A method for pickling high-roughness titanium stencils

Abstract

The present invention provides a method for pickling a titanium mesh with high roughness, comprising: S1: acid solution proportioning: preparing an oil stain treatment tank, a pickling tank, and a cleaning tank in sequence, and sequentially adding water, hydrofluoric acid solution, oxalic acid solution, and nitric acid solution into the oil stain treatment tank and the pickling tank for acid preparation; S2: degreasing the titanium mesh: decontaminating the mesh with the acid solution in the oil stain treatment tank; S3: pickling the titanium mesh: pickling and bleaching the mesh with the acid solution in the pickling tank; S4: cleaning the titanium mesh: removing the residual acid solution from the titanium mesh after pickling. The method for pickling a titanium mesh with high roughness of the present invention comprehensively considers the characteristics of oil stains on the titanium mesh surface and the low surface roughness of the cold-rolled titanium plate, innovatively designs pickling tanks with different functions, utilizes the reaction characteristics of hydrofluoric acid, oxalic acid, and nitric acid with titanium, and solves the problems of oil stains and low roughness on the titanium mesh surface at one time through a reasonable acid solution proportioning, shortens the process flow, has a short cycle, and is highly efficient.

Description

Technical Field

[0001] The invention relates to the technical field of nonferrous metal processing, in particular to a pickling method for a titanium mesh plate with high roughness. Background Art

[0002] The surface treatment processes for titanium and titanium alloys mainly include grinding and polishing, sandblasting and pickling, alkaline pickling, etc., which are common surface treatment methods for plates thicker than 3mm.

[0003] In recent years, with the continuous promotion and application of titanium and titanium alloys in the fields of hydrometallurgy, fuel cells, etc., the use of titanium mesh as a plate support material has also increased. Titanium mesh with titanium plate edge strips on all sides is a common structure in the plate. At the same time, in order to ensure the screening, filtration and separation effects, the titanium plate often needs to be further vulcanized and sealed. Moreover, the bonding strength between the rubber and the edge strips after vulcanization directly determines the sealing effect and service life. Under normal circumstances, the greater the roughness of the titanium plate, the higher the bonding strength. In particular, the thickness of the pure titanium mesh formed by the drawing method is generally between 1.0 and 2.0 mm. The raw material used is the cold-rolled vacuum annealed surface of the pure titanium strip coil, with a smooth surface and a roughness of Ra ≤ 0.3 μm, which is very unfavorable for the adhesion of rubber and titanium plate. In addition, oil stains are likely to remain on the surface of the titanium mesh after drawing.

[0004] Alkaline pickling and sandblasting / shot blasting are commonly used to remove surface oxidation on titanium and titanium alloys. Titanium is chemically active, easily forming a dense oxide film on its surface. At room temperature, it reacts only with a few acids, such as hydrofluoric acid. Nitric acid, a strong oxidizing acid, does not react with titanium at room temperature, but it can inhibit hydrogen absorption by titanium and bleach titanium plates. Therefore, the conventional pickling ratio for titanium and titanium alloys is generally hydrofluoric acid, nitric acid, and water. This solution is only intended to clean oil stains on titanium and titanium alloys and is not conducive to the adhesion of rubber to titanium plates.

[0005] Chinese patent publication number CN 110499514 A discloses a TC4 titanium alloy plate pickling process. The process, specifically targeting TC4 titanium alloy plates, involves first annealing the TC4 titanium alloy plates; then, shot blasting the plates. The plates are then cleaned and placed in an acid tank for pickling using a mixture of HNO3 and HF. Finally, the pickled plates are rinsed with water and dried in a dryer. Because TC4 titanium alloy plates easily form a dense oxide layer on their surfaces after hot rolling, this method involves first annealing and shot blasting the surfaces, followed by cleaning with a mixture of HNO3 and HF. However, the pickling processes for hot-rolled titanium alloy plates, pure titanium plates, and pure titanium mesh plates differ significantly, resulting in significantly different surface smoothness. Furthermore, this method addresses the issues of low pickling efficiency and uneven reaction, and is not conducive to improved adhesion between rubber and titanium plates.

[0006] Therefore, it is urgent to develop a reasonable surface treatment method to remove the oil stains on the titanium mesh and at the same time improve the bonding strength between the rubber and the titanium mesh frame. Summary of the Invention

[0007] In view of this, the present invention aims to propose a method for pickling a titanium mesh plate with high roughness, so as to solve the problem that the high roughness of the titanium mesh frame requires a relatively complex production process and a long cycle.

