Method for regulating and controlling surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment

Abstract

The invention belongs to the technical field of metal material processing, and discloses a method for regulating and controlling corrosion resistance of a TiZrNb alloy surface based on surface mechanical wear treatment. The method comprises the following steps: preparing a TiZrNb alloy cast ingot through a vacuum arc melting method; the TiZrNb alloy cast ingot is subjected to homogenization treatment and then is cut, and a TiZrNb alloy plate is obtained; and the TiZrNb alloy plate is subjected to surface mechanical wear treatment, and the TiZrNb alloy with the layered nanometer gradient structure is obtained. According to the method, surface grain refinement can be achieved on the premise that the chemical composition and the crystal structure are not changed, the surface corrosion resistance of the TiZrNb alloy can be regulated and controlled by adjusting surface mechanical wear treatment parameters on the basis that the mechanical property of the TiZrNb alloy is improved, and the method has a great prospect in the aspect of biomedical alloy application.

Description

Technical Field

[0001] The present invention relates to the technical field of metal material processing, and particularly to a method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical attrition treatment. Background Art

[0002] TiZrNb alloy has good biocompatibility, so it is a preferred choice for biomedical materials, such as being used as the electrode material of a glucose sensor. The core task of a glucose sensor is to accurately and quickly monitor blood glucose levels and provide real-time data in clinical or personal health management. The electrode material of the sensor directly affects the oxidation reaction of glucose and the stability and sensitivity of the sensor.

[0003] Since the overly corrosion-resistant surface of TiZrNb alloy will inhibit the interaction between the electrode and the glucose solution, thereby reducing the oxidation reaction rate of glucose, which greatly limits its application. In addition, in some high-temperature environments, due to its high-temperature resistance characteristics, TiZrNb alloy has unique advantages in certain catalyst carriers. However, if the surface of TiZrNb alloy is too stable and corrosion-resistant, it may lead to insufficient active sites for the reaction, inhibiting the decomposition or transformation of reactants. In summary, appropriately reducing the corrosion resistance is beneficial for the better application of TiZrNb alloy in related fields.

[0004] In order to appropriately reduce the corrosion resistance of TiZrNb alloy, the existing technology mainly conducts physical or chemical treatments on the surface of TiZrNb alloy, such as acid etching treatment, structure-changing treatment, or chemical composition-changing treatment. However, although the above methods can reduce the surface corrosion resistance of TiZrNb alloy, they will also reduce its mechanical properties. For example, acid etching may cause certain corrosive damage on the surface, making the surface rougher, and this change in roughness may affect the fatigue strength and surface stress distribution of the alloy. And the composition-changing treatment method will also cause a reduction in mechanical properties, such as the generation of secondary phases, intermetallic compounds, etc. Moreover, the above composition-changing treatment method is not easy to regulate and has great limitations. For example, changing the composition will have multiple effects on workability, corrosion resistance, mechanical properties, and biocompatibility. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical attrition treatment.

[0006] A method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical attrition treatment of the present invention is achieved through the following technical solutions:

[0007] A method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical attrition treatment includes the following steps:

[0008] Step 1, Weigh each preparation raw material:

[0009] According to the atomic ratio of the TiZrNb alloy to be modified, weigh the corresponding masses of each preparation raw material: Ti source, Zr source, and Nb source, and set aside for later use.

[0010] Step 2, Vacuum arc melting treatment:

[0011] Place the weighed preparation raw materials in a vacuum arc melting furnace, and use the vacuum arc melting method to perform mixed vacuum arc melting treatment on each preparation raw material to obtain a TiZrNb alloy ingot.

[0012] Step 3, Homogenization treatment:

[0013] Perform homogenization treatment on the TiZrNb alloy ingot, and then cool it to room temperature to obtain a TiZrNb ingot with uniform composition.

[0014] Step 4, Cutting treatment:

[0015] Use a wire cutting machine to perform cutting treatment on the TiZrNb alloy ingot with uniform composition to obtain TiZrNb alloy plates.

[0016] Step 5, Grinding and polishing treatment:

[0017] After grinding and polishing the surface of the TiZrNb alloy plates until the surface becomes mirror-like, obtain TiZrNb alloy plates with a smooth surface.

[0018] Step 6, Surface mechanical attrition treatment:

[0019] Using zirconia balls with a diameter of 2 mm to 4 mm as the grinding medium, perform surface mechanical attrition treatment on the TiZrNb alloy plates with a smooth surface, and achieve surface self-nanocrystallization of the TiZrNb alloy plates by impacting the surface of the TiZrNb alloy plates with a smooth surface through the grinding medium, to obtain a TiZrNb alloy with a layered nano-gradient structure.

[0020] In Step 1, it should be noted that the present invention does not limit the specific composition of the TiZrNb alloy to be modified. According to actual requirements, weigh the corresponding masses of each preparation raw material according to the atomic percentage ratio of the corresponding TiZrNb alloy. For example, taking the TiZrNb alloy with an atomic ratio of 1:1:1 as an example, that is, the atomic percentage of this TiZrNb alloy is Ti 33.3%, Zr 33.3%, Nb 33.3%, that is, the mass fractions are 20.63%, 39.32%, 40.05% respectively. Weigh the corresponding masses of the Ti source, Zr source, and Nb source according to these mass fractions.

