Surface-activated polyether-ether-ketone and preparation method thereof

Abstract

The invention relates to the technical field of surface treatment, and particularly discloses a thermal in-situ reduction preparation method of palladium nanoparticles on the surface of polyether-ether-ketone, which comprises the following steps: performing thermal in-situ reduction on palladium ions loaded in a polystyrene-poly (2-vinylpyridine) film into palladium nanoparticles; the surface of the polyether-ether-ketone is uniformly coated with a layer of palladium active particles with good binding force, the palladium active particles serve as a catalytic activity center of chemical plating, a coating on the surface of the polyether-ether-ketone is uniform, compact and high-binding-force attachment is achieved, and the pull-off strength of a welding spot of the coating is obviously improved; and the coating on the surface of the polyether-ether-ketone still keeps good bonding strength in a wide-temperature-range environment.

Description

Technical Field

[0001] The present application relates to the field of surface treatment technology, and in particular to a surface-activated polyetheretherketone and a preparation method thereof. Background Art

[0002] Polyetheretherketone (PEEK) is a semi-crystalline aromatic thermoplastic engineering resin. Its macromolecular chain contains numerous rigid benzene rings, flexible ether bonds, and carbonyl groups that enhance intermolecular forces. These properties give it numerous excellent properties, such as excellent high-temperature and chemical corrosion resistance, good mechanical properties, radiation resistance, self-lubrication, and friction resistance. This makes PEEK a suitable substrate for microwave components, radar antennas, and other products in aerospace, aviation, and weaponry, and it has broad application prospects in aerospace, electronics, and other fields. However, due to its non-conductive surface, it cannot be used to replace metal materials and requires surface metallization.

[0003] Polyetheretherketone (PEEK) materials have high volume and surface resistivity. When used in products such as antennas, a surface metal layer must be prepared to achieve functional requirements such as conductivity and welding. However, the surface of PEEK is smooth and dense, with few polar groups, and exhibits high chemical inertness. Metal catalysts cannot effectively adhere to the surface of the material, resulting in discontinuous coating or even inability to plate. In addition, PEEK materials have a high linear thermal expansion coefficient, resulting in relatively poor bonding strength between the metal coating and the PEEK material over a wide temperature range. Therefore, surface activation treatment of the PEEK material is required. Summary of the Invention

[0004] In view of this, the purpose of the present application is to provide a surface-activated polyetheretherketone and a preparation method thereof, so that the bonding strength of the metal layer plated on the surface of the surface-activated polyetheretherketone is significantly improved and can adapt to a wider temperature range environment.

[0005] In order to solve the above technical problems / achieve the above objectives or at least partially solve the above technical problems / achieve the above objectives, as a first aspect of the present application, a method for preparing a surface-activated polyetheretherketone is provided, comprising:

[0006] S1. Roughening and modifying the surface of polyetheretherketone;

[0007] S2. An activation solution comprising palladium ions and polystyrene-poly(2-vinylpyridine) is applied to the polyetheretherketone surface and cured;

[0008] S3. The surface-cured polyetheretherketone in S2 is subjected to thermal in-situ reduction to complete surface activation.

[0009] Optionally, the roughening modification is performed using a mixed solution of sulfuric acid and chromium trioxide for surface treatment. Further optionally, the concentration of sulfuric acid in the mixed solution is 300-400 mL / L, and the concentration of chromium trioxide is 125-200 g / L.

[0010] Optionally, the activation solution is a solution of polystyrene-poly(2-vinylpyridine) loaded with palladium ions, and the molar ratio of the palladium ions to the polystyrene-poly(2-vinylpyridine) is 1:2-1:2.5.

[0011] Optionally, the thermal in situ reduction is a heat treatment at 150-160°C.

[0012] Optionally, the polyetheretherketone includes any one or more of unmodified polyetheretherketone, carbon nanotube-modified polyetheretherketone, carbon fiber-modified polyetheretherketone, and glass fiber-modified polyetheretherketone.

[0013] Optionally, the preparation method further comprises performing metal plating on the surface-activated polyetheretherketone.

[0014] As a second aspect of the present application, provided is a surface-activated polyetheretherketone prepared by the preparation method described in the present application.