[0008] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0009] A method for pickling a high-roughness titanium stencil, comprising:

[0010] S1: Acid ratio: prepare an oil treatment tank, a pickling tank, and a cleaning tank in sequence, and add water, hydrofluoric acid solution, oxalic acid solution, and nitric acid solution into the oil treatment tank and the pickling tank in sequence for acid preparation. The acid mass ratio in the oil treatment tank is HF solution: water = 1:10-15, and the solution mass ratio of HF solution, H2C2O4 solution, HNO3 solution, and water in the pickling tank is 1-3:20-30:2-5:25-40, wherein the concentration of HF solution is 40%-50%, the concentration of H2C2O4 solution is 15-20%, and the concentration of HNO3 solution is 50%-60%. Inject cleaning water into the cleaning tank;

[0011] S2: Degreasing the titanium mesh: Place the titanium mesh in the partition rack, lift it up and place it in the oil treatment tank, and decontaminate it with the acid solution in the oil treatment tank. The cleaning time is T1;

[0012] S3: Pickling of titanium mesh: After cleaning the titanium mesh, lift the partition frame with the titanium mesh and place it in the pickling tank. Pickling and bleaching are carried out with the acid solution in the pickling tank. The pickling time is T2.

[0013] S4: Titanium stencil cleaning: lift the pickled titanium stencil and place it in the cleaning tank to remove the residual acid on the titanium stencil;

[0014] Among them, T1 and T2 are preset times.

[0015] Furthermore, the titanium mesh plate is a titanium mesh plate produced by a cold rolling process and has a thickness of 1.0 to 2.0 mm.

[0016] Furthermore, the surface roughness of the titanium mesh plate after pickling in step S3 is Ra≥1.0 μm.

[0017] Furthermore, in step S2, the cleaning time T1 ranges from 1 min to 5 min.

[0018] Furthermore, in step S3, the pickling time T2 is in the range of 10 min to 50 min.

[0019] Furthermore, in step S1, the cleaning water having a temperature of T is injected into the cleaning tank. 清洗水 Not less than 30℃.

[0020] Furthermore, T 清洗水 The value range is 30℃~40℃.

[0021] Furthermore, step S5 is added after step S4:

[0022] S5: Drying: After the titanium mesh is lifted out of the cleaning tank, it is placed in the drying room for rapid drying.

[0023] Compared with the prior art, the high-roughness titanium mesh pickling method of the present invention has the following advantages:

[0024] (1) The pickling method for high-roughness titanium mesh described in the present invention comprehensively considers the characteristics of oil stains on the surface of titanium mesh and low surface roughness of cold-rolled titanium plate, innovatively designs pickling tanks with different functions, utilizes the reaction characteristics of hydrofluoric acid, oxalic acid and nitric acid with titanium, and solves the problems of oil stains and low roughness on the surface of titanium mesh at one time through a reasonable acid ratio, shortens the process flow, shortens the cycle and increases efficiency.

[0025] (2) The high-roughness titanium mesh pickling method described in the present invention has invented a pickling method with a clean surface and high roughness Ra ≥ 1.0 μm through reasonable acid solution ratio and process flow design. The equipment and process are simple, the production efficiency is high, and batch production can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0027] Figure 1 Schematic diagram of the numerical value of roughness detection in Example 1 of the pickling method for a titanium mesh with high roughness according to the present invention;

[0028] Figure 2 This is a schematic diagram of the structure of the destructive test of the bonding strength between the titanium mesh and the rubber after pickling in Example 1;

[0029] Figure 3 Schematic diagram of the numerical value of roughness detection in Example 2 of the pickling method for a titanium mesh with high roughness according to the present invention;

[0030] Figure 4 This is a schematic diagram of the structure of the destructive test of the bonding strength between the titanium mesh and the rubber after pickling in Example 2;

[0031] Figure 5Schematic diagram of the roughness test in comparative example 1;

[0032] Figure 6 This is a schematic diagram of the structure of the titanium mesh and rubber bonding strength destruction test in comparative example 1. DETAILED DESCRIPTION

[0033] In order to make the technical means, objectives and effects of the present invention easier to understand, embodiments of the present invention are described in detail below with reference to specific figures.

