Method and device for preparing metal ceramic composite coating through friction-assisted electrodeposition

Abstract

According to the method and device for preparing the metal ceramic composite coating through friction-assisted electro-deposition, the stable electro-deposition coating is formed in the friction area on the metal substrate through the friction effect between the anode bar and the metal substrate, mask-free localized deposition is achieved, and the metal ceramic composite coating is formed. According to the method, the deposition efficiency can be improved, the ceramic particles are embedded into the surface of the cathode more tightly, the mechanical property of a deposition layer is improved, and the microstructure and performance of the deposition layer are improved; and hydrogen generated in the electrolysis process can be rapidly discharged out of the electrolytic tank, the defects of air holes and the like existing in a deposition layer are eliminated, and the deposition quality is improved. The average hardness of the prepared metal ceramic composite coating can reach 140-180 HV, and the wear resistance of a matrix is greatly improved; and the metal ceramic composite coating and the metal substrate have a good bonding characteristic, so that the crack sensitivity of a deposition layer is obviously reduced. The deposition material used in the method is low in price, the method is easy to operate, the deposition layer forming quality is good, no mask exists, the deposition speed is high, and the method is suitable for batch production.

Description

Technical Field

[0001] The invention belongs to the technical field of electrodeposition, and relates to a method and a device for preparing a metal-ceramic composite coating by friction-assisted electrodeposition. Background Art

[0002] Localized electrodeposition coating technology is a technology that precisely deposits metal or composite metal materials in a specified area through electrochemical effects. The characteristic of localized electrodeposition forming at room temperature allows it to avoid the problems of high thermal residual stress, oxidation phase transformation segregation, pores, cracks, inclusions, chaos, poor mechanical properties of formed parts and low dimensional accuracy caused by traditional additive manufacturing technology using lasers and electron beams as heat sources. At the same time, the material transfer in the electrochemical deposition process is carried out on the ionic scale, which can achieve the advantages of micro-nano processing accuracy, thereby achieving the processing goals of high-precision, complex three-dimensional metal microstructures. Therefore, localized electrodeposition coating technology is widely used in machinery, aerospace, electronic packaging and other fields.

[0003] In the localized electrodeposition coating technology, the commonly used base metals for composite electroplating are nickel, copper, chromium, iron, etc., and the main dispersed phases are metal oxides, carbides, nitrides and polymer particles. The most widely studied is the composite coating with copper as the matrix and inorganic compound particles as the reinforcement phase. Among them, the Cu-SiC composite electrodeposition layer has been successfully used in the automotive and aerospace industries due to its excellent corrosion resistance and tribological properties.

[0004] Although localized electrodeposition coating technology can avoid the generation of pores, cracks, inclusions and other problems, localized electrodeposition coating technology faces many shortcomings, mainly manifested in low deposition rate and uneven surface of the deposited layer. During the electrodeposition process, due to factors such as uneven current density distribution, poor electrolyte flow state or differences in electrode surface state, the deposited layer may be uneven in thickness, composition and morphology. This unevenness will affect the overall performance of the coating, such as hardness, wear resistance, corrosion resistance, and aesthetics. In addition, during the electrodeposition process, the generation of new crystal nuclei and the growth of crystals are key factors in determining the mechanical properties of the deposited layer. If the deposition conditions are not properly controlled, it may lead to coarse grains, thereby affecting the hardness and wear resistance of the coating. Pores, cracks, low bonding strength and other defects and deficiencies are also prone to occur inside the coating and between the coating and the substrate, causing the coating to fall off, thereby affecting the service life of the coating. Therefore, the preparation of high-quality deposited layers requires harsh process conditions, low production efficiency and high production costs. Summary of the invention

[0005] The purpose of the present invention is to provide a method and device for preparing a metal-ceramic composite coating by friction-assisted electrodeposition, so as to solve the problems of low deposition rate and uneven deposition layer surface in the existing electrodeposition coating preparation process.

[0006] To achieve the above object, the present invention adopts the following technical solutions: The present application provides a method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition, the method comprising: S01: preparing an electrodeposition solution and subjecting a metal substrate to an acid-base treatment to obtain a pretreated metal substrate; wherein the metal substrate is one of a copper plate, an iron plate, a chromium plate or a nickel plate.