[0015] As a third aspect of the present application, provided is the use of polystyrene-poly(2-vinylpyridine) in preparing a polyetheretherketone surface activation solution.

[0016] As a fourth aspect of the present application, a polyetheretherketone surface activation solution is provided, comprising polystyrene-poly(2-vinylpyridine), palladium ions and a non-polar solvent.

[0017] The present application specifically proposes a method for preparing palladium nanoparticles on the surface of polyetheretherketone by thermal in-situ reduction. By thermally reducing the palladium ions loaded in a polystyrene-poly(2-vinylpyridine) film into palladium nanoparticles in situ, the surface of the polyetheretherketone is uniformly coated with a layer of palladium active particles with good bonding strength, which serve as catalytic active centers for chemical plating. The surface coating of the polyetheretherketone is uniform, dense, and has high bonding strength. The pull-out strength of the coating solder joints is significantly improved, and the surface coating of the polyetheretherketone still maintains good bonding strength in a wide temperature range environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The exemplary embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application.

[0019] Figure 1 Shown is the microscopic morphology of the surface of the unmodified polyetheretherketone of Example 1 after roughening modification;

[0020] Figure 2 Shown are the microscopic morphology and EDS analysis of the unmodified polyetheretherketone after activation and attachment of palladium ions to its surface in Example 1;

[0021] Figure 3 The figure shows the microscopic morphology of the surface of the glass fiber modified polyetheretherketone after roughening modification in Example 2;

[0022] Figure 4 The figure shows the microscopic morphology of the surface of the carbon fiber-modified polyetheretherketone after roughening modification in Example 3;

[0023] Figure 5 Shown are the microscopic morphology and EDS analysis of the carbon fiber modified polyetheretherketone after activation and attachment of palladium ions on its surface in Example 3;

[0024] Figure 6 The graphs show the sample before and after the -196°C to +120°C hot and cold cycle of the chemically plated nickel layer after activation of the unmodified polyetheretherketone in Example 1;

[0025] Figure 7 The graphs show the sample before and after the activation of the chemical nickel plating layer of the glass fiber modified polyetheretherketone in Example 2 at -196°C to +120°C hot and cold cycle;

[0026] Figure 8 Shown are sample images of the chemically plated copper layer of glass fiber modified polyetheretherketone activated in Example 2 before and after hot and cold cycles at -196°C to +120°C;

[0027] Figure 9 The graphs show the sample before and after the -196°C to +120°C hot and cold cycle of the chemically plated nickel layer of the carbon fiber modified polyetheretherketone activated in Example 3;

[0028] Figure 10 The graphs show the sample before and after the -196°C to +120°C hot and cold cycle of the chemically plated copper layer of the carbon fiber modified polyetheretherketone activated in Example 3;

[0029] Figure 11 The figure shows the sample of the chemical nickel plating layer after activation of carbon fiber modified polyetheretherketone in comparative example 1 after -196℃~+120℃ hot and cold cycle;

[0030] Figure 12 Shown is a sample image of the chemically plated copper layer of the carbon fiber modified polyetheretherketone activated in comparative example 1 after hot and cold cycling at -196°C to +120°C. DETAILED DESCRIPTION

[0031] The present application discloses a surface-activated polyetheretherketone and a preparation method thereof. Those skilled in the art can refer to the contents of this article and appropriately improve the process parameters to achieve the desired effect. It should be noted in particular that all similar replacements and modifications are obvious to those skilled in the art, and they are all deemed to be included in this application. The products, processes and applications described in this application have been described through preferred embodiments. It is obvious that relevant personnel can modify or appropriately change and combine the methods described herein without departing from the content, spirit and scope of this application to implement and apply the technology of this application. Obviously, the described embodiments are part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of this application.

[0032] It should be noted that, in this document, if relational terms such as "first" and "second", "step 1" and "step 2", and "(1)" and "(2)" appear, they are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "including a..." do not exclude the presence of other identical elements in the process, method, article or device comprising the elements. At the same time, the embodiments in this application and the features in the embodiments can be combined with each other in the absence of conflict.

