Titanium alloy etching coarsening method and titanium alloy complex

Abstract

The invention relates to a titanium alloy etching and coarsening method and a titanium alloy complex, in particular to the field of titanium alloy surface treatment.The etching and coarsening method comprises the steps that the titanium alloy is sequentially subjected to sulfuric acid treatment and alkali treatment; wherein the concentration of sulfuric acid used in the sulfuric acid treatment is 1000-1100 g / L, the temperature is 70-90 DEG C, and the treatment time is 12-18 min. According to the etching coarsening method provided by the invention, the surface of the titanium alloy is coarsened by adopting a specific sulfuric acid treatment process and cooperating with alkali treatment, so that connection of the titanium alloy and the non-metallic material is facilitated, the connection effect of the titanium alloy and the non-metallic material is improved, and the risk that the non-metallic material falls off in the use process is avoided.

Description

Technical Field

[0001] The invention relates to the field of titanium alloy surface treatment, and in particular to an etching roughening method for titanium alloy and a titanium alloy composite. Background Art

[0002] Electronic products receive signals from base stations or other wireless devices through antennas and convert them into electrical signals that can be processed by electronic products to achieve information reception. At the same time, electronic products also convert the electrical signals generated internally into electromagnetic waves and send them out through antennas to achieve information transmission.

[0003] Plastic is the channel for sending and receiving signals. Without plastic, the metal shell, due to its high conductivity, may shield the wireless signals of electronic products and affect the quality of signal transmission and reception. This is especially obvious when using products that require good wireless communication functions, such as mobile phones and tablets.

[0004] A full metal casing may also shield some network signals, causing the device to perform poorly when receiving Wi-Fi or cellular network signals, requiring an external antenna to enhance signal reception.

[0005] However, the bonding strength between the titanium alloy and the plastic obtained by etching the existing titanium alloy is not strong enough, which has a certain impact on the overall performance and durability of the product. Summary of the invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide a titanium alloy etching roughening method and a titanium alloy composite to solve the defect that the bonding force between the titanium alloy and the plastic obtained by the existing titanium alloy etching process is not strong enough to ensure the overall performance and durability of the product.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an etching roughening method for a titanium alloy, the etching roughening method comprising:

[0009] The titanium alloy is sequentially subjected to sulfuric acid treatment and alkali treatment;

[0010] The concentration of sulfuric acid used in the sulfuric acid treatment is 1000-1100 g / L, the temperature is 70-90° C., and the treatment time is 12-18 min.

[0011] The etching roughening method provided by the present invention achieves the roughening of the titanium alloy surface by adopting a specific sulfuric acid treatment process in combination with alkali treatment, which is beneficial to the connection between the titanium alloy and the non-metallic material, improves the connection effect between the titanium alloy and the non-metallic material, and avoids the risk of non-metallic material falling off during use.

[0012] As a preferred technical solution of the present invention, the titanium alloy is sequentially subjected to a degreasing treatment and a neutralization treatment before being subjected to a sulfuric acid treatment.

[0013] As a preferred technical solution of the present invention, the degreasing agent used in the degreasing treatment includes R105 degreasing agent.

[0014] Preferably, the concentration of the degreasing agent used in the degreasing treatment is 50-70 g / L.

[0015] Preferably, the temperature of the degreasing treatment is 60-70°C.

[0016] Preferably, the degreasing treatment time is ≥ 3 min.

[0017] As a preferred technical solution of the present invention, the neutralizing agent used in the neutralization treatment includes one or a combination of at least two of nitric acid, sulfuric acid or hydrochloric acid.

[0018] Preferably, the concentration of the neutralizer used in the neutralization treatment is 250-350 g / L.

[0019] Preferably, the neutralization treatment time is ≥ 3 min.

[0020] As a preferred technical solution of the present invention, ultrasonic water washing is arranged between the sulfuric acid treatment and the alkali treatment.

[0021] Preferably, the ultrasonic power of the ultrasonic water washing is 1200-1500W.

[0022] Preferably, the ultrasonic washing time is ≥3 min.

[0023] As a preferred technical solution of the present invention, the alkali solution used for the alkali treatment includes sodium hydroxide solution and / or potassium hydroxide solution.

[0024] Preferably, the concentration of the alkali solution used in the alkali treatment is 50-70 g / L.