[0007] The electroplating solution is prepared according to the materials of the metal substrate and the deposited coating. The metal substrate in the present application is one of a copper plate, an iron plate, a chromium plate or a nickel plate. For example, when the metal substrate is a copper plate, an electroplating solution for forming a Cu-SiC composite coating is prepared. At this time, the preparation of the electroplating solution is as follows: SiC powders with particle sizes of 3 μm, 5 μm and 10 μm are mixed in a mass ratio of 1:1:1 to form a SiC mixed powder. CuSO 4 7H 2 O, H 2 SO 4 and SiC mixed powder to form an electrodeposition solution. In the electrodeposition solution, CuSO 4 7H 2 O, H 2 SO 4 The concentrations of the mixed SiC powders are 100-200 g / L, 30-60 g / L and 10-20 g / L respectively.

[0008] In order to make SiC easier to deposit on the copper plate, SiC powders of different particle sizes are used in this application to prevent SiC powders of the same particle size from settling in the electrodeposition solution. At the same time, SiC powders of different particle sizes are more easily driven by electrophoretic force in the electric field, and then stably migrate to the surface of the copper plate, which is convenient for electrodeposition.

[0009] The concentration of 15g / L NaOH and 25g / L Na 2 CO 3 Mix them in a volume ratio of 1:(2-3) to form an alkaline solution. 2 SO 4 and H with a concentration of 80 g / L 2 O 2 Mix in a volume ratio of 3: (2-3) to form an acidic solution with a pH of 3-4. Immerse a metal substrate with a thickness of 1-5 mm in the alkaline solution for 10-20 minutes, wash it with clean water and blow it dry to remove the oil stains on the surface of the metal substrate. Then, immerse the metal substrate in the acidic solution for activation for 20-40 seconds, wash it with clean water and blow it dry to form a pre-treated metal substrate for use.

[0010] S02: placing the pretreated metal substrate inside an electrolytic tank, with a portion of the pretreated metal substrate located at the bottom of the electrolytic tank and another portion of the pretreated metal substrate located on the inner wall of the electrolytic tank, and pouring the electrodeposition solution.

[0011] The pre-treated metal substrate is placed inside the electrolytic tank, with one part located at the bottom of the electrolytic tank and the other part located on the inner wall of the electrolytic tank to form an L-shaped structure. The electrodeposition solution is poured into the electrolytic tank and submerged in the pre-treated metal substrate at the bottom of the electrolytic tank.

[0012] S03: Using the pretreated metal substrate as a cathode and the stainless steel ball-head rod as an anode, friction electrodeposition is performed under the reciprocating motion of the electrolytic cell to obtain a metal-ceramic composite coating deposited on the pretreated metal substrate; wherein the distance between the bottom of the anode and the pretreated metal substrate located at the bottom of the electrolytic cell is 1-3 mm.

[0013] Specifically, the pretreated metal substrate is used as a cathode to form a cathode plate, which is connected to the negative electrode of a DC power supply. The stainless steel ball head rod is used as an anode to form an anode rod, which is connected to the positive electrode of a DC power supply, and the distance between the bottom of the anode rod and the pretreated metal substrate located at the bottom of the electrolytic cell is 1-3 mm. The diameter of the stainless steel ball head rod is 6-14 mm, the diameter of the ball head is 8-20 mm, and the current of the DC power supply is 50-100 mA / cm 2 .

[0014] The electrolytic cell reciprocates at a reciprocating frequency of 5-50 mm / s within a stroke range of 10-100 mm. Under the condition of a temperature of 30-50°C and reciprocating operation of the electrolytic cell, the electrodeposition solution is deposited on the surface of the metal substrate by friction-assisted electrodeposition to form a metal-ceramic composite coating. The electrodeposition time is 5-15 min. The friction-assisted electrodeposition in this application refers to the rapid flow of the electrodeposition solution in the narrow area between the anode rod and the metal substrate caused by the movement of the anode rod, thereby forming an electrodeposition effect under the friction effect.

[0015] The present application also provides a device for preparing metal-ceramic composite coating by friction-assisted electrodeposition, which includes: a fixed table, a reciprocating workbench and a DC power supply; a support arm is provided on the fixed table, and the end of the support arm clamps the anode rod through an insulating clamp; a heating plate is provided on the reciprocating workbench, and an electrolytic cell is arranged on the heating plate, wherein an electrolyte and a cathode plate are arranged in the electrolytic cell, wherein a portion of the cathode plate is located at the bottom of the electrolytic cell, and another portion is located on the side wall of the electrolytic cell; the distance between the anode rod and the cathode plate located at the bottom of the electrolytic cell is 1-3 mm; and the DC power supply is electrically connected to the anode rod and the cathode plate, respectively.