[0021] In some preferred embodiments of the present invention, in order to ensure the purity of the alloy material, the Ti source used is pure Ti particles with a purity of ≥99.95%.

[0022] In some preferred embodiments of the present invention, in order to ensure the purity of the alloy material, the Zr source is pure Zr particles with a purity of ≥99.95%.

[0023] In some preferred embodiments of the present invention, in order to ensure the purity of the alloy material, the Nb source is pure Nb particles with a purity of ≥99.95%.

[0024] In step 2, the present invention can be prepared by using the conventional vacuum arc melting treatment process for preparing TiZrNb alloy in the art. Those skilled in the art should be aware of this, so the present invention will not elaborate here.

[0025] In step 3, it should be noted that, in order to ensure the composition homogenization of the TiZrNb alloy ingot, in some preferred embodiments of the present invention, the temperature of the homogenization treatment is 1050°C to 1150°C, and the holding time is 90 min to 150 min, so as to ensure that the composition segregation and microstructure segregation in the TiZrNb alloy ingot can be eliminated through the homogenization treatment, and a TiZrNb alloy ingot with uniform β grains can be obtained.

[0026] In some preferred embodiments of the present invention, before the homogenization treatment, the temperature of the homogenization treatment equipment is first raised to 1050°C to 1150°C at a heating rate of 10°C / min, so as to avoid the furnace temperature deviating from the target homogenization treatment temperature due to too slow or too fast heating rate, and then the TiZrNb alloy ingot is placed in the homogenization treatment equipment for homogenization treatment.

[0027] In step 4, it should be noted that the present invention does not limit the specific cutting thickness of the cutting treatment. It can be cut into the required thickness according to actual needs. For example, in some preferred embodiments of the present invention, a wire cutting machine is used to cut TiZrNb alloy plates with a thickness of 1.5 mm to 3 mm from the composition-uniform TiZrNb alloy ingot.

[0028] In step 5, the present invention considers that impurities or surface defects may exist on the surface of the cut TiZrNb alloy plate, which will affect the effect of subsequent surface mechanical wear treatment. Therefore, before the surface mechanical wear treatment, the present invention first performs grinding and polishing treatment on the surface of the TiZrNb alloy plate to remove the impurities and surface defects that may exist on the surface of the TiZrNb alloy plate. And in some preferred embodiments of the present invention, the grinding and polishing treatment is carried out through the following steps:

[0029] The surface of the TiZrNb alloy sheet is polished successively with 800-mesh, 1200-mesh, 1500-mesh, 2000-mesh and 3000-mesh sandpapers, and then polished to a mirror surface with 0.05μm SiO 2 polishing liquid.

[0030] In step 6, the present invention preferably uses zirconia balls with a diameter of 2 mm to 4 mm as the grinding medium, and realizes the surface mechanical abrasion treatment of the surface of the smooth TiZrNb alloy sheet by impacting the surface of the smooth TiZrNb alloy sheet through the grinding medium. This surface mechanical abrasion treatment can refine the surface grains of the material only by physical means without optimizing the composition. Moreover, the surface mechanical abrasion treatment adopted by the present invention does not refine the overall grains of the material, but refines the local surface grains. And due to the different impacts of the impact force, the closer to the surface in the overall alloy material, the finer the grains, and the closer to the core of the material, the coarser the grains, that is, the grain size in the overall alloy material increases with the increase of the distance from the processed surface, so that a nano-gradient structure can be formed by self-nanocrystallization, and a TiZrNb alloy with a layered nano-gradient structure can be obtained, so that the mechanical properties of the material can be significantly improved through the formed nano-gradient structure. Moreover, the surface mechanical abrasion treatment method of the present invention is simpler, has lower cost, and does not require additional heat treatment, and can effectively simplify the steps of the treatment process. And the surface mechanical abrasion treatment of the present invention can effectively control the grain size in the range of nanometers to micrometers by adjusting the treatment process parameters, so that the surface corrosion resistance of the TiZrNb alloy can be adjusted by controlling the grain size, making the prepared TiZrNb alloy have great prospects in the application of biomedical alloys.

[0031] In some more preferred embodiments of the present invention, the diameter of each zirconia ball is 3 mm and the mass is 15 g.

[0032] In some preferred embodiments of the present invention, the treatment power of the surface mechanical abrasion treatment is 2.2 kw 50% - 80%. Among them, those skilled in the art should know that 50% - 80% refers to the frequency at a power of 2.2 kw.