[0025] Preferably, the alkali treatment time is ≥15 min.

[0026] Preferably, the temperature of the alkali treatment is 80-95°C.

[0027] As a preferred technical solution of the present invention, water washing is performed after the alkali treatment.

[0028] Preferably, the water washing temperature is 80-90°C.

[0029] Preferably, the water washing time is ≥ 1 min.

[0030] In a second aspect, the present invention provides a titanium alloy composite, which is prepared by using the titanium alloy and non-metallic material obtained by the etching and roughening method described in the first aspect.

[0031] As a preferred technical solution of the present invention, the non-metallic material used for the titanium alloy composite includes plastic or resin.

[0032] As a preferred technical solution of the present invention, the pull-out force between the titanium alloy and the non-metallic material in the titanium alloy composite is ≥1389.8N.

[0033] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0034] The etching roughening method provided by the present invention forms a gully-like or microporous structure on the surface of the titanium alloy after processing, thereby increasing its surface roughness and improving the bonding strength between the titanium alloy and the plastic. The obtained titanium alloy surface roughness root mean square height Sq≤0.904, the minimum autocorrelation length Sal≤25.326, the pore diameter of the corrosion hole ≥53nm, and after being connected with the plastic by injection molding, the pulling force is ≥1379.8N. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is a SEM photograph of the etched and roughened titanium alloy obtained in Example 1 of the present invention;

[0036] Figure 2 is a SEM photograph of the etched and roughened titanium alloy obtained in Comparative Example 1 of the present invention;

[0037] Figure 3 This is a SEM photograph of the etched and roughened titanium alloy obtained in Comparative Example 2 of the present invention.

[0038] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0039] To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting embodiments of the present invention are as follows:

[0040] This embodiment provides an etching roughening method for titanium alloy, the etching roughening method comprising:

[0041] The titanium alloy is sequentially subjected to sulfuric acid treatment and alkali treatment;

[0042] The concentration of sulfuric acid used in the sulfuric acid treatment is 1000-1100 g / L, the temperature is 70-90° C., and the treatment time is 12-18 min.

[0043] In the present invention, the titanium alloy can be exemplarily selected from commonly used titanium alloys in the art such as TC4 or TA4.

[0044] In the present invention, the concentration of sulfuric acid used in the sulfuric acid treatment is 1000-1100 g / L, for example, it can be 1000 g / L, 1010 g / L, 1020 g / L, 1030 g / L, 1040 g / L, 1050 g / L, 1060 g / L, 1070 g / L, 1080 g / L, 1090 g / L or 1100 g / L, but is not limited to the listed values, and other unlisted values ​​within this range also meet the requirements.

[0045] In the present invention, the temperature of the sulfuric acid treatment is 70-90°C, for example, it can be 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C or 90°C, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0046] In the present invention, the time for sulfuric acid treatment is 12-18 min, for example, it can be 12 min, 12.5 min, 13 min, 13.5 min, 14 min, 14.5 min, 15 min, 15.5 min, 16 min, 16.5 min, 17 min, 17.5 min or 18 min, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0047] Wherein, the titanium alloy is subjected to degreasing treatment and neutralization treatment in sequence before being subjected to sulfuric acid treatment.

[0048] Wherein, the degreasing agent used in the degreasing treatment includes R105 degreasing agent.

[0049] Wherein, the concentration of the degreasing agent used in the degreasing treatment is 50-70g / L, for example, it can be 50g / L, 52g / L, 54g / L, 56g / L, 58g / L, 60g / L, 62g / L, 64g / L, 66g / L, 68g / L or 70g / L, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0050] The degreasing treatment temperature is 60-70°C, for example, 60°C, 62°C, 64°C, 66°C, 68°C or 70°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0051] The degreasing treatment time is ≥ 3 min, for example, it can be 3 min, 3.5 min, 4 min, 4.5 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0052] Wherein, the neutralizing agent used in the neutralization treatment includes one or a combination of at least two of nitric acid, sulfuric acid or hydrochloric acid.

[0053] Illustratively, the combination of neutralizing agents includes a combination of nitric acid and hydrochloric acid, a combination of nitric acid and hydrochloric acid, a combination of sulfuric acid and hydrochloric acid, and the like.