[0033] Due to the high chemical inertness of the surface of polyetheretherketone, it is usually sensitized (stannous chloride solution) and activated (palladium chloride solution) in the prior art so that the subsequent metal coating can effectively adhere. However, this activation method still faces the disadvantages of poor coating adhesion and incompatibility with a wide temperature range. In response to the existing technical problems, in the first aspect of the present application, a method for preparing surface-activated polyetheretherketone is provided, comprising:

[0034] S1. Roughening and modifying the surface of polyetheretherketone;

[0035] S2. An activation solution comprising palladium ions and polystyrene-poly(2-vinylpyridine) is applied to the polyetheretherketone surface and cured;

[0036] S3. The surface-cured polyetheretherketone in S2 is subjected to thermal in-situ reduction to complete surface activation.

[0037] In certain embodiments of the present application, the roughening modification is performed using a mixed solution of sulfuric acid and chromium trioxide for surface treatment. Sulfuric acid and chromium trioxide coexist at room temperature in a mainly dissolved and coordinated form to form a strong oxidizing solution. CrO3 exists in the form of chromic acid (H2CrO4) or dichromic acid (H2Cr2O7) and reacts with H in sulfuric acid. + Combined to form a high oxidation state Cr(VI) solution. Compared with the conventional roughening method using sulfuric acid solution, after the surface of polyetheretherketone is roughened by a mixed solution of sulfuric acid and chromium trioxide, sulfonation and protonation occur between sulfuric acid and polyetheretherketone, and the surface of polyetheretherketone material obtains a regular network surface microstructure, and the polar oxygen-containing groups C=O, COOH and -SO3H on the surface of the material increase. The increased oxygen-containing polar groups are conducive to the attachment of active particles on the surface of the material, and the coating has good adhesion after plating. However, if only sulfuric acid is used for roughening, the strong corrosiveness of concentrated sulfuric acid causes obvious sulfonation and protonation reactions on the surface of polyetheretherketone, loosening and disentanglement of the polyetheretherketone molecular chain, and gradually diffuses into the sulfuric acid, causing the PEEK surface layer to dissolve significantly. In the subsequent activation and chemical plating process, the PEEK dissolution layer affects the coating adhesion.

[0038] In some other embodiments of the present application, the concentration of sulfuric acid in the mixed solution is 300-400 mL / L, for example, 300 mL / L, 320 mL / L, 340 mL / L, 360 mL / L, 380 mL / L, 400 mL / L, etc., and the concentration of chromium trioxide is 125-200 g / L, for example, 125 g / L, 150 g / L, 175 g / L, 200 g / L, etc.

[0039] In some other embodiments of the present application, step S1 includes: treating the surface of polyetheretherketone with a mixed solution of sulfuric acid and chromium trioxide at a temperature of 70-75°C for 10-30 minutes, and after treatment, immersing it in N,N-dimethylformamide (DMF) solvent and deionized water respectively, ultrasonically stirring, and then blowing dry.

[0040] The present application adopts amphiphilic self-assembling block copolymer polystyrene-poly (2-vinyl pyridine) and palladium chloride together to form an activation solution to activate the surface of polyetheretherketone. Polystyrene-poly (2-vinyl pyridine) can cause phase separation due to the unfavorable interaction between the blocks. This phase separation can produce an ordered morphology, such as lamellar, columnar and spherical, which can become the matrix for the synthesis of palladium nanoparticles, serve as a nanoreactor and create an ordered array of nanoparticles. In addition, the nitrogen atoms in the polystyrene-poly (2-vinyl pyridine) block pyridine group can selectively interact with palladium ions, better load palladium ions. The molar weight of polystyrene-poly (2-vinyl pyridine) and the concentration of palladium ions determine the size, morphology and spatial arrangement of palladium nanoparticles. In certain embodiments of the present application, the molar ratio of the palladium ions to polystyrene-poly(2-vinylpyridine) is 1:2-1:2.5, for example, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, etc. Within this ratio range, the palladium ions are fully and evenly loaded on the polystyrene-poly(2-vinylpyridine) without agglomeration. When the nitrogen atoms in the polystyrene-poly(2-vinylpyridine) are constant, if the palladium ion concentration is too high, agglomeration is likely to occur when the binding points with nitrogen are constant, which in turn reduces the catalytic activity. If the palladium ion concentration is too low, the active particles are evenly loaded, but the active particle concentration is low, and the catalytic activity is also reduced.