[0033] In some preferred embodiments of the present invention, the treatment time of the surface mechanical abrasion treatment is 15 min - 45 min.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The present invention prepares a TiZrNb alloy ingot by a vacuum arc melting method; the TiZrNb alloy ingot is subjected to homogenization treatment to obtain a TiZrNb ingot with uniform composition; a TiZrNb alloy plate is cut from the TiZrNb alloy ingot using a wire cutting machine; the TiZrNb alloy plate is subjected to surface mechanical abrasion treatment to obtain a TiZrNb alloy with a layered nano-gradient structure. The method of the present invention can achieve surface grain refinement without changing the chemical composition and crystal structure, and on the basis of improving the mechanical properties of the TiZrNb alloy, can regulate the surface corrosion resistance of the TiZrNb alloy by adjusting the surface mechanical abrasion treatment parameters, and has great prospects in the application of biomedical alloys. Description of the Drawings

[0036] Figure 1 XRD spectra of the TiZrNb alloys obtained in Example 1, Example 2 and Comparative Examples 1-3.

[0037] Figure 2 Electrochemical impedance spectra of the TiZrNb alloys obtained in Example 1, Example 2 and Comparative Examples 1-3 in 0.9 wt% NaCl solution, Figure 2 The inset in is a partial enlarged view of the red box area.

[0038] Figure 3 Polarization curves of the TiZrNb alloys obtained in Example 1, Example 2 and Comparative Examples 1-3 in 0.9 wt% NaCl solution.

[0039] Figure 4 Grain size distribution of the TiZrNb alloy of Example 1 in the direction perpendicular to the processing surface.

[0040] Figure 5 Grain size distribution of the TiZrNb alloy of Example 2 in the direction perpendicular to the processing surface.

[0041] Figure 6 Scanning electron microscope image of the TiZrNb alloy of Example 2 after soaking in 0.9 wt% NaCl solution for 72 h. Detailed Description of the Invention

[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below.

[0043] Example 1

[0044] This example provides a method for regulating the surface corrosion resistance of a TiZrNb alloy based on surface mechanical abrasion treatment, including the following steps:

[0045] Step 1, weighing each preparation raw material:

[0046] In this embodiment, a TiZrNb alloy with an atomic ratio of Ti, Zr, and Nb of 1:1:1 and a single-phase BCC structure is used as the TiZrNb alloy to be modified. Its atomic percentages are 33.3% for Ti, 33.3% for Zr, and 33.3% for Nb, that is, their corresponding mass fractions are 20.63%, 39.32%, and 40.05% respectively. Weigh corresponding masses of pure Ti particles with a purity ≥99.95%, pure Zr particles with a purity ≥99.95%, and pure Nb particles with a purity ≥99.95% according to these mass fractions, totaling 100 g, and set them aside for later use.

[0047] Step 2, vacuum arc melting treatment:

[0048] Step 2.1, Place the weighed preparation raw materials in a crucible in the furnace cavity of the vacuum arc melting furnace in the order of increasing melting point. Among them, the Nb particles are placed on the top, the Zr particles are in the middle, and the Ti particles are at the bottom.

[0049] Step 2.2, Weigh another 100 g of Ti particles and put them into another crucible in the furnace cavity.

[0050] Step 2.3, After loading the materials, close the melting furnace. Use a mechanical pump and a molecular pump to evacuate the furnace cavity to a vacuum of 10 -4 Pa, and then fill it with argon with a purity of 99.999% as the protective gas.

[0051] Step 2.4, Using the vacuum arc melting method, first melt the 100 g of Ti particles to absorb residual oxygen, and then perform a mixed vacuum arc melting treatment on each preparation raw material. After the raw materials are melted, turn on the electromagnetic stirring system to make it more uniform. After melting, use a manipulator to flip the button ingot obtained by melting by 180°. Repeat the above operations 5 times. After cooling to room temperature, take out the ingot from the furnace chamber to obtain a button-shaped TiZrNb alloy ingot.

[0052] Step 3, homogenization treatment:

[0053] Step 3.1, Place the obtained button-shaped TiZrNb alloy ingot into a quartz tube, and then seal the quartz tube with a plastic plug. Subsequently, use a molecular pump to evacuate the air in the quartz tube to a vacuum of 10 -4 Pa, and then fill it with the high-purity argon as the protective gas. Then use a blowtorch to melt the contact part between the quartz tube and the plastic plug. After cooling, remove the quartz tube.

[0054] Step 3.2, First, increase the temperature of the homogenization treatment equipment at a heating rate of 10 °C / min to 1100 °C. Place the TiZrNb alloy ingot after the tube sealing treatment into the furnace and keep it at 1100 °C for 120 min.

[0055] Step 3.3: Quickly take out the TiZrNb alloy ingot after heat preservation and place it in water at room temperature for cooling to finally obtain a TiZrNb alloy ingot with uniform composition.

[0056] Step 4: Cutting treatment:

[0057] Use a wire cutting machine to cut a 2-mm-thick TiZrNb alloy plate from the TiZrNb alloy ingot with uniform composition, and then use 800-mesh sandpaper to polish off the oxide scale on the surface of the TiZrNb alloy plate to obtain a TiZrNb alloy plate.