[0016] The present invention has the following beneficial effects: (1) In the present application, a stable electrodeposition coating is formed on the metal substrate in the friction area between the anode rod and the metal substrate, thereby realizing maskless localized deposition.

[0017] (2) The friction in the narrow area between the anode rod and the metal substrate can increase the movement speed of ions in the electrodeposition solution, thereby greatly improving the deposition efficiency; it can also embed the ceramic particles more tightly into the cathode surface, thereby improving the mechanical properties of the deposited layer and improving the microstructure and performance of the deposited layer; at the same time, it can also quickly discharge the hydrogen generated during the electrolysis process out of the electrolytic cell, eliminate defects such as pores in the deposited layer, and improve the deposition quality.

[0018] (3) The friction speed in this application is adjustable and suitable for different materials and application requirements.

[0019] (4) The average hardness of the Cu-SiC composite coating formed in the present application can reach 140-180 HV, which can increase the hardness of the substrate material by more than 2 times, and the wear resistance of the substrate is greatly improved.

[0020] (5) The Cu-SiC composite coating formed in the present application has good bonding properties with the copper substrate, which significantly reduces the crack sensitivity of the deposited layer.

[0021] (6) The deposition material used in this application is inexpensive, the method is easy to operate, the deposition layer has good molding quality, and is suitable for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 A schematic diagram of the structure of a device for preparing a metal-ceramic composite coating by friction-assisted electrodeposition provided in an embodiment of the present application; Figure 2 A schematic diagram of the structure of the anode rod provided in the embodiment of the present application; Figure 3 A schematic diagram of the principle structure of friction-assisted electrodeposition provided in an embodiment of the present application; Figure 4 This is a macroscopic morphology of a copper plate during the preparation of a Cu-SiC composite coating in Example 1 of the present application; Figure 5 This is a macroscopic morphology of the Cu-SiC composite coating prepared in Example 1 of the present application; Figure 6 The microstructure diagram of the Cu-SiC composite coating prepared in Example 1 of the present application; Figure 7 This is a microstructure diagram of the Cu-SiC composite coating and the copper plate prepared in Example 1 of the present application; Figure 8The XRD (English name: X-raydiffraction; Chinese name: X-ray diffraction) diagram of the Cu-SiC composite coating prepared in Example 1 of the present application; Fig. 9 This is a hardness test diagram of the Cu-SiC composite coating prepared in Example 1 of the present application; Symbols represent: 1-fixed table, 2-support arm, 3-insulating clamp, 4-anode rod, 5-electrolytic cell, 6-cathode plate, 7-electrolyte, 8-reciprocating workbench, 9-heating plate, 10-DC power supply. DETAILED DESCRIPTION

[0023] The present application embodiment provides a device for preparing a metal-ceramic composite coating by friction-assisted electrodeposition, the device comprising a fixed table 1, a reciprocating worktable 8 and a DC power supply 10, as shown in the attached Figure 1 As shown. A support arm 2 is provided on the fixing platform 1, and the end of the support arm 2 clamps the anode rod 4 through an insulating clamp 3 to fix the anode rod 4. The anode rod 4 in the embodiment of the present application is a stainless steel ball head rod, which includes a ball rod and a ball head, as shown in the attached Figure 2 The diameter of the ball shaft is 6-14mm, the diameter of the ball head is 8-20mm, and the total length of the stainless steel ball head rod is 50-100mm.

[0024] The reciprocating workbench 8 is a component that realizes reciprocating motion through a driving mechanism, which can drive the electrolytic cell 5 to reciprocate. In the embodiment of the present application, the reciprocating stroke of the reciprocating workbench 8 is 10-100mm, and the reciprocating motion frequency is 5-50mm / s. A heating plate 9 is provided on the reciprocating workbench 8, and the heating plate 9 is used to heat the electrolytic cell 5, and the heating temperature is 30-50°C. The electrolytic cell 5 is arranged on the heating plate 9, and the electrolytic cell 5 is provided with an electrolyte 7 and a cathode plate 6, wherein part of the cathode plate 6 is located at the bottom of the electrolytic cell 5, and the other part is located on the side wall of the electrolytic cell 5, and the electrolyte 7 is submerged in the cathode plate 6 located at the bottom of the electrolytic cell 5.