[0041] In certain embodiments of the present application, the activation solution is prepared as follows:

[0042] Polystyrene-poly (2-vinyl pyridine) was dissolved in toluene, and then palladium chloride was added to the polystyrene-poly (2-vinyl pyridine) solution, and then vigorously stirred at room temperature to prepare polystyrene-poly (2-vinyl pyridine) loaded palladium ions (Pd 2+ ) mixed solution as the activation solution.

[0043] Toluene is a higher polystyrene solvent than poly(2-vinylpyridine), so micelles consisting of a polystyrene core and a poly(2-vinylpyridine) corona are formed in the activated solution. Generally speaking, amphiphilic block copolymers dissolved in non-polar solvents (toluene) will form reverse micelles. 2+ When added to the assembled block copolymer solution, Pd 2+ The ions diffuse into the core of the micelle, where the only nitrogen pair in poly(2-vinylpyridine) binds to the Pd 2+ Ion action produces Pd 2+ / polystyrene-poly (2-vinyl pyridine) micelle complex. In certain embodiments of the present application, Pd 2+The polystyrene-poly(2-vinylpyridine) micelle complex solution was sprayed onto the surface of polyetheretherketone to form a film. The film consisted of a layer of Pd 2+ The polystyrene-poly(2-vinylpyridine) micelles are covered on the surface of polyetheretherketone. This "top-down" coating technology combined with the "bottom-up" self-assembly of polystyrene-poly(2-vinylpyridine) in the activation solution can give the polyetheretherketone surface a more complex morphology, which is more conducive to the subsequent bonding of metal plating.

[0044] In some other embodiments of the present application, the activation solution is sprayed onto the surface of the polyetheretherketone using a spray gun, or is brushed onto the surface of the polyetheretherketone with a clean brush. The total thickness of the sprayed or brushed coating is ≤10 microns. Each time the spraying or brushing is completed, it is dried in the shade for 15 minutes, and finally placed in an 80°C oven for 30 to 35 minutes to remove the solvent for solidification, thereby obtaining a polyetheretherketone surface containing palladium ions (Pd 2+ ) polystyrene-poly(2-vinylpyridine) film.

[0045] In certain embodiments of the present application, after thermal in situ reduction, the aforementioned polymer film self-reconstructs, and Pd 2+ ions are reduced to Pd by the nitrogen in the poly(2-vinylpyridine) chain. 0 , thus forming Pd 0 / polystyrene-poly(2-vinylpyridine) film to complete the activation treatment. In some other embodiments of the present application, the thermal in-situ reduction is a heat treatment at 150-160° C., and the heat treatment time can be 1.5-2 hours.

[0046] In certain embodiments of the present application, the palladium ions can be formed by a catalyst capable of releasing Pd 2+ The polyetheretherketone activated in this application is applicable to any one or more of unmodified polyetheretherketone, carbon nanotube-modified polyetheretherketone, carbon fiber-modified polyetheretherketone, and glass fiber-modified polyetheretherketone.

[0047] In certain embodiments of the present application, the preparation method further comprises performing metal plating on the surface-activated polyetheretherketone, wherein the metal comprises copper, nickel, silver, gold, or tin. In other embodiments of the present application, chemical nickel plating is performed on the surface of the activated polyetheretherketone, and the nickel plating layer is uniform and dense, and the plated solder joint tensile strength is ≥2MPa, and can withstand a -196°C to +120°C hot and cold cycle test. The nickel metal plating on the polyetheretherketone surface still maintains good bonding strength in a wide temperature range environment.

[0048] In the second aspect of the present application, a surface-activated polyetheretherketone prepared by the preparation method is provided, which may be polyetheretherketone that has been surface-activated only, or polyetheretherketone that has been surface-activated and then plated with a metal layer.