[0058] Step 5: Grinding and polishing treatment:

[0059] Successively use 800-mesh, 1200-mesh, 1500-mesh, 2000-mesh, and 3000-mesh sandpaper to polish the surface of the TiZrNb alloy plate, and then use 0.05-μm SiO 2 polishing liquid to polish it to a mirror surface to obtain a TiZrNb alloy plate with a smooth surface.

[0060] Step 6: Surface mechanical attrition treatment:

[0061] Use zirconia balls with a diameter of 3 mm and a mass of 15 g as the grinding medium. Put the zirconia balls and the TiZrNb alloy plate with a smooth surface into a surface mechanical grinder, set the processing power of the surface mechanical attrition treatment to 2.2 kw 80%, and the processing time to 30 min, so as to realize the surface self-nanocrystallization of the TiZrNb alloy plate by impacting the surface of the TiZrNb alloy plate with a smooth surface through the grinding medium, and obtain a TiZrNb alloy with a layered nano-gradient structure and the surface grains refined to the nanoscale, denoted as SMAT1.

[0062] Example 2

[0063] This example provides a method for regulating the surface corrosion resistance of a TiZrNb alloy based on surface mechanical attrition treatment, including the following steps:

[0064] Step 1: Weigh each preparation raw material:

[0065] In this embodiment, a TiZrNb alloy with an atomic ratio of Ti, Zr, and Nb of 1:1:1 is used as the TiZrNb alloy to be modified. Their atomic percentages are 33.3% for Ti, 33.3% for Zr, and 33.3% for Nb, that is, their corresponding mass fractions are 20.63%, 39.32%, and 40.05% respectively. Weigh corresponding masses of pure Ti particles with a purity ≥99.95%, pure Zr particles with a purity ≥99.95%, and pure Nb particles with a purity ≥99.95% according to these mass fractions, totaling 100 g, and set aside for later use.

[0066] Step 2, vacuum arc melting treatment:

[0067] Step 2.1, Place the weighed preparation raw materials in a crucible in the furnace cavity of a vacuum arc melting furnace in the order of increasing melting point. The Nb particles are on the top, the Zr particles are in the middle, and the Ti particles are at the bottom.

[0068] Step 2.2, Weigh another 100 g of Ti particles and put them into another crucible in the furnace cavity.

[0069] Step 2.3, After placing the materials, close the melting furnace and pump the furnace cavity vacuum to 10 -4 Pa using a mechanical pump and a molecular pump, and then fill it with argon with a purity of 99.999% as the protective gas.

[0070] Step 2.4, Using the vacuum arc melting method, first melt the 100 g of Ti particles to absorb residual oxygen, and then perform a mixed vacuum arc melting treatment on each preparation raw material. After the raw materials melt, turn on the electromagnetic stirring system to make it more uniform. After melting, use a manipulator to flip the button ingot obtained by melting 180°. Repeat the above operations 5 times. After cooling to room temperature, take out the ingot from the furnace chamber to obtain a button-shaped TiZrNb alloy ingot.

[0071] Step 3, homogenization treatment:

[0072] Step 3.1, Place the obtained button-shaped TiZrNb alloy ingot into a quartz tube, and then seal the quartz tube with a plastic plug. Subsequently, use a molecular pump to extract the air inside the quartz tube, and pump the vacuum to 10 -4 Pa, and then fill it with the high-purity argon as the protective gas. Then use a blowtorch to melt the contact part between the quartz tube and the plastic plug, and remove the quartz tube after cooling.

[0073] Step 3.2, First, increase the temperature of the homogenization treatment equipment at a heating rate of 10°C / min to 1100°C. Place the TiZrNb alloy ingot after the tube sealing treatment into the furnace and hold it at 1100°C for 120 min.

[0074] Step 3.3: Quickly take out the TiZrNb alloy ingot after heat preservation, and place it in water at room temperature for cooling to finally obtain a TiZrNb alloy ingot with uniform composition.

[0075] Step 4: Cutting treatment:

[0076] Use a wire cutting machine to cut a 2-mm-thick TiZrNb alloy sheet from the TiZrNb alloy ingot with uniform composition, and then use 800-mesh sandpaper to polish off the oxide scale on the surface of the TiZrNb alloy sheet to obtain a TiZrNb alloy sheet.

[0077] Step 5: Grinding and polishing treatment:

[0078] Successively use 800-mesh, 1200-mesh, 1500-mesh, 2000-mesh, and 3000-mesh sandpaper to polish the surface of the TiZrNb alloy sheet, and then use 0.05-μm SiO 2 polishing liquid to polish it to a mirror surface to obtain a TiZrNb alloy sheet with a smooth surface.

[0079] Step 6: Surface mechanical wear treatment:

[0080] Use zirconia balls with a diameter of 3 mm and a mass of 15 g as the grinding medium. Put the zirconia balls and the TiZrNb alloy sheet with a smooth surface into a surface mechanical grinder, set the processing power of the surface mechanical wear treatment to 2.2 kw 50%, and the processing time to 30 min. Through the impact of the grinding medium on the surface of the TiZrNb alloy sheet with a smooth surface, the surface of the TiZrNb alloy sheet is self-nanocrystallized to obtain a TiZrNb alloy with a layered nano-gradient structure and the outermost surface grains refined to the nanoscale, denoted as SMAT2.