[0025] The anode rod 4 is located above the cathode plate 6, and the distance between the anode rod 4 and the cathode plate 6 located at the bottom of the electrolytic cell 5 is 1-3 mm. Since the anode rod 4 is fixed on the support arm 2, the cathode plate 6 reciprocates under the anode rod 4 under the reciprocating motion of the reciprocating workbench 8. A DC power supply 10 is electrically connected to the anode rod 4 and the cathode plate 6, respectively, so as to provide 50-100 mA / cm 2 of DC current.

[0026] The present application provides a method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition, the method comprising: S01: Prepare the electrodeposition solution according to the metal substrate and the material of the deposited coating. Mix 15g / L NaOH and 25g / L Na 2 CO 3 Mix them in a volume ratio of 1:(2-3) to form an alkaline solution. 2 SO 4 and H with a concentration of 80 g / L 2 O 2 Mix in a volume ratio of 3: (2-3) to form an acidic solution with a pH of 3-4. Immerse a metal substrate with a thickness of 1-5 mm in the alkaline solution for 10-20 minutes, wash it with clean water and blow it dry to remove the oil stains on the surface of the metal substrate. Then, immerse the metal substrate in the acidic solution for activation for 20-40 seconds, wash it with clean water and blow it dry to form a pre-treated metal substrate for use.

[0027] S02: Place the pretreated metal substrate inside the electrolytic tank, with one part located at the bottom of the electrolytic tank and the other part located on the inner wall of the electrolytic tank to form an L-shaped structure. Pour the electrodeposition solution into the electrolytic tank and immerse the pretreated metal substrate at the bottom of the electrolytic tank.

[0028] S03: The pretreated metal substrate is used as the cathode to form a cathode plate, which is connected to the negative pole of the DC power supply. The stainless steel ball head rod is used as the anode to form an anode rod, which is connected to the positive pole of the DC power supply, and the distance between the bottom of the anode rod and the pretreated metal substrate located at the bottom of the electrolytic cell is 1-3mm. The electrolytic cell reciprocates at a reciprocating frequency of 5-50mm / s within a stroke range of 10-100mm. Under the conditions of a temperature of 30-50℃ and reciprocating operation of the electrolytic cell, the electroplating solution is deposited by friction-assisted electroplating for 5-15min to form a metal-ceramic composite coating on the surface of the metal substrate.

[0029] As attached Figure 3 As shown, taking the metal substrate as a copper plate and the ceramic particles as SiC solid particles as an example, the principle of friction-assisted electrodeposition in the embodiment of the present application is: under the action of a DC power supply, the SiC solid particles in the electrodeposition solution are positively charged; during the reciprocating movement of the electrolytic cell, friction stirring is formed in the narrow area between the anode rod and the copper plate, and under this friction stirring, the flow of the electrodeposition solution causes the positively charged SiC solid particles to suspend and move to the vicinity of the cathode; the positively charged SiC solid particles are captured by the cathode and attached to the cathode surface; under the friction of the anode rod, the SiC solid particles attached to the cathode surface are squeezed and embedded in the cathode surface to form a coating.

[0030] In the embodiment of the present application, the friction in the narrow area between the anode rod and the copper plate has the following effects: (1) Friction increases the movement speed of ions in the electrodeposition solution, thereby greatly improving the deposition efficiency. (2) During the friction process, the anode rod squeezes the SiC solid particles attached to the cathode surface, so that the SiC solid particles are more tightly embedded in the cathode surface, thereby improving the mechanical properties of the deposited layer. (3) During the friction-assisted deposition process, the friction can also quickly discharge the hydrogen generated during the electrolysis process out of the electrolytic cell, eliminate defects such as pores in the deposited layer, and improve the deposition quality.

[0031] The technical solution of the present invention is further explained and illustrated by means of specific embodiments below.