[0049] In the third aspect of the present application, given that polystyrene-poly(2-vinylpyridine) as an activation solution can produce significantly excellent effects on the surface activation of polyetheretherketone, the present application provides the use of polystyrene-poly(2-vinylpyridine) in the preparation of a polyetheretherketone surface activation solution; further, it can be the use of polystyrene-poly(2-vinylpyridine) and palladium ions and non-polar solvents in the preparation of a polyetheretherketone surface activation solution.

[0050] In a fourth aspect of the present application, a polyetheretherketone (PEEK) surface activation solution is provided, comprising polystyrene-poly(2-vinylpyridine), palladium ions, and a non-polar solvent. The palladium ions are provided by palladium chloride, and the molar ratio of palladium ions to polystyrene-poly(2-vinylpyridine) is 1:2 to 1:2.5. The non-polar solvent may be toluene.

[0051] In the comparative experiments provided in this application, unless otherwise specified, all experimental conditions and materials, except for the differences noted in each group, were kept consistent to ensure comparability. In addition, all materials used in this application can be purchased from commercial sources.

[0052] The following further describes a surface-activated polyetheretherketone and its preparation method provided in this application.

[0053] Example 1:

[0054] The polyetheretherketone material was treated with a mixed solution of sulfuric acid and chromium trioxide (the concentrations of sulfuric acid and chromium trioxide were 400mL / L and 200g / L, respectively) at a temperature of 75°C for 10 minutes. After treatment, it was immersed in N,N-dimethylformamide (DMF) solvent and deionized water, respectively, and ultrasonically stirred for 10 minutes, and then blown dry. The microscopic picture after surface roughening is shown in Figure 1 .

[0055] Polystyrene-poly(2-vinylpyridine) (PS 389 -b-P2VP 381, purchased from PolymerSource Inc., Quebec, Canada) was dissolved in toluene to obtain a 0.8-1.0 wt% solution. Ultrasonic stirring was then performed at room temperature for 12 hours, and toluene was then added while stirring to dilute the solution to a 0.08-0.1 wt% solution. Palladium chloride was then added to the polystyrene-poly(2-vinylpyridine) solution at a molar ratio of 1:2.5. The mixture was then vigorously stirred at room temperature for 12 hours to prepare a polystyrene-poly(2-vinylpyridine)-loaded palladium ion mixed solution, which served as the activation treatment solution.

[0056] The activation treatment solution is sprayed onto the surface of the polyetheretherketone using a spray gun. The total thickness of the sprayed coating is ≤10 microns. After each spraying is completed, it is dried in the shade for 15 minutes and finally placed in an 80°C oven for 30-35 minutes to remove the solvent in order to solidify and obtain a coating containing palladium ions (Pd 2+ ) polystyrene-poly(2-vinylpyridine) film.

[0057] The polyetheretherketone with the film attached is placed in an oven for heat treatment at 150-160°C for 1.5-2 hours to obtain palladium nanoparticles attached to the surface of the polyetheretherketone. The micromorphology of the surface after palladium ions are attached and the EDS analysis diagram are shown in Figure 2 .

[0058] Example 2:

[0059] Glass fiber modified polyetheretherketone was treated with a mixed solution of sulfuric acid and chromium trioxide (the concentrations of sulfuric acid and chromium trioxide were 400 mL / L and 200 g / L, respectively) at 75°C for 10 minutes. After treatment, it was immersed in N,N-dimethylformamide (DMF) solvent and deionized water, respectively, and ultrasonically stirred for 10 minutes, and then blown dry. The microscopic picture after surface roughening is shown in Figure 3 .

[0060] Polystyrene-poly(2-vinylpyridine) (PS 389 -b-P2VP 381 , purchased from PolymerSource Inc., Quebec, Canada) was dissolved in toluene to obtain a 0.8-1.0 wt% solution. Ultrasonic stirring was then performed at room temperature for 12 hours, and toluene was then added while stirring to dilute the solution to a 0.08-0.1 wt% solution. Palladium chloride was then added to the polystyrene-poly(2-vinylpyridine) solution at a molar ratio of 1:2. The mixture was then vigorously stirred at room temperature for 12 hours to prepare a polystyrene-poly(2-vinylpyridine)-loaded palladium ion mixed solution, which served as the activation treatment solution.

