force and impact energy, which causes the hydrogenated dehydrogenated titanium powder to be subjected to collision, compression and shear forces, thereby achieving spheroidization of the powder and ultimately controlling its particle size and morphology.

[0037] (3) The method of the present invention achieves deoxidation and morphology optimization of titanium powder at a lower temperature, with low energy consumption and low cost; the powder shaping and deoxidation processes are carried out in one step, which is highly efficient and reduces the time and cost consumption caused by multiple steps.

[0038] (4) The titanium powder treated by the method of the present invention has a significantly reduced oxygen content (e.g., not higher than 1000 ppm) and an optimized morphology of near-spherical or ellipsoidal shape, which improves the flowability and molding performance of the titanium powder and is suitable for the needs of the metal injection molding (MIM) and 3D printing industries.

[0039] In summary, this invention achieves deoxidation and morphology optimization of titanium powder by combining ball milling shaping and mechanical alloying. It has the advantages of low-temperature deoxidation, low energy consumption, low cost, and high efficiency, and is suitable for the preparation of titanium alloy materials. Attached Figure Description

[0040] Figure 1 This is a SEM image of the hydrogenated and dehydrogenated titanium powder used as raw material in Example 1.

[0041] Figure 2 This is an SEM image of the titanium powder after ball milling in Example 1. Detailed Implementation

[0042] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0043] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0044] Example 1

[0045] 1. Mix hydrogenated dehydrogenated titanium powder (with an irregular morphology and sharp corners), calcium particles with a particle size of 1-3 mm, and grinding balls (such as agate balls or titanium alloy balls) in a weight ratio of 1:0.1:5 and load them into the grinding hopper.

[0046] 2. Argon gas is introduced into the ball mill container, the ball mill speed is set to 300 rpm, the ball milling time is 4 hours, and the ball milling is carried out at room temperature.

[0047] 3. After ball milling, the material is poured out into a glove box protected by argon gas, and the milling balls are separated by sieving to obtain titanium powder with low oxygen content and residual calcium particles.

[0048] 4. Place the titanium powder with low oxygen content and the residual calcium particles in a tray and expose it to air for 1 day until the calcium particles oxidize to form calcium oxide, thus obtaining a mixed powder.

[0049] 5. Slowly pour the mixed powder into a container containing dilute hydrochloric acid solution, stirring the solution while pouring the mixed powder in batches until the calcium oxide completely reacts with the hydrochloric acid to form calcium chloride, keeping the pH of the solution between 3 and 4.

[0050] 6. After pickling, the solution and powder are separated by centrifugation. Deionized water is added back to the pickling container to wash the powder. The washing is repeated 5 times until the pH of the water is 7.

[0051] 7. The thoroughly washed titanium powder is placed in a tray and put into a vacuum dryer for drying for 24 hours.

[0052] 8. After drying, the oxygen content of the titanium powder is less than 1000 ppm, and the morphology of the titanium powder changes from an irregular shape with sharp corners to a near-spherical shape.

[0053] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A one-step method for shaping and deoxidizing titanium powder, characterized in that, The method includes: (1) Under an inert atmosphere, the ball milling balls, hydrogenated dehydrogenated titanium powder and metal reducing agent are mixed and ball milled; the ball milling temperature is controlled at 15-50 degrees Celsius; (2) Place the ball-milled titanium powder and the residual metal reducing agent in the air to oxidize the reducing agent and obtain a mixed powder; (3) The mixed powder obtained in step (2) is acid washed. After acid washing, the solution is separated from the powder. (4) The powder obtained in step (3) is washed and dried to obtain titanium powder with an oxygen content of less than 1000 ppm; In step (1), the metal reducing agent is calcium and / or magnesium.

2. The method according to claim 1, characterized in that, In step (1), the mass ratio of hydrogenated dehydrogenated titanium powder, metal reducing agent and ball milling ball is 1:(0.03-0.3):(1-10).

3. The method according to claim 1, characterized in that, In step (1), the ball milling time is 2-8 hours and the ball milling speed is 200-600 revolutions per minute.

4. The method according to claim 1, characterized in that, In step (4), the titanium powder with low oxygen content is nearly spherical or ellipsoidal.

Images