[0032] Example 1 The present application provides a method for preparing a Cu-SiC composite coating by friction-assisted electrodeposition, the method comprising: S101: SiC powders with particle sizes of 3 μm, 5 μm and 10 μm are mixed in a mass ratio of 1:1:1 to form SiC mixed powder. 4 7H 2 O, H 2 SO 4 and SiC mixed powder to form an electrodeposition solution. In the electrodeposition solution, CuSO 4 7H 2 O, H 2 SO 4 The concentrations of the SiC mixed powders are 200 g / L, 60 g / L and 20 g / L, respectively.

[0033] The concentration of 15g / L NaOH and 25g / L Na 2 CO 3 Mix them in a volume ratio of 1:2 to form an alkaline solution. 2 SO 4 and H with a concentration of 80 g / L 2 O 2 Mix according to the volume ratio of 3: 2 to form an acidic solution with a pH of 3.5. Immerse a copper plate with a thickness of 1.5 mm in the alkaline solution for 15 min, wash it with clean water and blow it dry to remove the oil stain on the surface of the copper plate. Then, immerse the copper plate in the acidic solution for activation for 30 s, wash it with clean water and blow it dry to form a pretreated copper plate for standby use.

[0034] S102: placing the pretreated copper plate inside the electrolytic tank, with a portion of the pretreated copper plate located at the bottom of the electrolytic tank and another portion located on the inner wall of the electrolytic tank, forming an L-shaped structure. Pour the electrodeposition solution into the electrolytic tank and immerse the pretreated copper plate at the bottom of the electrolytic tank.

[0035] S103: The pretreated copper plate is used as the cathode to form a cathode plate, which is connected to the negative pole of the DC power supply. A stainless steel ball head rod with a ball rod diameter of 14 mm, a ball head diameter of 20 mm, and a total length of 100 mm is used as the anode to form an anode rod, which is connected to the positive pole of the DC power supply, and the distance between the bottom of the anode rod and the pretreated copper plate at the bottom of the electrolytic cell is 2 mm. The DC current is 80 mA / cm 2 The electrolytic cell reciprocated at a reciprocating frequency of 38 mm / s within a stroke of 60 mm. Under the condition of a temperature of 40°C and reciprocating operation of the electrolytic cell, the electrodeposition solution was deposited by friction-assisted electrodeposition for 10 minutes to form a Cu-SiC composite coating on the surface of the copper plate.

[0036] Example 2 The present application provides a method for preparing a Cu-SiC composite coating by friction-assisted electrodeposition, the method comprising: S201: SiC powders with particle sizes of 3 μm, 5 μm and 10 μm are mixed in a mass ratio of 1:1:1 to form SiC mixed powder. 4 7H 2 O, H 2 SO 4 and SiC mixed powder to form an electrodeposition solution. In the electrodeposition solution, CuSO 4 7H 2 O, H 2 SO 4 The concentrations of the SiC mixed powders are 100 g / L, 30 g / L and 10 g / L, respectively.

[0037] The concentration of 15g / L NaOH and 25g / L Na 2 CO 3 Mix them in a volume ratio of 1:3 to form an alkaline solution. 2 SO 4 and H with a concentration of 80 g / L 2 O 2 The mixture was mixed in a volume ratio of 3:3 to form an acidic solution with a pH of 3. A copper plate with a thickness of 1 mm was immersed in the alkaline solution for 10 min, washed with clean water and then dried to remove the oil stains on the surface of the copper plate. Then, the copper plate was immersed in the acidic solution for activation for 20 s, washed with clean water and then dried to form a pretreated copper plate for standby use.

[0038] S202: placing the pretreated copper plate inside the electrolytic tank, with a portion of the pretreated copper plate located at the bottom of the electrolytic tank and another portion located on the inner wall of the electrolytic tank, forming an L-shaped structure. Pour the electrodeposition solution into the electrolytic tank and immerse the pretreated copper plate at the bottom of the electrolytic tank.

[0039] S203: The pretreated copper plate is used as the cathode to form a cathode plate, which is connected to the negative pole of the DC power supply. A stainless steel ball head rod with a ball rod diameter of 6mm, a ball head diameter of 8mm, and a total length of 50mm is used as the anode to form an anode rod, which is connected to the positive pole of the DC power supply, and the distance between the bottom of the anode rod and the pretreated copper plate at the bottom of the electrolytic cell is 1mm. The DC current is 50mA / cm 2 The electrolytic cell reciprocated at a reciprocating frequency of 5 mm / s within a stroke of 10 mm. Under the condition of a temperature of 30°C and reciprocating operation of the electrolytic cell, the electrodeposition solution was deposited by friction-assisted electrodeposition for 5 minutes to form a Cu-SiC composite coating on the surface of the copper plate.

