A wear-resistant hydrogen permeation layer of a titanium alloy sheet and a method for preparing the same

Abstract

The application discloses a preparation method of a wear-resistant hydrogen permeation layer of a titanium alloy thin plate, and comprises the following steps: step 1, surface treatment of cathode and anode, polishing and then polishing the surface of the titanium alloy and another metal with a lower potential than the titanium alloy; step 2, placing a NaCl solution into a hydrogen production container, and the material of the hydrogen production container is used to avoid chemical reaction with hydrogen atoms; step 3, spontaneous hydrogen permeation for preparing the hydrogen permeation layer, taking the metal with a lower potential than the titanium alloy as an anode, taking the titanium alloy as a cathode, connecting the cathode and the anode by a wire, and placing the cathode and the anode into the NaCl solution, the current size is controlled to be 5-100 mA, the hydrogen permeation temperature is 25-100 DEG C, the hydrogen permeation time is 10 h-60 h, and the hydrogen permeation layer is prepared on the surface of the titanium alloy; and the hydrogen permeation layer can improve the hardness of the titanium alloy and improve the wear resistance of the titanium alloy.

Description

Technical Field

[0001] This invention belongs to the field of surface modification technology, specifically relating to a thin-plate titanium alloy wear-resistant hydrogen permeation layer and its preparation method. Background Technology

[0002] Titanium and titanium alloys are widely used in petrochemical, tableware, and packaging industries due to their high specific strength and good biocompatibility. However, titanium and titanium alloys have a high coefficient of friction, are prone to adhesion, and have poor wear resistance, which may lead to premature wear of titanium alloy devices, reduce their service life, and limit their application in the preparation of new titanium alloy devices.

[0003] Hydrogen infiltration alters the microstructure of titanium alloys, leading to an increase in lattice parameters and the generation of microscopic internal stresses. If the hydrogen content increase does not exceed a threshold, the room-temperature hardness and strength of the alloy surface are significantly improved. While hydrogen infiltration techniques, such as hot hydrogen infiltration, can improve the high-temperature formability of titanium alloys, few studies have focused on improving the surface hardness of room-temperature hydrogen-infiltrated alloys. This is because vacuum hot hydrogen infiltration, with its high temperature, often alters the initial microstructure of the alloy, thus hindering the improvement of mechanical properties. Spontaneous electrolytic hydrogen infiltration is carried out at low temperatures (<100℃), and the hydrogen content can be controlled by adjusting the infiltration time. Furthermore, the TiNi in the alloy... x The high surface energy of the precipitates hinders the accumulation of hydrogen adsorption, preventing a significant decrease in alloy toughness and thus greatly improving the wear resistance of the alloy surface. It is suitable for surface hydrogen-hardening treatment of small-sized titanium alloy structural parts, enabling low-cost mass production of surface-hardened titanium alloy products. Summary of the Invention

[0004] The purpose of this invention is to provide a wear-resistant hydrogen-permeable layer for thin-plate titanium alloys and its preparation method. The hydrogen-permeable layer can improve the surface hardness and wear resistance of TiNi alloys.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for preparing a wear-resistant hydrogen-permeable layer on a thin-plate titanium alloy specifically includes the following steps:

[0007] Step 1, cathode and anode surface treatment: grind the surfaces of the titanium alloy and another metal with a lower potential than the titanium alloy, and then polish them;

[0008] Step 2: Place a 4.6% NaCl solution into the hydrogen production container. The material used in the hydrogen production container should be designed to avoid chemical reaction with hydrogen atoms.

[0009] Step 3: Spontaneous hydrogen permeation to prepare a hydrogen-permeated layer. A metal with a lower potential than the titanium alloy is used as the anode, and the titanium alloy is used as the cathode. The cathode and anode are connected by a wire and placed in a NaCl solution. The current is controlled at 5-100 mA, the hydrogen permeation temperature is 25-100℃, and the hydrogen permeation time is 10h-60h. A hydrogen-permeated layer is prepared on the surface of the titanium alloy. By adjusting the hydrogen permeation temperature and time, the hydrogen content in the prepared hydrogen-permeated layer is 0.001%-0.018%.

