Resin matrix composite cylindrical part and inner surface metallization method thereof

Abstract

The invention belongs to the technical field of nonmetal surface metallization, and provides a resin-based composite cylindrical part and an inner surface metallization method thereof.The cylindrical part comprises a polymer extruded tube, the outer surface of the polymer extruded tube is wound with a resin-based fiber reinforced composite, and the inner surface of the polymer extruded tube is sprayed with metal powder. The method comprises the following steps: sleeving a polymer extruded tube on a core mold, and carrying out pretreatment such as surface roughening, plasma activation and adhesive coating on the outer surface of the polymer extruded tube; winding the resin-based fiber reinforced composite material on the pretreated polymer extruded tube, and removing the core mold to obtain a middleware; and metal powder is sprayed to the inner surface of the middleware in a cold spraying mode at the set preheating temperature and the set pressure, and the metalized resin-based composite material barrel-shaped part is obtained. On the premise that the structure of the cylindrical part is not obviously changed, it is guaranteed that the product has the advantages of being high in specific strength, high in specific modulus and the like, and meanwhile it is guaranteed that the inner surface of the cylindrical part has the good corrosion resistance, electric conduction and heat conduction capacity.

Description

Technical Field

[0001] The present invention belongs to the technical field of non-metal surface metallization, and relates to a resin matrix composite cylindrical part and a method for metallizing its inner surface. Background Art

[0002] Reinforced resin matrix composites are highly favored in fields such as aerospace and clean energy due to their high specific strength and specific modulus, and the advantage of performance designability at the same time. Typical resin matrix fiber-reinforced composite materials or ceramic fiber-reinforced composite material structural parts, such as pressure vessels, thin-walled cylinders, hollow discs, curved special-shaped structures, etc., often need to have one or more characteristics such as anti-corrosion, sealing, conductivity, and heat conduction according to the differences in the service environment on the premise of providing sufficient structural strength and stiffness.

[0003] To achieve the above purposes, a metal layer is deposited on the surface of the composite material for metallization treatment, such as deposition by electroplating, electroless plating, physical vapor deposition, chemical vapor deposition, etc., to endow the composite material with better electrical conductivity, corrosion resistance, wear resistance or other special functions. However, there are problems such as environmental protection, low vacuum treatment efficiency, and a large increase in cost during the implementation of the above processes.

[0004] Cold spraying is a newly emerging rapid additive manufacturing technology means in this century. By utilizing the special structure of a convergent-divergent Laval nozzle, metal particles are deposited on the substrate in a solid state under the action of high-speed gas. This method greatly reduces the influence of oxygen on metal particles, making cold spraying the fastest solution with the lowest porosity and oxidation degree in additive manufacturing processes.

[0005] However, due to the inherent characteristics of the resin matrix composite material substrate, it is determined that metal particles cannot undergo effective plastic deformation during the deposition process, which brings great difficulties to directly implementing the surface metallization of resin matrix composite materials by the cold spraying process. Summary of the Invention

[0006] In order to solve the technical problem that it is difficult to achieve the surface metallization of resin matrix composite materials by cold spraying technology, the present invention discloses a resin matrix composite cylindrical part, including a polymer extrusion tube, a resin matrix fiber-reinforced composite material is wound on the outer surface of the polymer extrusion tube, and metal powder is sprayed on the inner surface of the polymer extrusion tube.

[0007] Further, an adhesive is coated on the contact surface between the polymer extrusion tube and the resin matrix fiber-reinforced composite material.

[0008] Further, the metal powder is one or more of aluminum powder, copper powder, tin powder, zinc powder, titanium powder, nickel powder, tungsten powder, cobalt powder, iron powder, tantalum powder, molybdenum powder, zirconium powder or alloy powder.

[0009] Furthermore, the particle size of the metal powder is 5 μm to 100 μm.

[0010] Further, the polymer extrusion tube is prepared from any one of polyamide and its modified materials, polyimide and its modified materials, polyetheretherketone and its modified materials, polyetherketoneketone and its modified materials, polyphenylene sulfide and its modified materials, polyethyleneimine and its modified materials, polysulfone raw materials and its modified materials, polyurethane and its modified materials, and polycarbonate and its modified materials.

[0011] Further, the resin matrix fiber-reinforced composite material is made of any one of epoxy resin, phenolic resin, polyamide, polyimide, polyetheretherketone, polyetherketoneketone, polyphenylene sulfide, polyethyleneimine, polysulfone, polyurethane, or polycarbonate.