[0081] Example 3

[0082] This example provides a method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment, including the following steps:

[0083] Step 1: Weigh each preparation raw material:

[0084] In this example, a TiZrNb alloy with an atomic ratio of Ti, Zr, and Nb of 1:1:1 is used as the TiZrNb alloy to be modified. Its atomic percentages are Ti 33.3%, Zr 33.3%, and Nb 33.3% respectively, that is, their corresponding mass fractions are 20.63%, 39.32%, and 40.05% respectively. Weigh the corresponding masses of pure Ti particles with a purity ≥ 99.95%, pure Zr particles with a purity ≥ 99.95%, and pure Nb particles with a purity ≥ 99.95% according to this mass fraction, totaling 100 g, and set aside.

[0085] Step 2, vacuum arc melting treatment:

[0086] Step 2.1, Place the weighed preparation raw materials in a crucible in the furnace cavity of a vacuum arc melting furnace in the order of melting points from high to low. Among them, the Nb particles are at the top, the Zr particles are in the middle, and the Ti particles are at the bottom.

[0087] Step 2.2, Weigh another 100 g of Ti particles and put them into another crucible in the furnace cavity.

[0088] Step 2.3, After placing the materials, seal the melting furnace, and use a mechanical pump and a molecular pump to pump the vacuum degree of the furnace cavity to 10 -4 Pa, and then fill it with argon with a purity of 99.999% as the protective gas.

[0089] Step 2.4, Adopt the vacuum arc melting method. First, melt the 100 g of Ti particles to absorb the residual oxygen, and then conduct a mixed vacuum arc melting treatment on each preparation raw material. After the raw materials are melted, turn on the electromagnetic stirring system to make it more uniform. After melting, use a manipulator to turn the button ingot obtained by melting over 180°. Repeat the above operations 5 times. After cooling to room temperature, take out the ingot from the furnace chamber to obtain a button-shaped TiZrNb alloy ingot.

[0090] Step 3, homogenization treatment:

[0091] Step 3.1, Place the obtained button-shaped TiZrNb alloy ingot into a quartz tube, and then seal the quartz tube with a plastic plug. Subsequently, use a molecular pump to extract the air in the quartz tube, and pump the vacuum degree to 10 -4 Pa, and then fill it with the high-purity argon as the protective gas. Then use a blowtorch to melt the contact part between the quartz tube and the plastic plug, and remove the quartz tube after cooling.

[0092] Step 3.2, First, increase the temperature of the homogenization treatment equipment to 1050 °C at a heating rate of 10 °C / min. Place the TiZrNb alloy ingot after the tube sealing treatment into the furnace and keep it at 1050 °C for 150 min.

[0093] Step 3.3, Quickly take out the TiZrNb alloy ingot after heat preservation and place it in room-temperature water for cooling to finally obtain a TiZrNb alloy ingot with uniform composition.

[0094] Step 4, cutting treatment:

[0095] Use a wire cutting machine to cut a 1.5-mm-thick TiZrNb alloy plate from the TiZrNb alloy ingot with uniform composition, and then use 800-mesh sandpaper to polish off the oxide scale on the surface of the TiZrNb alloy plate to obtain a TiZrNb alloy plate.

[0096] Step 5, grinding and polishing treatment:

[0097] The surface of the TiZrNb alloy sheet is polished successively with sandpapers of 800 mesh, 1200 mesh, 1500 mesh, 2000 mesh and 3000 mesh, and then polished to a mirror surface with 0.05 μm SiO 2 polishing liquid to obtain a TiZrNb alloy sheet with a smooth surface.

[0098] Step 6, surface mechanical abrasion treatment:

[0099] Using zirconia balls with a diameter of 2 mm as the grinding medium, the zirconia balls and the smooth-surfaced TiZrNb alloy sheet are placed in a surface mechanical grinder. Set the processing power of the surface mechanical abrasion treatment to 2.2 kw 60%, and the processing time to 15 min, so as to realize the surface self-nanocrystallization of the smooth-surfaced TiZrNb alloy sheet through the impact of the grinding medium on the surface of the smooth-surfaced TiZrNb alloy sheet, and obtain a TiZrNb alloy with a layered nano-gradient structure and the surface grains refined to the nanoscale.

[0100] Example 4

[0101] This example provides a method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical abrasion treatment, including the following steps:

[0102] Step 1, weighing each preparation raw material:

[0103] In this example, a TiZrNb alloy with an atomic ratio of Ti, Zr, and Nb of 1:1:1 is used as the TiZrNb alloy to be modified. Its atomic percentages are Ti 33.3%, Zr 33.3% and Nb 33.3% respectively, that is, their corresponding mass fractions are 20.63%, 39.32% and 40.05% respectively. Weigh the corresponding masses of pure Ti particles with a purity ≥99.95%, pure Zr particles with a purity ≥99.95% and pure Nb particles with a purity ≥99.95% according to this mass fraction, a total of 100 g, and set aside.