[0010] Further, the specific steps of step 1 are as follows: the surfaces of the titanium alloy and another metal with a lower potential than the titanium alloy are polished sequentially with 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution.

[0011] Furthermore, in step 1, the titanium alloy is a titanium-nickel alloy, and the stable potential of the titanium-nickel alloy in NaCl solution is +0.09V.

[0012] Furthermore, in step 1, another metal with a lower potential than titanium alloy is zinc, which has a potential of -0.76V.

[0013] Furthermore, in step 2, the hydrogen production container is a polyurethane square container.

[0014] Furthermore, in step 3, the connection between the wire and the cathode and anode is made by soldering, and the connection joint is not immersed in the NaCl solution.

[0015] The hydrogen-permeable layer prepared according to the above-described method for preparing a wear-resistant hydrogen-permeable layer of thin-plate titanium alloy consists of a matrix phase with lattice distortion and a high-hardness TiNi alloy. X The precipitated phase composition is such that the hydrogen atoms in the hydrogen permeation layer come from hydrogen gas from the electrolysis of water.

[0016] Compared with the prior art, the beneficial effects of the present invention are:

[0017] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared by this invention can form a hydrogen-permeable strengthened alloy, effectively improving the surface strength and wear resistance of the alloy.

[0018] The thin-plate titanium alloy wear-resistant hydrogen permeation layer prepared by this invention effectively controls the uniform distribution of hydrogen in the alloy by the precipitated phase, with no hydride precipitation and no significant reduction in toughness.

[0019] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared by this invention uses potential difference as the driving force for hydrogen permeation, thereby reducing the hydrogen permeation rate and allowing for quantitative control of the amount of hydrogen permeation.

[0020] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared by this invention uses a low hydrogen content to prepare the hydrogenated layer, eliminating the need for subsequent vacuum annealing to control the hydrogen content, resulting in low cost and easy operation. Attached Figure Description

[0021] Figure 1 The XRD patterns of lattice distortion in a thin-plate titanium alloy wear-resistant hydrogen permeation layer prepared in Examples 1-5 of this invention are shown.

[0022] Figure 2 This is a distribution diagram of the titanium alloy precipitates in a thin-plate titanium alloy wear-resistant hydrogen permeation layer prepared in Example 3 of the present invention. Detailed Implementation

[0023] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0024] This invention provides a thin-plate titanium alloy wear-resistant hydrogen-permeable layer, which is composed of a matrix phase with lattice distortion and a high-hardness precipitated phase. The hydrogen atoms in the hydrogen-permeable layer come from hydrogen gas in electrolyzed water.

[0025] The hydrogen permeation process in water electrolysis involves using a high-potential titanium alloy as the cathode and another metal with a lower potential as the anode. The two metals are connected by a wire and placed in a conductive NaCl solution. The current is controlled between 5-100 mA, the hydrogen permeation temperature is 35-100℃, and the hydrogen permeation time is 10-60 h.

[0026] The reason for using the potential difference between two metals as the driving force for water electrolysis is as follows:

[0027] 1. The potential difference between titanium-nickel alloy and zinc is 0.67V. By adjusting the hydrogen absorption temperature and time, the amount and rate of hydrogen absorption of titanium-nickel alloy can be controlled, and the workpiece is not limited by its shape.

[0028] 2. Titanium-nickel alloys retain high strength and toughness even with a hydrogen absorption of only 0.018%, and the alloy contains a large amount of TiNi. X The precipitated phase helps to distribute hydrogen atoms evenly and avoids the formation of brittle hydrides.

[0029] 3. The hydrogen content of the hydrogen permeation layer of the alloy is controlled between 0.001% and 0.018%, and the hardness of the alloy is improved by lattice distortion of the matrix phase.