[0012] The present invention also provides a method for metallizing the inner surface of a resin matrix composite cylindrical part, and the method includes the following steps:

[0013] S1. Sleeve the polymer extrusion tube on the core mold, and successively perform pretreatment operations of surface roughening, plasma activation, and coating of an adhesive on the outer surface of the polymer extrusion tube;

[0014] S2. Wind the resin matrix fiber-reinforced composite material onto the pretreated polymer extrusion tube within a set time, and remove the core mold to obtain a resin matrix composite cylindrical intermediate part;

[0015] S3. Spray the metal powder onto the inner surface of the resin matrix composite cylindrical intermediate part by means of cold spraying under a set preheating temperature and a set pressure to obtain a metallized resin matrix composite cylindrical part.

[0016] Further, in step S1, before sleeving the polymer extrusion tube on the core mold, coat a release agent on the inner wall of the polymer extrusion tube; after removing the core mold, remove the release agent on the inner wall of the polymer extrusion tube.

[0017] Further, in step S1, a laser surface treatment method is used to perform surface roughening treatment on the outer surface of the polymer extrusion tube, and the control parameters of the laser surface treatment method are a galvanometer frequency of 25 Hz to 100 Hz, an amplitude of 10 μm to 50 μm, and a laser rate of moving along the axial direction of the polymer extrusion tube of 10 mm / s to 50 mm / s.

[0018] Further, in step S1, at least one plasma spray gun is reciprocally moved in a direction perpendicular to the polymer extrusion tube to perform plasma activation pretreatment on the outer surface of the polymer extrusion tube. The control parameters of the plasma activation pretreatment are an output limit voltage of 8 kV to 10 kV, an output current limit of 500 mA to 700 mA, an output power of 700 W to 1000 W, and a moving rate of 50 mm / s to 250 mm / s.

[0019] Compared with the prior art, the beneficial effects that can be achieved by at least one of the above technical solutions adopted in the embodiments of the present specification at least include: For the resin-based composite cylindrical part and its inner surface metallization method of the present invention, by winding a resin-based fiber-reinforced composite material on the outer surface of a polymer extrusion tube and simultaneously metallizing the inner surface of the polymer extrusion tube, a resin-based composite cylindrical part including the polymer extrusion tube, a resin-based fiber-reinforced composite material layer, and a metal layer is obtained. Without significantly changing its original structural characteristics, this resin-based composite cylindrical part still has advantages such as high specific strength and high specific modulus, and at the same time, it is convenient to metallize its inner surface to endow it with good corrosion resistance, electrical conductivity, and thermal conductivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0021] Figure 1 It is a flowchart of the inner surface metallization method of the resin-based composite cylindrical part disclosed in the embodiments of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0022] The embodiments of the present application will be described in detail below with reference to the drawings.

[0023] The following specific examples illustrate the implementation manners of the present application. Those skilled in the art can easily understand other advantages and effects of the present application from the content disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The present application can also be implemented or applied through other different specific implementation manners. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present application. It should be noted that, without conflict, the following embodiments and the features of the embodiments can be combined with each other. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts belong to the scope of protection of the present application.

[0024] It should also be noted that the diagrams provided in the following embodiments only illustrate the basic concept of the present disclosure in a schematic manner. The diagrams only show the components related to the present disclosure, rather than being drawn according to the number, shape, and size of the components in actual implementation. The type, quantity, and proportion of each component in actual implementation can be arbitrarily changed, and the component layout type may also be more complex.

[0025] An embodiment of the present invention provides a resin-based composite cylindrical part, including a polymer extrusion tube, with a resin-based fiber-reinforced composite material wound around the outer surface of the polymer extrusion tube, and a metal powder sprayed on the inner surface of the polymer extrusion tube.

[0026] Furthermore, an adhesive is coated on the contact surface between the polymer extrusion tube and the resin-based fiber-reinforced composite material. The adhesive can be any one of epoxy resin glue, acrylic glue, polyether ether ketone sealant, and modified adhesive.

[0027] Furthermore, the metal powder is one or more of aluminum powder, copper powder, tin powder, zinc powder, titanium powder, nickel powder, tungsten powder, cobalt powder, iron powder, tantalum powder, molybdenum powder, zirconium powder, or alloy powder.

[0028] Even further, the particle size of the metal powder is 5μm to 100μm.

[0029] Furthermore, the polymer extrusion tube is prepared from any one of polyamide and its modified materials, polyimide and its modified materials, polyether ether ketone and its modified materials, polyether ketone ketone and its modified materials, polyphenylene sulfide and its modified materials, polyethylene imine and its modified materials, polysulfone raw materials and its modified materials, polyurethane and its modified materials, and polycarbonate and its modified materials.