[0104] Step 2, vacuum arc melting treatment:

[0105] Step 2.1, place the weighed preparation raw materials in a crucible in the furnace cavity of a vacuum arc melting furnace in the order of melting points from high to low, and the Nb particles are on the top, the Zr particles are in the middle, and the Ti particles are at the bottom.

[0106] Step 2.2, weigh another 100 g of Ti particles and put them into another crucible in the furnace cavity.

[0107] Step 2.3, After the feeding is completed, close the smelting furnace, and use a mechanical pump and a molecular pump to pump the vacuum degree of the furnace chamber to 10 -4 Pa, and then fill in argon with a purity of 99.999% as the protective gas.

[0108] Step 2.4, Adopt the vacuum arc melting method. First, melt the 100 g of Ti particles to absorb residual oxygen, and then perform a mixed vacuum arc melting treatment on each preparation raw material. After the raw materials are melted, turn on the electromagnetic stirring system to make it more uniform. After the melting is completed, use a manipulator to turn the button ingot obtained by melting over 180°. The above operations are repeated 5 times. After cooling to room temperature, take out the ingot from the furnace chamber to obtain a button-shaped TiZrNb alloy ingot.

[0109] Step 3, Homogenization treatment:

[0110] Step 3.1, Put the obtained button-shaped TiZrNb alloy ingot into a quartz tube, and then seal the quartz tube with a plastic plug. Subsequently, use a molecular pump to extract the air in the quartz tube, and pump the vacuum degree to 10 -4 Pa, and then fill in the high-purity argon as the protective gas. Then use a blowtorch to melt the contact part between the quartz tube and the plastic plug, and remove the quartz tube after cooling.

[0111] Step 3.2, First, raise the temperature of the homogenization treatment equipment to 1150 °C at a heating rate of 10 °C / min, put the TiZrNb alloy ingot after the tube sealing treatment into the furnace, and keep it at 1150 °C for 90 min.

[0112] Step 3.3, Quickly take out the TiZrNb alloy ingot after the heat preservation is completed, and place it in room-temperature water for cooling to finally obtain a TiZrNb alloy ingot with uniform composition.

[0113] Step 4, Cutting treatment:

[0114] Use a wire cutting machine to cut a 2.5-mm-thick TiZrNb alloy plate from the TiZrNb alloy ingot with uniform composition, and then use 800-mesh sandpaper to polish off the oxide scale on the surface of the TiZrNb alloy plate to obtain a TiZrNb alloy plate.

[0115] Step 5, Grinding and polishing treatment:

[0116] Successively use 800-mesh, 1200-mesh, 1500-mesh, 2000-mesh, and 3000-mesh sandpaper to polish the surface of the TiZrNb alloy plate, and then use 0.05-μm SiO 2 polishing liquid for polishing to a mirror surface to obtain a TiZrNb alloy plate with a smooth surface.

[0117] Step 6, Surface mechanical wear treatment:

[0118] Using zirconia balls with a diameter of 4 mm as the grinding medium, the zirconia balls and the smooth-surface TiZrNb alloy sheet are placed in a surface mechanical grinding machine. Set the processing power of the surface mechanical wear treatment to 2.2 kw 70%, and the processing time to 45 min. The surface self-nanocrystallization of the smooth-surface TiZrNb alloy sheet is achieved by impacting the surface of the smooth-surface TiZrNb alloy sheet through the grinding medium, and a TiZrNb alloy with a layered nano-gradient structure and the surface grains refined to the nanoscale is obtained.

[0119] Comparative Example 1

[0120] This comparative example provides a method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment. The difference between this comparative example and Example 1 lies in the different subsequent treatment processes for the homogeneous TiZrNb alloy ingot, and specifically includes the following steps:

[0121] Step 4': Wire cutting treatment:

[0122] A 5-mm-thick TiZrNb alloy sheet is cut from the homogeneous TiZrNb alloy ingot using a wire cutting machine, and then the oxide scale on the surface of the TiZrNb alloy sheet is polished off using 800-mesh sandpaper to obtain a TiZrNb alloy sheet.

[0123] Step 5': Cold rolling treatment:

[0124] The TiZrNb alloy sheet obtained in the above step 4' is cold-rolled on a two-high rolling mill. The cold rolling temperature is 25°C, and multi-pass rolling is adopted. The deformation amount of each pass is 2%, and the final deformation amount of the sheet is 80%. After cold rolling, a 1-mm-thick TiZrNb alloy sheet is obtained.

[0125] Step 6': Heat treatment:

[0126] The muffle furnace is heated to 800°C at a heating rate of 10°C / min. The sealed-tube-treated TiZrNb alloy sheet is placed in the muffle furnace, held for 5 min, and then quickly taken out and cooled in room-temperature water. Subsequently, the TiZrNb alloy sheet is taken out from the quartz tube, and the oxide scale on the surface is polished off using 800-mesh sandpaper. The obtained TiZrNb alloy is denoted as CRA1.