[0054] Wherein, the concentration of the neutralizer used in the neutralization treatment is 250-350g / L, for example, it can be 250g / L, 260g / L, 270g / L, 280g / L, 290g / L, 300g / L, 310g / L, 320g / L, 330g / L, 340g / L or 350g / L, but is not limited to the listed values, and other unlisted values ​​within this range also meet the requirements.

[0055] The neutralization treatment time is ≥ 3 min, for example, it can be 3 min, 3.5 min, 4 min, 4.5 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0056] Wherein, ultrasonic water washing is arranged between the sulfuric acid treatment and the alkali treatment.

[0057] The ultrasonic power of the ultrasonic water washing is 1200-1500W, for example, it can be 1200W, 1250W, 1300W, 1350W, 1400W, 1450W or 1500W, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0058] Among them, the time of ultrasonic washing is ≥3 min, for example, it can be 3 min, 3.5 min, 4 min, 4.5 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0059] Wherein, the alkali solution used for the alkali treatment includes sodium hydroxide solution and / or potassium hydroxide solution.

[0060] Wherein, the concentration of the alkali solution used in the alkali treatment is 50-70g / L, for example, it can be 50g / L, 52g / L, 54g / L, 56g / L, 58g / L, 60g / L, 62g / L, 64g / L, 66g / L, 68g / L or 70g / L, but is not limited to the listed values, and other unlisted values ​​within this range also meet the requirements.

[0061] The alkali treatment time is ≥15 min, for example, it can be 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0062] The temperature of the alkali treatment is 80-95°C, for example, it can be 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, 92°C, 94°C or 95°C, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0063] Wherein, the alkali treatment is followed by water washing.

[0064] The water washing temperature is 80-90°C, for example, 80°C, 82°C, 84°C, 86°C, 88°C or 90°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0065] The washing time is ≥ 1 min, for example, it can be 1 min, 2 min, 3 min, 4 min, 5 min, 6 min or 8 min, but is not limited to the listed values. Other values ​​not listed within the range also meet the requirements.

[0066] Furthermore, this embodiment provides a titanium alloy composite, which is prepared by using the titanium alloy and non-metallic material obtained by the etching and roughening method as described above.

[0067] Wherein, the non-metallic material used for the titanium alloy composite includes plastic or resin.

[0068] Wherein, the pull-out force between the titanium alloy and the non-metallic material in the titanium alloy composite is ≥1389.8N.

[0069] Further, in order to illustrate the etching effect that can be achieved by the etching roughening method provided by the present invention, the following actual example is used for exemplary description, as follows:

[0070] Example 1

[0071] This embodiment provides a titanium alloy etching roughening method, which is as follows:

[0072] 1. Degreasing treatment: Use 60g / L R105 degreasing agent to clean for 3 minutes at a temperature of 60°C to remove grease and impurities on the surface of the titanium alloy and improve the cleanliness of the titanium alloy surface;

[0073] 2. Neutralization treatment: using 300g / L HNO 3 The purpose of cleaning for 3 minutes is to remove the degreasing agent residues by chemically reacting with them and converting them into harmless or easy-to-clean substances;

[0074] 3. Sulfuric acid treatment: using 1050g / L H 2 SO 4 Soaking for 15 minutes at 80°C, the purpose is to chemically etch the surface of the titanium alloy to form a gully or microporous structure on the surface, thereby increasing its surface roughness and improving the bonding strength between the titanium alloy and the plastic;

[0075] 4. Ultrasonic water washing: Cleaning for 3 minutes, the ultrasonic power is 1350W, the purpose is to use the cavitation effect to effectively remove the dirt and other impurities attached to the surface of the titanium alloy after sulfuric acid coarsening and disperse them into the cleaning liquid;

[0076] 5. Alkali washing: Soak in 60g / L NaOH solution for 15 minutes at 90°C to increase the surface roughness to a certain extent;

[0077] 6. Hot water washing: Soak at 80℃ for 1 minute to clean the residual medicine on the surface of titanium alloy and prepare for drying.