[0034] It should be noted that all terms used in the present invention to indicate direction and position, such as "up", "down", "left", "right", "front", "back", "vertical", "horizontal", "inside", "outside", "top", "low", "lateral", "longitudinal", "center", etc., are only used to explain the relative positional relationship and connection status between the various components in a certain specific state (as shown in the accompanying drawings). They are only for the convenience of describing the present invention, and do not require that the present invention must be constructed and operated in a specific orientation. Therefore, they cannot be understood as limiting the present invention. In addition, the descriptions of "first", "second", etc. in the present invention are only for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features.

[0035] In the description of the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood broadly. For example, they may refer to fixed, detachable, or integral connections; mechanical connections; direct connections or indirect connections through an intermediary; and internal communication between two components. Those skilled in the art will understand the specific meanings of these terms in the present invention based on the specific circumstances.

[0036] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, illustrative uses of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0037] The present invention discloses a method for pickling a titanium mesh plate with high roughness, comprising:

[0038] S1: Acid ratio: prepare an oil treatment tank, a pickling tank, and a cleaning tank in sequence, and add water, hydrofluoric acid solution, oxalic acid solution, and nitric acid solution into the oil treatment tank and the pickling tank in sequence for acid preparation. The acid mass ratio in the oil treatment tank is HF solution: water = 1:10-15, and the solution mass ratio of HF solution, H2C2O4 solution, HNO3 solution, and water in the pickling tank is 1-3:20-30:2-5:25-40, wherein the concentration of HF solution is 40%-50%, the concentration of H2C2O4 solution is 15-20%, and the concentration of HNO3 solution is 50%-60%. Inject cleaning water into the cleaning tank;

[0039] S2: Degreasing the titanium mesh: Place the titanium mesh in the partition rack, lift it up and place it in the oil treatment tank, and decontaminate it with the acid solution in the oil treatment tank. The cleaning time is T1;

[0040] S3: Pickling of titanium mesh: After cleaning the titanium mesh, lift the partition frame with the titanium mesh and place it in the pickling tank. Pickling and bleaching are carried out with the acid solution in the pickling tank. The pickling time is T2.

[0041] S4: Titanium stencil cleaning: lift the pickled titanium stencil and place it in the cleaning tank to remove the residual acid on the titanium stencil;

[0042] Among them, T1 and T2 are preset times.

[0043] In the pickling method for a high-roughness titanium mesh plate described in the present invention, oxalic acid solution, as an organic reducing acid, can complex a variety of metal ions. By adjusting the acid concentrations of water, hydrofluoric acid solution, oxalic acid solution and nitric acid solution, an oxidizing acid solution is used to reduce the effect of oxalic acid solution on etching the titanium mesh plate, while improving the roughness of the titanium mesh plate after pickling. Through the above-mentioned pickling method, the titanium mesh plate can be quickly and reliably decontaminated and its roughness improved.

[0044] As a preferred example of the present invention, the titanium mesh plate is a titanium mesh plate produced by a cold rolling process and has a thickness of 1.0 to 2.0 mm.

[0045] The high-roughness titanium mesh pickling method described in the present invention comprehensively considers the characteristics of oil stains on the surface of the titanium mesh and low surface roughness of the cold-rolled titanium plate, innovatively designs pickling tanks with different functions, utilizes the reaction characteristics of hydrofluoric acid, oxalic acid and nitric acid with titanium, and solves the problems of oil stains and low roughness on the surface of the titanium mesh at one time through a reasonable acid solution ratio, shortens the process flow, has a short cycle and high efficiency.

[0046] As a preferred example of the present invention, the surface roughness of the titanium mesh plate after pickling in step S3 is Ra≥1.0 μm.

[0047] This setting ensures the reliability of the bonding between the titanium mesh frame and the rubber.

[0048] As a preferred example of the present invention, the cleaning time T1 ranges from 1 min to 5 min, and preferably, 1 min ≤ T1 ≤ 2 min.

[0049] As a preferred example of the present invention, the pickling time T2 ranges from 10 min to 50 min, and preferably, 15 min ≤ T2 ≤ 25 min.

[0050] By rationally designing pickling tanks with different functions, as well as reasonable acid ratios, cleaning time, and pickling time limits, titanium mesh pickling can be achieved quickly and efficiently.

[0051] As a preferred example of the present invention, in step S1, the washing water of temperature T is injected into the washing tank. 清洗水 Not less than 30℃, preferably, T 清洗水 The value range is 30℃~40℃.

[0052] This setting ensures the reliability of improving the pickling effect and roughness of the titanium mesh plate through the interaction of the hydrofluoric acid solution, the oxalic acid solution and the nitric acid solution.