[0030] Furthermore, the resin-based fiber-reinforced composite material is made of any one of epoxy resin, phenolic resin, polyamide, polyimide, polyether ether ketone, polyether ketone ketone, polyphenylene sulfide, polyethylene imine, polysulfone, polyurethane, or polycarbonate.

[0031] An embodiment of the present invention also provides a method for metallizing the inner surface of a resin-based composite cylindrical part, as Figure 1 shown. The method includes the following steps:

[0032] S1. Put the polymer extrusion tube on the core mold, and perform pre-treatment operations on the outer surface of the polymer extrusion tube, including surface roughening, plasma activation, and coating of adhesive.

[0033] S2. Wind the resin-based fiber-reinforced composite material onto the pre-treated polymer extrusion tube within a set time, and remove the core mold to obtain a resin-based composite cylindrical intermediate part.

[0034] S3. Spray the metal powder onto the inner surface of the resin matrix composite cylindrical intermediate member by cold spraying under the set preheating temperature and set pressure to obtain a metalized resin matrix composite cylindrical part.

[0035] Further, in step S1, before sleeving the polymer extrusion tube on the core mold, apply a release agent to the inner wall of the polymer extrusion tube; after removing the core mold, remove the release agent on the inner wall of the polymer extrusion tube.

[0036] Further, in step S1, use a laser surface treatment method to perform surface roughening on the outer surface of the polymer extrusion tube. The control parameters of the laser surface treatment method are galvanometer frequency of 25 Hz to 100 Hz and amplitude of 10 μm to 50 μm. In specific implementation, the outer surface of the polymer extrusion tube can also be surface roughened by sandpaper polishing. When performing the roughening treatment, operate by controlling the rotation speed of the core mold. Among them, the rotation direction of the core mold is to move along the axial direction of the polymer extrusion tube, and the moving speed, that is, the laser speed of the laser, is 10 mm / s to 50 mm / s. After the roughening treatment is completed, a volatile and residue-free cleaning agent such as alcohol can be used to clean the outer surface of the polymer extrusion tube.

[0037] Further, in step S1, use at least one plasma spray gun to reciprocate along the direction perpendicular to the polymer extrusion tube to perform plasma activation pretreatment on the outer surface of the polymer extrusion tube. The control parameters of the plasma activation pretreatment are output limiting voltage of 8 kV to 10 kV, output limiting current of 500 mA to 700 mA, output power of 700 W to 1000 W, and moving rate of 50 mm / s to 250 mm / s. At the same time, the nozzle of the plasma spray gun can be controlled to be 10 mm to 30 mm away from the outer surface of the polymer extrusion tube to perform the plasma activation pretreatment operation. Among them, the number of plasma spray guns is not less than 1. Horizontally move the plasma spray gun through single-point or symmetrically placed planetary distribution to achieve different activation efficiencies on the outer surface of the entire polymer extrusion tube

[0038] Further, in step S1, during the process of winding the resin matrix fiber-reinforced composite material around the polymer extrusion tube, control the core mold not to be disengaged from the polymer extrusion tube to ensure the overall straightness of the resin matrix composite cylindrical part.

[0039] Further, in the specific implementation of step S2, the set time is 0 to 40 minutes, that is, within 40 minutes after the plasma activation treatment, apply an adhesive on the outer surface of the polymer extrusion tube, and complete the winding, laying or molding of the resin matrix fiber-reinforced composite cylindrical part.

[0040] Furthermore, in the specific implementation of step S3, the set preheating temperature is 150°C to 800°C, the set pressure is 0.5 MPa to 8.0 Mpa. At the same time, the gas supply pressure of the metal powder can be controlled at 0.5 MPa to 8.0 Mpa, and spraying is carried out at a position 10 mm to 30 mm away from the inner surface of the polymer extrusion tube.

[0041] For the resin-based composite cylindrical part and its inner surface metallization method of the present invention, by winding the resin-based fiber-reinforced composite material on the outer surface of the polymer extrusion tube and simultaneously metallizing the inner surface of the polymer extrusion tube, a resin-based composite cylindrical part including a polymer extrusion tube, a resin-based fiber-reinforced composite material layer, and a metal layer is obtained. Without significantly changing its original structural characteristics, this resin-based composite cylindrical part ensures that it still has advantages such as high specific strength and high specific modulus. At the same time, it is convenient to metallize its inner surface to make it have good corrosion resistance, electrical conductivity, and thermal conductivity.