[0078] Example 2

[0079] This embodiment provides a titanium alloy etching roughening method, which is as follows:

[0080] 1. Degreasing treatment: Use 50g / L R105 degreasing agent to clean for 4 minutes at a temperature of 70°C to remove grease and impurities on the surface of the titanium alloy and improve the cleanliness of the titanium alloy surface;

[0081] 2. Neutralization treatment: using 250g / L HNO 3 Cleaning for 5 minutes, the purpose is to remove these residues by chemically reacting with the degreasing agent residues and converting them into harmless or easy-to-clean substances;

[0082] 3. Sulfuric acid treatment: Use 1100g / L H 2 SO 4 Soaking for 15 minutes at a temperature of 70°C, the purpose is to chemically etch the surface of the titanium alloy to form a gully or microporous structure on the surface, thereby increasing its surface roughness and improving the bonding strength between the titanium alloy and the plastic;

[0083] 4. Ultrasonic water washing: Cleaning for 5 minutes, the ultrasonic power is 1200W, the purpose is to use the cavitation effect to effectively remove the dirt and other impurities attached to the surface of the titanium alloy after sulfuric acid coarsening and disperse them into the cleaning liquid;

[0084] 5. Alkali washing: Soak in 50g / L NaOH solution for 15 minutes at 95°C to increase the surface roughness to a certain extent;

[0085] 6. Hot water washing: Soak at 90℃ for 1 minute to clean the residual medicine on the surface of titanium alloy and prepare for drying.

[0086] Example 3

[0087] This embodiment provides a titanium alloy etching roughening method, which is as follows:

[0088] 1. Degreasing treatment: Use 70g / L R105 degreasing agent to clean for 3 minutes at a temperature of 50°C to remove grease and impurities on the surface of the titanium alloy and improve the cleanliness of the titanium alloy surface;

[0089] 2. Neutralization treatment: using 350g / L HNO 3 The purpose of cleaning for 4 minutes is to remove the degreasing agent residues by chemically reacting with them and converting them into harmless or easy-to-clean substances;

[0090] 3. Sulfuric acid treatment: Use 1000g / L H 2 SO 4 Soaking for 15 minutes at 90°C, the purpose is to chemically etch the surface of the titanium alloy to form a gully or microporous structure on the surface, thereby increasing its surface roughness and improving the bonding strength between the titanium alloy and the plastic;

[0091] 4. Ultrasonic water washing: Cleaning for 3 minutes, the ultrasonic power is 1500W, the purpose is to use the cavitation effect to effectively remove the dirt and other impurities attached to the surface of the titanium alloy after sulfuric acid coarsening and disperse them into the cleaning liquid;

[0092] 5. Alkali washing: Soak in 70g / L NaOH solution for 15 minutes at 80°C to increase the surface roughness to a certain extent;

[0093] 6. Hot water washing: Soak at 80℃ for 2 minutes to clean the residual medicine on the surface of titanium alloy and prepare for drying.

[0094] Comparative Example 1

[0095] The titanium alloy sample of Example 1 was sent to manufacturer A for etching proofing.

[0096] Comparative Example 2

[0097] The titanium alloy sample of Example 1 was sent to manufacturer B for etching proofing.

[0098] Comparative Example 3

[0099] The only difference from Example 1 is that sulfuric acid is replaced by hydrochloric acid with a mass concentration of 10%.

[0100] Comparative Example 4

[0101] The only difference from Example 1 is that the concentration of sulfuric acid used in the sulfuric acid treatment is 500 g / L.

[0102] Comparative Example 5

[0103] The only difference from Example 1 is that the temperature of the sulfuric acid treatment is 25°C.

[0104] Example 4

[0105] The only difference from Example 1 is that the concentration of the alkali solution used in the alkali treatment is 280 g / L.

[0106] Example 5

[0107] The only difference from Example 1 is that the temperature of the alkali treatment is 25°C.

[0108] The roughened titanium alloy obtained in the above example was used to measure the pore size of the surface corrosion holes using a scanning electron microscope. Sq (root mean square height) and Sal (minimum autocorrelation length) are two important parameters in surface roughness evaluation. Sq is a parameter that reflects the spatial distribution characteristics of surface roughness, which represents the standard deviation or root mean square value of the surface height. It measures the degree of fluctuation of the surface height relative to the average plane. The larger the Sq value, the rougher the surface. Sal represents the minimum repetition or correlation length of the surface morphology features in space. A smaller Sal value may mean that the surface has a denser texture or shorter periodic features. The results are shown in Table 1 below; wherein, the SEM photographs of Example 1, Comparative Example 1 and Comparative Example 2 are shown in Table 1 below. Figure 1 , Figure 2 and Figure 3 shown.