[0053] As a preferred example of the present invention, step S5 is added after step S4:

[0054] S5: Drying: After the titanium stencil is removed from the cleaning tank, it is placed in a drying chamber for rapid drying. This setting not only prevents watermarks from remaining, but also allows the surface quality and roughness of the titanium stencil to be detected, ensuring the pickling effect of the titanium stencil.

[0055] The high-roughness titanium mesh pickling method described in the present invention, aimed at the high roughness requirements of the titanium mesh frame, utilizes the reaction characteristics of various acids with titanium, and through reasonable proportions, invents a short-cycle and efficient surface treatment method to remove oil stains on the titanium mesh, while improving the roughness of the titanium mesh frame, which has very important practical significance.

[0056] Example 1

[0057] Step 1: Acid Proportioning: Prepare the oil treatment tank, pickling tank, and cleaning tank in sequence. Add water, hydrofluoric acid solution, oxalic acid solution, and nitric acid solution to the oil treatment tank and pickling tank in sequence. The acid solution mass ratios are HF:water = 1:10, HF solution:H2C2O4 solution:HNO3 solution:water = 1:30:5:40, with the HF solution concentration being 40%, the H2C2O4 solution concentration being 15%, and the HNO3 solution concentration being 50%. Pour an appropriate amount of 40°C warm water into the cleaning tank.

[0058] Continuing from the previous step, the second step is to remove oil stains from the titanium mesh: Place the TA1 titanium mesh into the partition rack, lift it up and place it into the oil stain treatment tank. The cleaning time is controlled within 2 minutes.

[0059] Following the previous step, the third step is pickling of the titanium mesh: after cleaning the oil cleaning tank, lift it into the pickling tank for pickling and bleaching. The pickling time is controlled within 25 minutes.

[0060] Continuing from the previous step, the fourth step is cleaning the titanium mesh: After pickling, lift it into the cleaning tank to remove the residual acid on the titanium mesh.

[0061] Continuing from the previous step, the fifth step is drying: the titanium stencil is lifted out of the cleaning tank and placed in the drying room for rapid drying to avoid watermark residue, and the surface quality and roughness of the titanium stencil are tested at the same time.

[0062] The surface of TA1 titanium mesh is clean after pickling, with a roughness of Ra=1.075μm. Figure 1 At the same time, the peel strength test of the synchronous sample after bonding was carried out, and the peel strength was 9.5KN / m, and the failure mode was rubber failure, see Figure 2 shown.

[0063] Example 2

[0064] Step 1: Acid Mixing: Prepare the oil treatment tank, pickling tank, and cleaning tank in sequence. Add water, hydrofluoric acid solution, oxalic acid solution, and nitric acid solution to the oil treatment tank and pickling tank, respectively, to prepare the acid. The acid mix ratios are HF solution: water = 1:10, HF solution: H2C2O4 solution: HNO3 solution: water = 3:20:5:25, with a concentration of 50% HF solution, 20% H2C2O4 solution, and 60% HNO3 solution. Pour an appropriate amount of 30°C warm water into the cleaning tank.

[0065] Continuing from the previous step, the second step is to remove oil stains from the titanium mesh: Place the TA2 titanium mesh into the partition rack, lift it up and place it into the oil stain treatment tank. The cleaning time is controlled within 1 minute.

[0066] Following the previous step, the third step is pickling of the titanium mesh: after cleaning the oil cleaning tank, lift it into the pickling tank for pickling and bleaching. The pickling time is controlled within 15 minutes.

[0067] Continuing from the previous step, the fourth step is cleaning the titanium stencil: After pickling, lift it into the cleaning tank to remove the residual acid on the stencil.

[0068] Continuing from the previous step, the fifth step is drying: the titanium stencil is lifted out of the cleaning tank and placed in the drying room for rapid drying to avoid watermark residue, and the surface quality and roughness of the titanium stencil are tested at the same time.

[0069] The surface of TA2 titanium mesh is clean after pickling, with a roughness of Ra=1.075μm. Figure 3At the same time, the peel strength test of the synchronous sample after bonding was carried out, and the peel strength was 9.7KN / m, and the failure mode was rubber failure, see Figure 4 shown.