[0030] This invention also provides a method for preparing a wear-resistant hydrogen-permeable layer on a thin-plate titanium alloy, the specific steps of which are as follows:

[0031] A method for preparing a wear-resistant hydrogen-permeable layer on a thin-plate titanium alloy specifically includes the following steps:

[0032] Step 1, cathode and anode surface treatment: The surfaces of the titanium-nickel alloy and another metal with a lower potential than the titanium-nickel alloy are polished sequentially with 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution. The stable potential of the titanium-nickel alloy in NaCl solution is +0.09V, and the potential of zinc is -0.76V.

[0033] Step 2: Place the NaCl solution into the hydrogen production container. The NaCl solution concentration is 4.6%. The hydrogen production container is a polyurethane square container. The material used in the hydrogen production container should avoid chemical reaction with hydrogen atoms.

[0034] Step 3: Spontaneous hydrogen permeation to prepare a hydrogen-permeated layer. A metal with a lower potential than the titanium alloy is used as the anode, and the titanium alloy is used as the cathode. The cathode and anode are connected by a wire and placed in a NaCl solution. The connection between the wire and the cathode / anode is made by soldering, and the joint is not immersed in the NaCl solution. The current is controlled at 5-100 mA, the hydrogen permeation temperature is 25-100℃, and the hydrogen permeation time is 10h-60h. A hydrogen-permeated layer is prepared on the surface of the titanium alloy. By controlling the hydrogen permeation temperature and time, the hydrogen content in the prepared hydrogen-permeated layer is 0.001%-0.018%.

[0035] The hydrogen-permeated alloy prepared in step 3 was placed in silicone oil in a glass tube and stored at room temperature in preparation for subsequent wear resistance tests.

[0036] Example 1

[0037] Step 1, Cathode and Anode Surface Treatment: The surfaces of the titanium-nickel alloy and zinc are polished sequentially using 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution.

[0038] Step 2, preparation of hydrogen production container: Put NaCl solution into hydrogen production container. The concentration of NaCl solution is 4.6%. The hydrogen production container is a polyurethane square container. The materials used avoid chemical reaction with hydrogen ions, and electrons can flow freely in the container solution.

[0039] Step 3: Spontaneous hydrogen permeation to prepare the hydrogen-permeated layer: Zinc is used as the anode and titanium-nickel alloy is used as the cathode. The cathode and anode are connected by wires and placed in NaCl solution. The connection between the wires and the cathode and anode is made by soldering, and the connection joint is not immersed in NaCl solution. The current is controlled at 5mA, the hydrogen permeation temperature is 27℃, and the hydrogen permeation time is 10h. A hydrogen-permeated layer is prepared on the surface of titanium alloy.

[0040] The hydrogen-permeated alloy prepared in step 3 was placed in silicone oil in a glass tube and stored at room temperature in preparation for subsequent wear resistance tests.

[0041] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared in this embodiment has a surface hydrogen content of 0.0012% after hydrogen content testing. After hardness testing, the surface hydrogen-permeable layer has a nano-hardness of 6.32 GPa, a wear amount of 3.2 mg, and a friction coefficient of 0.85, exhibiting good wear resistance.

[0042] Example 2

[0043] Step 1, Cathode and Anode Surface Treatment: The surfaces of the titanium-nickel alloy and zinc are polished sequentially using 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution.

[0044] Step 2, preparation of hydrogen production container: Put NaCl solution into hydrogen production container. The concentration of NaCl solution is 4.6%. The hydrogen production container is a polyurethane square container. The materials used avoid chemical reaction with hydrogen ions, and electrons can flow freely in the container solution.

[0045] Step 3: Spontaneous hydrogen permeation to prepare the hydrogen permeation layer: Zinc is used as the anode and titanium-nickel alloy is used as the cathode. The cathode and anode are connected by wires and placed in NaCl solution. The connection between the wires and the cathode and anode is made by soldering, and the connection joint is not immersed in NaCl solution. The current is controlled at 10mA, the hydrogen permeation temperature is 25℃, and the hydrogen permeation time is 60h.

[0046] The hydrogen-permeated alloy prepared in step 3 was placed in silicone oil in a glass tube and stored at room temperature in preparation for subsequent wear resistance tests.