[0042] Taking a resin-based carbon fiber-reinforced composite cylindrical part with a diameter of φ120 mm, a height of 200 mm, and a thickness of 5 mm as an example, cold spraying aluminum on its inner surface, its specific implementation method is explained.

[0043] First, a polyether ether ketone thin-walled extrusion tube with a diameter of φ120 mm, a height of 210 mm, and a thickness of 0.5 mm is sleeved on the winding mandrel after its inner wall is coated with a release agent.

[0044] Secondly, the outer surface of the extrusion tube is roughened with 600-grit sandpaper. During this process, the rotation rate of the mandrel is 1 rpm. After the roughening treatment is completed, surface dirt is removed with a vacuum cleaner, and the outer surface of the extrusion tube is wiped with ethanol. After drying, plasma activation is performed, and the mandrel is not removed during this process. A single plasma spray gun is used to activate the outer surface of the extrusion tube. The output limit voltage of the activation equipment is 9 kV, the output current limit is 600 mA, and the output power is 850 W. The plasma spray gun reciprocates horizontally perpendicular to the outer surface of the polyether ether ketone extrusion tube, with a moving rate of 200 mm / s and the nozzle 12 mm away from the outer surface of the extrusion tube.

[0045] Thirdly, after activation, a two-component epoxy adhesive is coated on the outer surface of the extrusion tube. After the winding and curing of the composite cylindrical part are completed, the mandrel is removed. After standing for 48 h, the two ends of the cylindrical part are turned to a height of 200 mm. After the inner surface of the removed cylindrical part is wiped thoroughly with ethanol, it is loaded into a lathe and rotated at a constant speed of 15 rpm.

[0046] Finally, start the dust suction and dust removal device, and the particle size D 50Aluminum powder with a size of about 30 μm and a purity of not less than 99% is preheated, and nitrogen is used as the conveying gas. The aluminum powder is deposited on the inner surface of the cylindrical part by a cold spraying device at a pressure of 3.3 MPa. During this process, the distance between the cold spraying nozzle and the inner surface of the cylindrical part is 15 mm. The spray gun moves uniformly from one side opening of the cylindrical part to the other side, and the moving speed along the axis.

[0047] The present invention also takes a cylindrical part made of epoxy resin carbon fiber reinforced composite material with a diameter of φ160 mm, a height of 400 mm, and a thickness of 2 mm as an example, and cold sprays an aluminum + aluminum oxide coating on its inner surface. The specific implementation method is as follows:

[0048] First, a polyether ether ketone thin-walled extrusion tube with an inner diameter of φ160 mm, a height of 410 mm, and a thickness of 0.3 mm is coated with a release agent on the inner wall and then sleeved on a winding mandrel. A laser cleaning device is used to roughen the outer surface of the extrusion tube. The galvanometer frequency of the laser is 50 Hz, the amplitude is 15 μm, the moving speed along the axis of the extrusion tube is 20 mm / s, and the laser cleaning width is about 50 mm. After the roughening treatment is completed, the surface dirt is removed by a vacuum cleaner, and the outer surface of the extrusion tube is wiped with ethanol. After drying, plasma activation is performed, and the mandrel is not removed during this process.

[0049] Second, a four-point planetary plasma spray gun is used to activate the outer surface of the extrusion tube. The output limiting voltage of the activation device is 10 kV, the output limiting current is 550 mA, and the output power is 800 W. The plasma spray gun moves horizontally back and forth perpendicular to the outer surface of the polyether ether ketone extrusion tube at a moving speed of 200 mm / s, and the distance between the nozzle and the outer surface of the extrusion tube is 12 mm. The activation treatment of the entire outer surface of the extrusion tube is quickly realized within 3 to 5 seconds. After the roughening treatment is completed, the outer surface of the extrusion tube is wiped with ethanol. After drying, a two-component epoxy adhesive is coated.

[0050] Third, the winding and laying of the 2-mm-thick epoxy resin carbon fiber reinforced composite cylindrical part are completed. After curing, the mandrel is removed and left standing for 48 h, and the two ends of the cylindrical part are turned to a height of 400 mm. After the inner surface of the removed cylindrical part is wiped thoroughly with ethanol, it is loaded into a lathe and rotated at a uniform speed of 15 rpm.