[0070] Comparative Example 1:

[0071] Step 1: Acid Mixing: Prepare the pickling tank and the cleaning tank. Add water, HF solution, and nitric acid solution to the pickling tank in order. The acid mix ratios are HF solution: water = 1:10, and HF solution: HNO3 solution: water = 1:5:10, with a 43% HF solution concentration and a 63% HNO3 solution concentration. Pour an appropriate amount of clean water into the cleaning tank.

[0072] Continuing from the previous step, the first step is pickling of the titanium mesh: after cleaning the oil cleaning tank, lift it into the pickling tank for pickling and bleaching. The pickling time is controlled within 10 minutes.

[0073] Continuing from the previous step, the fourth step is cleaning the titanium mesh: After pickling, lift it into the cleaning tank to remove the residual acid on the titanium mesh.

[0074] Continuing from the previous step, the fifth step is drying: the titanium stencil is lifted out of the cleaning tank and placed in the drying room for rapid drying to avoid watermark residue, and the surface quality and roughness of the titanium stencil are tested at the same time.

[0075] After pickling, there is oil residue on the surface of the TA1 titanium mesh, with a roughness of Ra = 0.768μm. Figure 5 At the same time, the peel strength test of the synchronous samples after bonding was carried out, and it was not fully bonded. Figure 6 shown.

[0076] The high-roughness titanium mesh pickling method of the present invention discloses a pickling method for 1.0-2.0 mm titanium mesh, which can not only remove oil stains but also improve the surface roughness to Ra≥1.0 μm or above.

[0077] The high-roughness titanium mesh pickling method of the present invention has the following innovations and advantages:

[0078] ① Taking into account the characteristics of oil stains on the surface of titanium mesh and low surface roughness of cold-rolled titanium plate, we innovatively designed pickling tanks with different functions. By utilizing the reaction characteristics of hydrofluoric acid, oxalic acid and nitric acid with titanium, and through a reasonable acid ratio, we solved the problems of oil stains and low roughness on the surface of titanium mesh at one time, shortened the process flow, and is a short-cycle and efficient titanium mesh pickling method;

[0079] ②Using conventional pickling process, the equipment and process are simple, the production efficiency is high, and batch production can be achieved.

[0080] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for pickling a high-roughness titanium mesh, characterized in that: include: S1: Acid ratio: prepare an oil treatment tank, a pickling tank, and a cleaning tank in sequence, and add water, hydrofluoric acid solution, oxalic acid solution, and nitric acid solution into the oil treatment tank and the pickling tank in sequence for acid preparation. The acid mass ratio in the oil treatment tank is HF solution: water = 1:10-15, and the solution mass ratio of HF solution, H2C2O4 solution, HNO3 solution, and water in the pickling tank is 1-3:20-30:2-5:25-40, wherein the concentration of HF solution is 40%-50%, the concentration of H2C2O4 solution is 15-20%, and the concentration of HNO3 solution is 50%-60%. Inject cleaning water into the cleaning tank; S2: Degreasing the titanium mesh: Place the titanium mesh in the partition rack, lift it up and place it in the oil treatment tank, and decontaminate it with the acid solution in the oil treatment tank. The cleaning time is T1; S3: Pickling of titanium mesh: After cleaning the titanium mesh, lift the partition frame with the titanium mesh and place it in the pickling tank. Pickling and bleaching are carried out with the acid solution in the pickling tank. The pickling time is T2. S4: Titanium stencil cleaning: lift the pickled titanium stencil and place it in the cleaning tank to remove the residual acid on the titanium stencil; Among them, T1 and T2 are preset times; the value range of T1 is 1min~5min, and the value range of T2 is 10min~50min.

2. The pickling method for a high-roughness titanium mesh according to claim 1, characterized in that: The titanium mesh plate is a titanium mesh plate produced by cold rolling process with a thickness of 1.0 to 2.0 mm.

3. The pickling method for a high-roughness titanium mesh according to claim 2, characterized in that: The surface roughness of the titanium mesh plate after pickling in step S3 is Ra≥1.0 μm.

4. The pickling method for a high-roughness titanium mesh according to claim 2, characterized in that: In step S1, the cleaning water of temperature T is injected into the cleaning tank. 清洗水 Not less than 30℃.

5. The pickling method for a high-roughness titanium mesh according to claim 4, characterized in that: T 清洗水 The value range is 30℃~40℃.

6. The pickling method for a high-roughness titanium mesh according to claim 1, characterized in that: Add step S5 after step S4: S5: Drying: After the titanium mesh is lifted out of the cleaning tank, it is placed in the drying room for rapid drying.

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