[0061] The activation treatment solution is sprayed onto the surface of the polyetheretherketone using a spray gun. The total thickness of the sprayed coating is ≤10 microns. After each spraying is completed, it is dried in the shade for 15 minutes and finally placed in an 80°C oven for 30-35 minutes to remove the solvent in order to solidify and obtain a coating containing palladium ions (Pd 2+ ) polystyrene-poly(2-vinylpyridine) film.

[0062] The polyetheretherketone with the film attached thereto is placed in an oven for heat treatment at 150-160° C. for 1.5-2 hours to obtain palladium nanoparticles attached to the surface of the polyetheretherketone.

[0063] Example 3:

[0064] The carbon fiber modified polyetheretherketone was treated with a mixed solution of sulfuric acid and chromium trioxide (the concentrations of sulfuric acid and chromium trioxide were 400mL / L and 150g / L respectively) at a temperature of 75°C for 10 minutes. After treatment, it was immersed in N,N-dimethylformamide (DMF) solvent and deionized water respectively, ultrasonically stirred for 10 minutes, and then blown dry. The microscopic picture after surface roughening is shown in Figure 4 .

[0065] Polystyrene-poly(2-vinylpyridine) (PS 389 -b-P2VP 381 , purchased from PolymerSource Inc., Quebec, Canada) was dissolved in toluene to obtain a 0.8-1.0 wt% solution. Ultrasonic stirring was then performed at room temperature for 12 hours, and toluene was then added while stirring to dilute the solution to a 0.08-0.1 wt% solution. Palladium chloride was then added to the polystyrene-poly(2-vinylpyridine) solution at a molar ratio of 1:2. The mixture was then vigorously stirred at room temperature for 12 hours to prepare a polystyrene-poly(2-vinylpyridine)-loaded palladium ion mixed solution, which served as the activation treatment solution.

[0066] The activation treatment solution is sprayed onto the surface of the polyetheretherketone using a spray gun. The total thickness of the sprayed coating is ≤10 microns. After each spraying is completed, it is dried in the shade for 15 minutes and finally placed in an 80°C oven for 30-35 minutes to remove the solvent in order to solidify and obtain a coating containing palladium ions (Pd 2+ ) polystyrene-poly(2-vinylpyridine) film.

[0067] The polyetheretherketone with the film attached is placed in an oven for heat treatment at 150-160°C for 1.5-2 hours to obtain palladium nanoparticles attached to the surface of the polyetheretherketone. The micromorphology of the surface after palladium ions are attached and the EDS analysis diagram are shown in Figure 5 .

[0068] Example 4:

[0069] The roughened and activated polyetheretherketone (PEEK) material was electrolessly plated with nickel using a medium-phosphorus nickel solution containing 12 g / L basic nickel carbonate, 22 g / L sodium hypophosphite, 18 mg / L citric acid, 3 g / L succinic acid, 10 g / L ammonium bifluoride, 1.5 mL / L sodium saccharin, 12 mL / L hydrofluoric acid (40%), 22 mL / L ammonia water, and 0.8 mL / L stabilizer. The nickel plating temperature was 78°C for 40 minutes. The resulting nickel layer, an electroless nickel-phosphorus alloy, was approximately 8 microns thick.

[0070] The polyetheretherketone material after roughening and activation treatment is subjected to chemical copper plating. The chemical copper plating solution includes 7 g / L copper sulfate, 10 mL / L formaldehyde, 5 g / L potassium hydroxide, 28 g / L potassium sodium tartrate, and 0.2 mg / L stabilizer. The solution temperature is 33°C, the chemical copper plating time is 2 hours, and the thickness of the chemical copper plating layer is about 4 microns.

[0071] Experimental example:

[0072] According to the "QJ832B-2011 Test Methods for Multilayer Printed Circuit Boards for Aerospace Use" standard, the surface mount pad pull-off strength test method is used to test the pull-off strength of the solder joints between the surface coating and the substrate of the polyetheretherketone material.