[0127] Comparative Example 2

[0128] This comparative example provides a method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment. The difference between this comparative example and Example 1 lies in the different subsequent treatment processes for the homogeneous TiZrNb alloy ingot, and specifically includes the following steps:

[0129] Step 4', wire cutting process:

[0130] Use a wire cutting machine to cut a 5-mm-thick TiZrNb alloy plate from the evenly-composed TiZrNb alloy ingot, and then use 800-mesh sandpaper to polish off the oxide skin on the surface of the TiZrNb alloy plate to obtain a TiZrNb alloy plate.

[0131] Step 5', cold rolling process:

[0132] Cold roll the TiZrNb alloy plate obtained in the above Step 4' on a two-high rolling mill at a temperature of 25°C. Use multi-pass rolling with a deformation of 2% for each pass, and the final deformation of the plate is 80%. After cold rolling, a 1-mm-thick TiZrNb alloy plate is obtained.

[0133] Step 6', heat treatment:

[0134] The muffle furnace is heated to 850°C at a heating rate of 10°C / min. Put the TiZrNb alloy plate treated by tube sealing into the muffle furnace, keep it warm for 5 min and then quickly take it out and put it into water at room temperature for cooling. Subsequently, take out the TiZrNb alloy plate from the quartz tube and use 800-mesh sandpaper to polish off the oxide skin on the surface. The obtained TiZrNb alloy is denoted as CRA2.

[0135] Comparative Example 3

[0136] This comparative example provides a method for regulating the surface corrosion resistance of a TiZrNb alloy based on surface mechanical attrition treatment. The difference between this comparative example and Example 1 lies in the subsequent treatment processes for the evenly-composed TiZrNb alloy ingot, and specifically includes the following steps:

[0137] Step 4', wire cutting process:

[0138] Use a wire cutting machine to cut a 5-mm-thick TiZrNb alloy plate from the evenly-composed TiZrNb alloy ingot, and then use 800-mesh sandpaper to polish off the oxide skin on the surface of the TiZrNb alloy plate to obtain a TiZrNb alloy plate.

[0139] Step 5', cold rolling process:

[0140] Cold roll the TiZrNb alloy plate obtained in the above Step 4' on a two-high rolling mill at a temperature of 25°C. Use multi-pass rolling with a deformation of 2% for each pass, and the final deformation of the plate is 80%. After cold rolling, a 1-mm-thick TiZrNb alloy plate is obtained.

[0141] Step 6', heat treatment:

[0142] The muffle furnace was heated to 950 °C at a heating rate of 10 °C / min. The sealed TiZrNb alloy sheet was placed in the muffle furnace, held for 5 min, and then quickly taken out and cooled in room-temperature water. Subsequently, the TiZrNb alloy sheet was taken out of the quartz tube, and the surface oxide scale was polished off with 800-mesh sandpaper. The obtained TiZrNb alloy was denoted as CRA3.

[0143] Experimental Section

[0144] (I) X-ray Diffraction Test

[0145] Taking the TiZrNb alloys obtained in Example 1, Example 2, and Comparative Examples 1 to 3 of the present invention as examples, X-ray diffraction tests were respectively carried out on them, and the test results are as Figure 1 shown.

[0146] Figure 1 are the XRD patterns of the TiZrNb alloys obtained in Example 1, Example 2, and Comparative Examples 1 to 3. It can be seen that the TiZrNb alloys obtained in Example 1, Example 2, and Comparative Examples 1 to 3 all exhibit a single-phase BCC structure, indicating that the surface mechanical wear treatment did not change the crystal structure of the TiZrNb alloy.

[0147] (II) Electrochemical Corrosion Performance Test

[0148] Taking the TiZrNb alloys obtained in Example 1, Example 2, and Comparative Examples 1 to 3 of the present invention as examples, using the traditional three-electrode method, in 0.9 wt% NaCl solution respectively, and testing their electrochemical impedance spectra and dynamic potential polarization curves, and the test results are as Figure 2 and Figure 3 shown.

[0149] Figure 2 is the electrochemical impedance spectrum of the TiZrNb alloys obtained in Example 1, Example 2, and Comparative Examples 1 to 3 in 0.9 wt% NaCl solution. Figure 2 The inset in Figure 2 is a partial enlarged view of the red box area, and from Figure 2 and the test results of the inset in 2 , it can be known that the charge transfer resistance of Comparative Example 1 is 13.866 Ω·cm 2 , the charge transfer resistance of Comparative Example 2 is 15.6 Ω·cm 2 , the charge transfer resistance of Comparative Example 3 is 41.05 Ω·cm 2 , while the charge transfer resistance of Example 1 is 0.479 Ω·cm 2, it can be seen that the charge transfer resistances of Example 1 and Example 2 of the present invention are significantly smaller than those of Comparative Example 1 to Comparative Example 3.