[0040] Example 3 The present application provides a method for preparing a Cu-SiC composite coating by friction-assisted electrodeposition, the method comprising: S301: SiC powders with particle sizes of 3 μm, 5 μm and 10 μm are mixed in a mass ratio of 1:1:1 to form SiC mixed powder. 4 7H 2 O, H 2 SO 4 and SiC mixed powder to form an electrodeposition solution. In the electrodeposition solution, CuSO 4 7H 2 O, H 2 SO 4 The concentrations of the SiC mixed powders were 150 g / L, 50 g / L and 15 g / L, respectively.

[0041] The concentration of 15g / L NaOH and 25g / L Na 2 CO 3 Mix them in a volume ratio of 1:2.5 to form an alkaline solution. 2 SO 4 and H with a concentration of 80 g / L 2 O 2 Mix them in a volume ratio of 3: 2.5 to form an acidic solution with a pH of 4. Immerse a 5 mm thick copper plate in the alkaline solution for 20 min, wash it with clean water and blow it dry to remove the oil stains on the surface of the copper plate. Then, immerse the copper plate in the acidic solution for activation for 40 s, wash it with clean water and blow it dry to form a pretreated copper plate for standby use.

[0042] S302: Place the pretreated copper plate inside the electrolytic tank, with part of it located at the bottom of the electrolytic tank and the other part located on the inner wall of the electrolytic tank to form an L-shaped structure. Pour the electrodeposition solution into the electrolytic tank and immerse the pretreated copper plate at the bottom of the electrolytic tank.

[0043] S303: The pretreated copper plate is used as the cathode to form a cathode plate, which is connected to the negative pole of the DC power supply. A stainless steel ball head rod with a ball rod diameter of 10 mm, a ball head diameter of 15 mm, and a total length of 70 mm is used as the anode to form an anode rod, which is connected to the positive pole of the DC power supply, and the distance between the bottom of the anode rod and the pretreated copper plate at the bottom of the electrolytic cell is 3 mm. The DC current is 100 mA / cm 2 The electrolytic cell reciprocates at a reciprocating frequency of 50 mm / s within a stroke of 100 mm. Under the condition of a temperature of 50°C and reciprocating operation of the electrolytic cell, the electrodeposition solution is deposited by friction-assisted electrodeposition for 15 minutes to form a Cu-SiC composite coating on the surface of the copper plate.

[0044] Example 4 The present application provides a method for preparing a Cu-WC composite coating by friction-assisted electrodeposition, the method comprising: S401: WC powders with particle sizes of 3 μm, 5 μm and 10 μm are mixed in a mass ratio of 1:1:1 to form WC mixed powder. 2 P 2 O 7 , 220g K 4 P 2 O 7 , 80g C 6 H 14 N 2 O 7 30g H 3 BO 3 Add to 45℃ deionized water, stirring each reagent continuously until completely dissolved. Then add mixed WC powder and make the WC powder well dispersed by ultrasonic oscillation. Finally, add deionized water to 1000 mL to form an electrodeposition solution.

[0045] The TC4 titanium alloy specimen was used as the substrate. The pretreatment process was as follows: After being polished with 1500# and 2000# sandpapers, it was immersed in CH 3 CH 2 OH for 10 min to remove debris on the surface of TC4 titanium alloy. After washing with deionized water, soak in C 3 H 6 O for 15 min to remove oil stains on the surface. Use 15% HF and 30% HNO 3The mixed solution was soaked at room temperature for 50 seconds for acid washing; then, a 50 g / L NaOH solution was used at 50°C for 1 min for alkaline washing. After the alkaline washing, the mixture was rinsed with deionized water and then added with a 40% volume fraction of HF and a 250 g / L mass concentration of NaOH. 2 CrO 4 The mixed solution was immersed in the solution at 50°C for 15 min for activation. After activation, the plate was washed with deionized water and dried to form a pretreated titanium alloy plate for later use.

[0046] S402: The pretreated titanium alloy plate is placed inside the electrolytic tank, with a portion of the plate located at the bottom of the electrolytic tank and another portion located on the inner wall of the electrolytic tank to form an L-shaped structure. The electrodeposition solution is poured into the electrolytic tank and the pretreated titanium alloy plate located at the bottom of the electrolytic tank is immersed.