[0051] Finally, start the dust suction and dust removal device, and mix D 50 Spherical aluminum powder with a size of about 40 μm and 30 wt.% spherical aluminum oxide powder are mixed, and nitrogen is used as the conveying gas. They are deposited on the inner surface of the cylindrical part by a cold spraying process at a pressure of 3 MPa. During this process, the distance between the cold spraying nozzle and the inner surface of the cylindrical part is 20 mm. The spray gun moves uniformly from one side opening of the cylindrical part to the other side, and the moving speed along the axis is 1.5 mm / s.

[0052] It has been verified that for the resin-based composite cylindrical parts obtained by the method of the present invention, the aluminum coating (or the mixed coating of aluminum powder + alumina powder) is dense and complete, with a thickness of not less than 100 μm, and the bonding strength with the polyetheretherketone extrusion tube is not less than 3 Mpa.

[0053] Obviously, those skilled in the art should understand that the above description is only the preferred embodiment of the present invention and is not used to limit the present invention. For those skilled in the art, various changes and modifications can be made to the embodiments of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

[0054] In addition, it should be understood that although this specification is described according to the embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A resin-based composite material cylindrical part, characterized in that: The invention comprises a polymer extruded tube, the outer surface of which is wound with a resin-based fiber-reinforced composite material, and the inner surface of which is sprayed with metal powder.

2. The resin-based composite material cylindrical part according to claim 1, characterized in that: The contact surface between the polymer extrusion tube and the resin-based fiber-reinforced composite material is coated with adhesive.

3. The resin-based composite material cylindrical part according to claim 1, characterized in that: The metal powder is one or more of aluminum powder, copper powder, tin powder, zinc powder, titanium powder, nickel powder, tungsten powder, cobalt powder, iron powder, tantalum powder, molybdenum powder, zirconium powder or alloy powder.

4. The resin-based composite material cylindrical member according to any one of claims 1 to 3, characterized in that: The particle size of the metal powder is 5 μm to 100 μm.

5. The resin-based composite material cylindrical member according to claim 1, characterized in that: The polymer extruded tube is prepared by adopting any one of polyamide and its modified materials, polyimide and its modified materials, polyetheretherketone and its modified materials, polyetherketoneketone and its modified materials, polyphenylene sulfide and its modified materials, polyethyleneimine and its modified materials, polysulfone raw materials and its modified materials, polyurethane and its modified materials, and polycarbonate and its modified materials.

6. The resin-based composite material cylindrical member according to claim 1, characterized in that: The resin-based fiber-reinforced composite material is made of any one of epoxy resin, phenolic resin, polyamide, polyimide, polyetheretherketone, polyetherketoneketone, polyphenylene sulfide, polyethyleneimine, polysulfone, polyurethane or polycarbonate.

7. A method for metallizing the inner surface of a resin-based composite tubular member according to any one of claims 1 to 6, characterized in that: The method comprises: The polymer extruded tube is put on the core mold, and the outer surface of the polymer extruded tube is subjected to pretreatment operations of surface roughening, plasma activation and coating with adhesive in sequence; Winding the resin-based fiber-reinforced composite material onto the pretreated polymer extrusion tube within a set time, and removing the core mold to obtain a resin-based composite material cylindrical intermediate piece; Under a set preheating temperature and a set pressure, metal powder is sprayed onto the inner surface of the resin-based composite material cylindrical intermediate piece by cold spraying to obtain a metallized resin-based composite material cylindrical piece.

8. The inner surface metallization method of a resin-based composite material cylindrical member according to claim 7, characterized in that: Before the polymer extrusion tube is sleeved on the core mold, a release agent is coated on the inner wall of the polymer extrusion tube; after the core mold is removed, the release agent on the inner wall of the polymer extrusion tube is removed.

9. The inner surface metallization method of a resin-based composite material cylindrical member according to claim 7, characterized in that: The outer surface of the polymer extruded tube is roughened by a laser surface treatment method, wherein the control parameters of the laser surface treatment method are a galvanometer frequency of 25 Hz to 100 Hz, an amplitude of 10 μm to 50 μm, and a laser speed of 10 mm / s to 50 mm / s moving along the axial direction of the polymer extruded tube.

10. The inner surface metallization method of a resin-based composite material cylindrical member according to claim 7, characterized in that: At least one plasma spray gun is used to reciprocate in a direction perpendicular to the polymer extruded tube to perform plasma activation pretreatment on the outer surface of the polymer extruded tube, wherein the control parameters of the plasma activation pretreatment are output limiting voltage 8kV-10kV, output limiting current 500mA-700mA, output power 700W-1000W and moving speed 50mm / s-250mm / s.

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