[0150] Figure 3 The polarization curves of the TiZrNb alloys obtained in Example 1, Example 2 and Comparative Example 1 to Comparative Example 3 in 0.9 wt% NaCl solution are shown, and from Figure 3 the test results, the corrosion current of Comparative Example 1 is 44.69 nA / cm 2 , the corrosion current of Comparative Example 2 is 23.335 nA / cm 2 , the corrosion current of Comparative Example 3 is 7.4972 nA / cm 2 , while the corrosion current of Example 1 is 410.14 nA / cm 2 , the corrosion current of Example 2 is 290.87 nA / cm 2 , it can be seen that the corrosion currents of Example 1 and Example 2 of the present invention are significantly greater than those of Comparative Example 1 to Comparative Example 3, and the maximum difference is two orders of magnitude.

[0151] Based on the test results of the above electrochemical impedance spectra and polarization curves, it can be shown that the corrosion resistance of the TiZrNb alloy can be appropriately reduced by the treatment solution of the present invention.

[0152] (III) Electron backscatter diffraction test

[0153] Taking the TiZrNb alloys of Example 1 and Example 2 of the present invention as examples, electron backscatter diffraction tests were respectively carried out on them to observe the grain size distribution of the TiZrNb alloys of Example 1 and Example 2 perpendicular to the processing surface direction by using an electron backscatter diffractometer, and the test results are respectively as Figure 4 and Figure 5 shown.

[0154] Among them, Figure 4 is the grain size distribution of the TiZrNb alloy of Example 1 perpendicular to the processing surface direction, Figure 5 is the grain size distribution of the TiZrNb alloy of Example 2 perpendicular to the processing surface direction. From Figure 4 and Figure 5 the test results, it can be seen that the TiZrNb alloys of Example 1 and Example 2 are both lamellar nanogradient structures. The farther away from the processing surface, the thicker the lamellar crystals, and the surface grains are refined to the nanoscale.

[0155] (IV) Scanning electron microscope test

[0156] Taking Example 2 as an example, the present invention was immersed in a 0.9 wt% NaCl solution for 72 h for a corrosion test, and the TiZrNb alloy after the corrosion test was subjected to a scanning electron microscope test, and the test results are as follows Figure 6 shown.

[0157] Figure 6 Figure Figure 6 is a scanning electron microscope image of the TiZrNb alloy of Example 2 after being immersed in a 0.9 wt% NaCl solution for 72 h. It can be seen that after the corrosion test of Example 2, the surface roughness of its material increases and local corrosion occurs, indicating that the electrochemical activity of the surface of Example 2 is improved.

[0158] Obviously, the above embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts fall within the scope of protection of the present invention.

Claims

1. A method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment, characterized in that: The following steps are involved: According to the atomic ratio of the TiZrNb alloy to be modified, weigh the corresponding mass of each preparation raw material: Ti source, Zr source and Nb source for use; The weighed raw materials are placed in a vacuum arc melting furnace, and the mixed raw materials are vacuum arc melted by a vacuum arc melting method to obtain a TiZrNb alloy ingot; The TiZrNb alloy ingot is homogenized and then cooled to room temperature to obtain a TiZrNb ingot with uniform composition; Cutting the TiZrNb alloy ingot with uniform composition to obtain a TiZrNb alloy plate; Grinding and polishing the surface of the TiZrNb alloy plate until the surface is mirror-like, thereby obtaining a TiZrNb alloy plate with a smooth surface; The surface of the TiZrNb alloy plate with a smooth surface is subjected to surface mechanical wear treatment by using zirconium oxide balls as grinding media, so that the surface of the TiZrNb alloy plate with a smooth surface is impacted by the grinding media, so that the surface of the TiZrNb alloy plate is self-nano-crystallized, and a TiZrNb alloy with a layered nano gradient structure is obtained.

2. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The processing power of the surface mechanical wear treatment is 2.2kw50%~80%.

3. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The treatment time of the surface mechanical wear treatment is 15 minutes to 45 minutes.

4. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The diameter of the grinding medium zirconium oxide ball is 2 mm to 4 mm.

5. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The temperature of the homogenization treatment is 1050° C. to 1150° C., and the insulation time is 90 min to 150 min.

6. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The thickness of the TiZrNb alloy plate is 1.5 mm to 3 mm.

7. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The Ti source is pure Ti particles with a purity of ≥99.95%.

8. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The Zr source is pure Zr particles with a purity of ≥99.95%.

9. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The Nb source is pure Nb particles with a purity of ≥99.95%.

10. The method for regulating the surface corrosion resistance of TiZrNb alloy based on surface mechanical wear treatment according to claim 1, characterized in that: The grinding and polishing process is carried out by the following steps: The surface of the TiZrNb alloy plate was polished using sandpapers of 800 mesh, 1200 mesh, 1500 mesh, 2000 mesh and 3000 mesh in sequence, and then polished to a mirror surface using 0.05 μm SiO2 polishing liquid.

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