[0047] S403: The pretreated titanium alloy plate is used as the cathode to form a cathode plate, which is connected to the negative pole of the DC power supply. A copper ball head rod with a ball shaft diameter of 14 mm, a ball head diameter of 20 mm, and a total length of 100 mm is used as the anode to form an anode rod, which is connected to the positive pole of the DC power supply, and the distance between the bottom of the anode rod and the pretreated titanium alloy plate at the bottom of the electrolytic cell is 2 mm. The DC current is 80 mA / cm 2 The electrolytic cell reciprocated at a reciprocating frequency of 38 mm / s within a stroke of 60 mm. Under the condition of a temperature of 40°C and reciprocating operation of the electrolytic cell, the electrodeposition solution was deposited by friction-assisted electrodeposition for 10 minutes to form a Cu-WC composite coating on the surface of the titanium alloy plate.

[0048] Example 5 The present application provides a method for preparing a Ni-SiC composite coating by friction-assisted electrodeposition, the method comprising: S501: SiC powders with particle sizes of 3 μm, 5 μm and 10 μm are mixed in a mass ratio of 1:1:1 to form SiC mixed powder. 4 6H 2 O、NiCl 2 6H 2 O, H 2 SO 4 and SiC mixed powder to form an electrodeposition solution. In the electrodeposition solution, NiSO 4 6H 2 O、NiCl 2 6H 2 O, H 2 SO 4 The concentrations of the mixed SiC powders are 200 g / L, 180 g / L, 60 g / L and 20 g / L, respectively.

[0049] The concentration of 15g / L NaOH and 25g / L Na 2 CO 3 Mix them in a volume ratio of 1:2 to form an alkaline solution. 2 SO 4 and H with a concentration of 80 g / L 2 O 2 Mix according to the volume ratio of 3: 2 to form an acidic solution with a pH of 3.5. Immerse a pure nickel plate with a thickness of 1.5 mm in an alkaline solution for 15 min, wash it with clean water and then blow it dry to remove the oil stain on the surface of the nickel plate. Then, immerse the nickel plate in an acidic solution for activation for 30 s, wash it with clean water and then blow it dry to form a pre-treated nickel plate for standby use.

[0050] S502: Place the pretreated nickel plate inside the electrolytic tank, with part of it located at the bottom of the electrolytic tank and the other part located on the inner wall of the electrolytic tank to form an L-shaped structure. Pour the electrodeposition solution into the electrolytic tank and immerse the pretreated nickel plate at the bottom of the electrolytic tank.

[0051] S503: The pretreated nickel plate is used as the cathode to form a cathode plate, which is connected to the negative pole of the DC power supply. A stainless steel ball head rod with a ball rod diameter of 14 mm, a ball head diameter of 20 mm, and a total length of 100 mm is used as the anode to form an anode rod, which is connected to the positive pole of the DC power supply, and the distance between the bottom of the anode rod and the pretreated nickel plate at the bottom of the electrolytic cell is 2 mm. The DC current is 80 mA / cm 2 The electrolytic cell reciprocated at a reciprocating frequency of 38 mm / s within a stroke of 60 mm. Under the condition of a temperature of 40°C and reciprocating operation of the electrolytic cell, the electrodeposition solution was deposited by friction-assisted electrodeposition for 10 minutes to form a Ni-SiC composite coating on the surface of the nickel plate.

[0052] The macroscopic morphology of the copper plate prepared in the process of preparing the Cu-SiC composite coating in Example 1 was detected. Figure 4 At the same time, the Cu-SiC composite coating prepared in Example 1 was subjected to macroscopic morphology, microscopic morphology, microstructure, XRD and hardness tests, and the coating was obtained. Figure 5-9 .

[0053] By the attached Figure 4 It can be seen that during the friction-assisted electrodeposition process, the deposited particles in the electrodeposition solution gradually approached the friction effect area and gradually formed a deposited layer, which is related to the Figure 3 Corresponding to the principle in.

[0054] By the attached Figure 5It can be seen that the Cu-SiC composite coating is formed only in the friction effect area of ​​the copper plate, and no Cu-SiC composite coating is formed in other areas of the copper plate, achieving the effect of localized electrodeposition coating. In addition, the coating is easier to form in the friction effect area than in the area without friction effect, which enables the coating to form a metal-ceramic composite coating in the selected friction effect area in a shorter time.