[0109] Table 1

[0110]

[0111] Furthermore, the injection pull-out force test of the roughened titanium alloy obtained in the above example is an important method to evaluate the connection strength between the injection molded part and the substrate. The pull-out force refers to the maximum force required for the injection molded part to detach from the substrate when subjected to the pull-out force. The test principle is to apply axial tensile force to the injection molded part, observe and record the process of the injection molded part detaching from the substrate, and thus calculate the required pull-out force. During the test, it is necessary to ensure the accuracy and reliability of the test equipment, the firm installation of the specimen, and the stability and controllability of the test conditions. Each roughened titanium alloy was tested 3 times, that is, multiple samples were etched and roughened in the same batch during the roughening. The plastic used for the injection molded parts in the test was polypropylene, and the test results are shown in Table 2 below.

[0112] Table 2

[0113]

[0114]

[0115] As can be seen from Table 1, in the solution provided by the present invention, sulfuric acid is replaced with 10% hydrochloric acid for roughening. Too high a hydrochloric acid concentration may cause excessive corrosion on the surface of the titanium alloy, thereby destroying its original surface structure; when the temperature is reduced during sulfuric acid roughening, it will lead to uneven roughening quality, and areas of insufficient or excessive roughening will appear on the surface. After the titanium alloy is roughened with sulfuric acid, alkaline washing in a high concentration of NaOH solution may cause excessive corrosion of the titanium alloy, resulting in excessive dissolution and unevenness on the surface. During the alkaline washing process, if the temperature is too low, the chemical reaction rate may slow down, making it impossible to fully remove stains and impurities on the surface of the titanium alloy, affecting the quality and effect of the surface.

[0116] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0117] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0118] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for etching and roughening a titanium alloy, characterized in that: The etching roughening method comprises: The titanium alloy is sequentially subjected to sulfuric acid treatment and alkali treatment; The concentration of sulfuric acid used in the sulfuric acid treatment is 1000-1100 g / L, the temperature is 70-90° C., and the treatment time is 12-18 min.

2. The etching roughening method according to claim 1, characterized in that: The titanium alloy is sequentially subjected to degreasing treatment and neutralization treatment before being subjected to sulfuric acid treatment.

3. The etching roughening method according to claim 2, characterized in that: The degreasing agent used in the degreasing treatment includes R105 degreasing agent; Preferably, the concentration of the degreasing agent used in the degreasing treatment is 50-70 g / L; Preferably, the temperature of the degreasing treatment is 60-70°C; Preferably, the degreasing treatment time is ≥ 3 min.

4. The etching roughening method according to claim 2 or 3, characterized in that: The neutralizing agent used in the neutralization treatment includes one or a combination of at least two of nitric acid, sulfuric acid or hydrochloric acid; Preferably, the concentration of the neutralizer used in the neutralization treatment is 250-350 g / L; Preferably, the neutralization treatment time is ≥ 3 min.

5. The etching roughening method according to any one of claims 1 to 4, characterized in that: Ultrasonic water washing is provided between the sulfuric acid treatment and the alkali treatment; Preferably, the ultrasonic power of the ultrasonic washing is 1200-1500W; Preferably, the ultrasonic washing time is ≥3 min.

6. The etching roughening method according to any one of claims 1 to 5, characterized in that: The alkali solution used for the alkali treatment includes sodium hydroxide solution and / or potassium hydroxide solution; Preferably, the concentration of the alkali solution used in the alkali treatment is 50-70 g / L; Preferably, the alkali treatment time is ≥15 min; Preferably, the temperature of the alkali treatment is 80-95°C.

7. The etching roughening method according to any one of claims 1 to 6, characterized in that: After the alkali treatment, washing is performed; Preferably, the water washing temperature is 80-90°C; Preferably, the water washing time is ≥ 1 min.

8. A titanium alloy composite, characterized in that: The titanium alloy composite is prepared by using the titanium alloy and non-metallic material obtained by the etching and roughening method according to any one of claims 1 to 7.

9. The titanium alloy composite according to claim 8, characterized in that: The non-metallic material used for the titanium alloy composite includes plastic or resin.

10. The titanium alloy composite according to claim 8 or 9, characterized in that: The pull-out force between the titanium alloy and the non-metallic material in the titanium alloy composite is ≥1389.8N.

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