[0047] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared in this embodiment has a surface hydrogen content of 0.0051%. After testing with a hardness tester, the surface hydrogen-permeable layer has a nano-hardness of 7.21 GPa, a wear amount of 3.03 mg, and a friction coefficient of 0.81, exhibiting good wear resistance.

[0048] Example 3

[0049] Step 1, Cathode and Anode Surface Treatment: The surfaces of the titanium-nickel alloy and zinc are polished sequentially using 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution.

[0050] Step 2, preparation of hydrogen production container: Put NaCl solution into hydrogen production container. The concentration of NaCl solution is 4.6%. The hydrogen production container is a polyurethane square container. The materials used avoid chemical reaction with hydrogen ions, and electrons can flow freely in the container solution.

[0051] Step 3: Spontaneous hydrogen permeation to prepare the hydrogen permeation layer: Zinc is used as the anode and titanium-nickel alloy is used as the cathode. The cathode and anode are connected by wires and placed in NaCl solution. The connection between the wires and the cathode and anode is made by soldering, and the connection joint is not immersed in NaCl solution. The current is controlled at 20mA, the hydrogen permeation temperature is 27℃, and the hydrogen permeation time is 20h.

[0052] The hydrogen-permeated alloy prepared in step 3 was placed in silicone oil in a glass tube and stored at room temperature in preparation for subsequent wear resistance tests.

[0053] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared in this embodiment has a surface hydrogen content of 0.0102%. After testing with a hardness tester, the surface hydrogen-permeable layer has a nano-hardness of 7.08 GPa, a wear amount of 2.98 mg, and a friction coefficient of 0.76, exhibiting good wear resistance.

[0054] Figure 2 This is a distribution diagram of the precipitated phases of a thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared in Embodiment 3. Figure 2 It can be seen that the precipitated phases are uniformly distributed in the titanium-nickel alloy matrix, and the quantitative interface promotes the uniform distribution of hydrogen atoms.

[0055] Example 4

[0056] Step 1, Cathode and Anode Surface Treatment: The surfaces of the titanium-nickel alloy and zinc are polished sequentially using 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution.

[0057] Step 2, preparation of hydrogen production container: Put NaCl solution into hydrogen production container. The concentration of NaCl solution is 4.6%. The hydrogen production container is a polyurethane square container. The materials used avoid chemical reaction with hydrogen ions, and electrons can flow freely in the container solution.

[0058] Step 3: Spontaneous hydrogen permeation to prepare the hydrogen permeation layer: Zinc is used as the anode and titanium-nickel alloy is used as the cathode. The cathode and anode are connected by wires and placed in NaCl solution. The connection between the wires and the cathode and anode is made by soldering, and the connection joint is not immersed in NaCl solution. The current is controlled at 100mA, the hydrogen permeation temperature is 50℃, and the hydrogen permeation time is 20h.

[0059] The hydrogen-permeated alloy prepared in step 3 was placed in silicone oil in a glass tube and stored at room temperature in preparation for subsequent wear resistance tests.

[0060] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared in this embodiment has a surface hydrogen content of 0.0125%. After testing with a hardness tester, the surface hydrogen-permeable layer has a nano-hardness of 7.11 GPa, a wear amount of 3.01 mg, and a friction coefficient of 0.78, exhibiting good wear resistance.

[0061] Example 5

[0062] Step 1, Cathode and Anode Surface Treatment: The surfaces of the titanium-nickel alloy and zinc are polished sequentially using 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution.

[0063] Step 2, preparation of hydrogen production container: Put NaCl solution into hydrogen production container. The concentration of NaCl solution is 4.6%. The hydrogen production container is a polyurethane square container. The materials used avoid chemical reaction with hydrogen ions, and electrons can flow freely in the container solution.