[0055] By the attached Figure 6 , 7 It can be seen that the microstructure of the Cu-SiC composite coating is dense, without defects such as pores and cracks, which indicates that the Cu-SiC composite coating has high quality. In addition, the Cu-SiC composite coating has good bonding properties with the copper plate, and there are no defects such as cracks at the interface.

[0056] By the attached Figure 8 It can be seen that the main phases of the Cu-SiC composite coating are Cu and SiC, and no other phases are produced.

[0057] By the attached Fig. 9 It can be seen that the average microhardness of the Cu-SiC composite coating can reach 170HV, which is twice the hardness of the substrate, showing good mechanical properties.

[0058] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition, characterized in that: include: Prepare an electrodeposition solution, and perform acid-base treatment on a metal substrate to obtain a pretreated metal substrate; wherein the metal substrate is one of a copper plate, an iron plate, a chromium plate or a nickel plate; Placing the pretreated metal substrate in an electrolytic tank, with one part of the substrate at the bottom of the electrolytic tank and the other part on the inner wall of the electrolytic tank, and pouring the electrodeposition solution; The pretreated metal substrate is used as a cathode and a stainless steel ball-head rod is used as an anode. Triboelectrodeposition is performed under the reciprocating motion of the electrolytic cell to obtain a metal-ceramic composite coating deposited on the pretreated metal substrate; wherein the distance between the bottom of the anode and the pretreated metal substrate located at the bottom of the electrolytic cell is 1-3 mm.

2. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 1, characterized in that: The reciprocating motion frequency of the electrolytic cell is 5-50 mm / s, and the reciprocating motion stroke is 10-100 mm.

3. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 1, characterized in that: The temperature of triboelectrodeposition is 30-50°C.

4. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 1, characterized in that: The DC current of triboelectrodeposition is 50-100mA / cm 2 .

5. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 1, characterized in that: The diameter of the shaft of the stainless steel ball head stick is 6-14 mm, and the diameter of the ball head is 8-20 mm.

6. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 1, characterized in that: The acid-base treatment of the metal substrate comprises: Immerse the metal substrate in an alkaline solution for 10-20 minutes, then clean and dry it; wherein the alkaline solution comprises NaOH and Na2CO3 in a volume ratio of 1:(2-3); The metal substrate is immersed in an acidic solution with a pH of 3-4 for 20-40 seconds, cleaned and blown dry; wherein the acidic solution comprises H2SO4 and H2O2 in a volume ratio of 3:(2-3).

7. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 6, characterized in that: The concentrations of NaOH, Na2CO3, H2SO4 and H2O2 are 15g / L, 25g / L, 160g / L and 80g / L respectively.

8. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 1, characterized in that: The metal substrate is a copper plate, and the metal ceramic composite coating is a Cu-SiC composite coating; CuSO4·7H2O, H2SO4 and SiC mixed powders are mixed to form an electroplating solution, in which the concentrations of CuSO4·7H2O, H2SO4 and SiC mixed powders are 100-200 g / L, 30-60 g / L and 10-20 g / L respectively.

9. The method for preparing a metal-ceramic composite coating by friction-assisted electrodeposition according to claim 8, characterized in that: The SiC mixed powder is formed by mixing SiC powders with particle sizes of 3 μm, 5 μm and 10 μm.

10. A device for preparing metal-ceramic composite coating by friction-assisted electrodeposition, characterized in that: The invention comprises a fixed table (1), a reciprocating worktable (8) and a direct current power supply (10); the fixed table (1) is provided with a support arm (2), the end of the support arm (2) clamps an anode rod (4) through an insulating clamp (3); the reciprocating worktable (8) is provided with a heating plate (9), an electrolytic cell (5) is arranged on the heating plate (9), an electrolyte (7) and a cathode plate (6) are arranged in the electrolytic cell (5), a part of the cathode plate (6) is located at the bottom of the electrolytic cell (5), and the other part is located on the side wall of the electrolytic cell (5); the distance between the anode rod (4) and the cathode plate (6) located at the bottom of the electrolytic cell (5) is 1-3 mm; the direct current power supply (10) is electrically connected to the anode rod (4) and the cathode plate (6) respectively.

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