[0073] Using the high and low temperature environment test (GJB 150.5A-2009), the test piece was placed in a +120℃ oven and baked at high temperature for 10 minutes. Then it was quickly taken out and placed in liquid nitrogen for 10 minutes. After the hot and cold shock, the metal layer on the surface of the polyetheretherketone material had no bulging or cracking, and the coating had good adhesion.

[0074] The above method was used to detect the chemical nickel plating layer and chemical copper plating layer of polyetheretherketone in Examples 1-3 and Comparative Example 1, respectively. Comparative Example 1 is a conventional activation method, specifically as follows:

[0075] Comparative Example 1: The carbon fiber-modified polyetheretherketone material was subjected to chemical roughening, sensitization, activation, and chemical nickel plating in sequence to test the bonding strength between the polyetheretherketone and the metal coating. The roughening solution included the following components: 200 g / L chromium trioxide and 400 mL / L sulfuric acid. The roughening temperature was 75°C and the roughening time was 10 min. After roughening, sensitization and activation treatment were performed using a stannous chloride solution (1.5 g / L) and a palladium chloride solution (0.5 g / L, the same concentration as in Example 3), respectively, followed by chemical nickel plating and chemical copper plating, using the same method as in Example 4.

[0076] Table 1

[0077]

[0078] As shown in Table 1, the pull-off strength of the solder joints after chemical nickel plating / copper plating of the activated polyetheretherketones in Examples 1-3 is significantly higher than the pull-off strength of the solder joints after chemical nickel plating of the polyetheretherketone in Comparative Example 1, indicating that the polyetheretherketone surface activated by the present invention has a higher coating bonding strength after plating.

[0079] also, Figures 6-10 The results of hot and cold cycles show that the nickel and copper coatings of Examples 1-3 are intact without bulging or cracking. Figure 11 The results after hot and cold cycles showed that the nickel coating of Comparative Example 1 was partially cracked; Figure 12 The results after hot and cold cycling showed that the copper plating of Comparative Example 1 was partially bulged and peeled off. The experimental results of hot and cold cycling at -196°C to +120°C showed that the surface-activated polyetheretherketone of the present invention had a high coating adhesion after plating and could withstand high and low temperature environments.

[0080] The foregoing is merely a list of specific embodiments of the present application, intended to enable those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application is not limited to the embodiments shown herein, but is intended to conform to the broadest scope consistent with the principles and novel features of the present application.

Claims

1. A method for preparing surface-activated polyetheretherketone, characterized in that: include: S1. Roughening and modifying the surface of polyetheretherketone; S2. An activation solution comprising palladium ions and polystyrene-poly(2-vinylpyridine) is applied to the polyetheretherketone surface and cured; S3. The surface-cured polyetheretherketone in S2 is subjected to thermal in-situ reduction to complete surface activation.

2. The preparation method according to claim 1, characterized in that The roughening modification adopts a mixed solution of sulfuric acid and chromium trioxide for surface treatment.

3. The preparation method according to claim 2, characterized in that The concentration of sulfuric acid in the mixed solution is 300-400 mL / L, and the concentration of chromium trioxide is 125-200 g / L.

4. The preparation method according to claim 1, characterized in that The activation solution is a solution of polystyrene-poly (2-vinyl pyridine) loaded with palladium ions, and the molar ratio of the palladium ions to the polystyrene-poly (2-vinyl pyridine) is 1:2-1:2.

5.

5. The preparation method according to claim 1, characterized in that The thermal in-situ reduction is a heat treatment at 150-160°C.

6. The preparation method according to claim 1, characterized in that The polyetheretherketone includes any one or more of unmodified polyetheretherketone, carbon nanotube-modified polyetheretherketone, carbon fiber-modified polyetheretherketone, and glass fiber-modified polyetheretherketone.

7. The preparation method according to any one of claims 1 to 6, characterized in that Also included is metal plating on surface activated polyetheretherketone.

8. The surface-activated polyetheretherketone prepared by the preparation method according to any one of claims 1 to 7.

9. Application of polystyrene-poly(2-vinylpyridine) in the preparation of polyetheretherketone surface activation solution.

10. A polyetheretherketone surface activation solution, characterized in that: Includes polystyrene-poly(2-vinylpyridine), palladium ions, and a non-polar solvent.

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