[0064] Step 3: Spontaneous hydrogen permeation to prepare the hydrogen permeation layer: Zinc is used as the anode and titanium-nickel alloy is used as the cathode. The cathode and anode are connected by wires and placed in NaCl solution. The connection between the wires and the cathode and anode is made by soldering, and the connection joint is not immersed in NaCl solution. The current is controlled at 20mA, the hydrogen permeation temperature is 100℃, and the hydrogen permeation time is 20h.

[0065] Step 4: Place the hydrogen-permeated alloy prepared in Step 3 in silicone oil in a glass tube and store it at room temperature to prepare for subsequent wear resistance tests.

[0066] The thin-plate titanium alloy wear-resistant hydrogen-permeable layer prepared in this embodiment has a surface hydrogen content of 0.0176%. After testing with a hardness tester, the surface hydrogen-permeable layer has a nano-hardness of 6.5 GPa, a wear amount of 3.02 mg, and a friction coefficient of 0.82, exhibiting good wear resistance.

[0067] XRD patterns of lattice distortion in the wear-resistant hydrogen-permeable layer of a thin-plate titanium alloy prepared in Examples 1-5 of this invention are shown below. Figure 1 As shown, with increasing hydrogen content, the 2θ angle of the matrix phase peak shifts to the left, and the lattice parameter changes from... Increase to The lattice distortion volume increased by 0.7%.

[0068] The embodiments described above merely illustrate specific implementations of the present invention, and while the descriptions are detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing a wear-resistant hydrogen-permeable layer on a thin-plate titanium alloy, characterized in that, Specifically, the following steps are included: Step 1, cathode and anode surface treatment: grind the surfaces of the titanium alloy and another metal with a lower potential than the titanium alloy, and then polish them; Step 2: Place a 4.6% NaCl solution into the hydrogen production container. The material used in the hydrogen production container should be designed to avoid chemical reaction with hydrogen atoms. Step 3: Spontaneous hydrogen permeation to prepare a hydrogen-permeated layer. A metal with a lower potential than the titanium alloy is used as the anode, and the titanium alloy is used as the cathode. The cathode and anode are connected by a wire and placed in a NaCl solution. The current is controlled at 5-100 mA, the hydrogen permeation temperature is 25-100℃, and the hydrogen permeation time is 10h-60h. A hydrogen-permeated layer is prepared on the surface of the titanium alloy. By adjusting the hydrogen permeation temperature and time, the hydrogen content in the prepared hydrogen-permeated layer is 0.001%-0.018%.

2. The method for preparing a wear-resistant hydrogen-permeable layer of thin-plate titanium alloy according to claim 1, characterized in that, The specific steps of step 1 are as follows: the surfaces of the titanium alloy and another metal with a lower potential than the titanium alloy are polished sequentially with 500, 1000, 1200 and 2000 grit wet sandpaper, and then polished with a silica aqueous solution.

3. A method for preparing a thin-plate titanium alloy wear-resistant hydrogen-permeable layer according to any one of claims 1 or 2, characterized in that, In step 1, the titanium alloy is a titanium-nickel alloy, and the stable potential of the titanium-nickel alloy in NaCl solution is +0.09V.

4. A method for preparing a thin-plate titanium alloy wear-resistant hydrogen-permeable layer according to any one of claims 1 or 2, characterized in that, In step 1, another metal with a lower potential than titanium alloy is zinc, which has a potential of -0.76V.

5. The method for preparing a wear-resistant hydrogen-permeable layer on a thin-plate titanium alloy according to claim 1, characterized in that, In step 2, a polyurethane square container is used for hydrogen production.

6. The method for preparing a wear-resistant hydrogen-permeable layer of a thin-plate titanium alloy according to claim 1, characterized in that, In step 3, the wires are connected to the cathode and anode using solder, and the connection joints are not immersed in the NaCl solution.

7. The hydrogen-permeable layer prepared by the method for preparing a wear-resistant hydrogen-permeable layer of a thin-plate titanium alloy according to any one of claims 1-6, characterized in that, The matrix phase with lattice distortion and high-hardness TiNi X The precipitated phase composition is such that the hydrogen atoms in the hydrogen permeation layer come from hydrogen gas from the electrolysis of water.

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