WO2018171076A1 - Combined piece of stainless steel and plastic and processing method therefor - Google Patents

Combined piece of stainless steel and plastic and processing method therefor Download PDF

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Publication number
WO2018171076A1
WO2018171076A1 PCT/CN2017/090914 CN2017090914W WO2018171076A1 WO 2018171076 A1 WO2018171076 A1 WO 2018171076A1 CN 2017090914 W CN2017090914 W CN 2017090914W WO 2018171076 A1 WO2018171076 A1 WO 2018171076A1
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WIPO (PCT)
Prior art keywords
stainless steel
plastic
recessed structure
steel substrate
acid
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PCT/CN2017/090914
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French (fr)
Chinese (zh)
Inventor
张法亮
董晓佳
王成
张孟军
刘鸿章
唐红平
刘利强
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歌尔股份有限公司
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Publication of WO2018171076A1 publication Critical patent/WO2018171076A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning

Definitions

  • the invention relates to the field of product compounding technology, and more particularly to a joint of stainless steel and plastic and a processing method thereof.
  • nano-scale pores are formed by processing in a plurality of processing steps on the surface of the metal substrate, and the nano-sized pores are generally perpendicular to the metal substrate.
  • the micro-scale macropores can be formed on the surface of the metal substrate, and further etched to form nano-sized pores.
  • the plastic is pressed directly into the surface of the metal substrate having several nanometer-sized pores.
  • this method can only be applied on a large scale on aluminum alloys and cannot be applied to other metals or alloys such as stainless steel. This is because nano-sized pores are not readily available in most other metals or alloys, or the size and distribution of the pores obtained by this method do not have the effect of making the metal firmly bonded to the plastic.
  • the nano-injection method is combined with plastic on stainless steel, the composite product formed after the combination has many problems such as unstable process and poor reliability. Therefore, it is necessary to improve the existing stainless steel and plastic composite products and their processing methods.
  • a combination of stainless steel and plastic comprises a stainless steel substrate, which is subjected to a heat treatment at 400-900 degrees Celsius and then etched by an etching solution.
  • the surface of the stainless steel substrate is formed with a plurality of recessed structures, the recessed structure has an average depth of 0.1-30 micrometers, the recessed structure has an average width of 0.2-15 micrometers, and the stainless steel substrate is injection molded with plastic. A portion of the structure in the plastic is embedded within the recessed structure.
  • the heat treatment temperature is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours.
  • the recessed structure has an average length greater than 0.2 microns.
  • the recess structure comprises at least one of a strip structure, a fold structure, and a curved structure.
  • the projection of the recessed structure on the surface of the stainless steel substrate comprises a closed pattern.
  • the cross-sectional shape of the recessed structure in a direction perpendicular to the surface of the stainless steel substrate comprises at least one of an inverted triangle, an arc, a U, and a quad.
  • the etching solution comprises at least one of nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, oxalic acid, acetic acid, hydrofluoric acid, maleic acid, phthalic acid, oxalic acid solution and a salt solution thereof.
  • the etching solution comprises: a combination of 5-30% oxalic acid solution and a chloride or sulfate, a combination of 1-60% nitric acid and chloride or oxide, 10-30% nitric acid and 5-15% At least one of a combination of a metal nitrate and a 2-10% sulfate.
  • the etching treatment has a temperature of 20-90 degrees Celsius and a time of 1-50 minutes.
  • an oxide film layer is formed on a surface of the recess structure, and the oxide film layer has a thickness of 1-20 nm.
  • the oxide film layer includes at least two of iron oxide, chromium oxide, and nickel oxide.
  • the plastic comprises a thermoplastic resin and a filler material
  • the filler material is 5-40% by mass in the plastic
  • the filler material comprises nylon fiber, carbon fiber, glass fiber, and aramid fiber.
  • the thermoplastic resin comprises at least one of a polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin.
  • a process for processing a joint of stainless steel and plastic law comprises: providing a stainless steel substrate; performing a heat treatment at 400-900 degrees Celsius and performing an etching solution etching process, and forming a plurality of average depths of 0.1-30 micrometers and an average width of 0.2-15 micrometers on the surface of the stainless steel substrate. a recessed structure; plastic is injection molded onto the surface of the stainless steel substrate such that a portion of the structure in the plastic is embedded into the recessed structure to form a joint of stainless steel and plastic.
  • the heat treatment temperature is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours.
  • the etching solution comprises at least one of nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, oxalic acid, acetic acid, hydrofluoric acid, maleic acid, phthalic acid, oxalic acid solution and a salt solution thereof.
  • the etching solution comprises: a combination of 5-30% oxalic acid solution and a chloride or sulfate, a combination of 1-60% nitric acid and chloride or oxide, 10-30% nitric acid and 5-15% At least one of a combination of a metal nitrate and a 2-10% sulfate.
  • the temperature during the etching of the etching solution is 20-90 degrees Celsius and the time is 1-50 minutes.
  • an oxide film layer is further formed on the surface of the stainless steel substrate, and the oxide film layer has a thickness of 1 to 20 nm.
  • the oxide film layer includes at least two of iron oxide, chromium oxide, and nickel oxide.
  • the plastic comprises a thermoplastic resin and a filler material
  • the filler material is 5-40% by mass in the plastic
  • the filler material comprises nylon fiber, carbon fiber, glass fiber, and aramid fiber.
  • the thermoplastic resin comprises at least one of a polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin.
  • the inventors of the present invention have found that the nano-injection method commonly used in the prior art is combined with plastic on stainless steel, and the composite product formed by nano-scale small-hole injection molding has many problems such as unstable process and poor reliability.
  • the stainless steel substrate in the present invention is subjected to heat treatment at 400-900 degrees Celsius, that is, sensitization treatment, which exacerbates precipitation and precipitation of carbon chromium compounds in crystal defects, and can be on a stainless steel substrate.
  • a severe chromium-depleted region is formed, which is etched through the etching solution to form a plurality of micron-sized recessed structures in the chromium-depleted region.
  • the bonding force of the stainless steel substrate and the plastic after injection molding by the recessed structure is greater.
  • the process flow is shortened, the production cost is reduced, and it is more suitable for mass production. There is no special material requirement for injection molding plastics, and the scope of application is wider.
  • FIG. 1 is a schematic structural view of a joint of stainless steel and plastic provided in an embodiment of the present invention
  • FIG. 2 is a schematic view showing a recessed structure on a stainless steel substrate provided in an embodiment of the present invention
  • FIG. 3 is a schematic view showing a recessed structure on a stainless steel substrate provided in an embodiment of the present invention.
  • Fig. 4 is a schematic cross-sectional view showing the combination of stainless steel and plastic in the embodiment of the present invention.
  • the present invention provides a joint of stainless steel and plastic that includes a stainless steel substrate and plastic.
  • the stainless steel substrate 1 is subjected to heat treatment at 400-900 degrees Celsius, that is, sensitization treatment, which exacerbates the precipitation and precipitation of carbides in the crystal defect portion, and can form a serious on the stainless steel substrate 1.
  • Chromium-poor area After etching through the etching solution, a plurality of micron-sized recessed structures 11 are formed in the chromium-depleted region, and the recessed structures 11 are micron-scale etch marks.
  • the obtained recessed structure 11 has an inclined angle with the surface of the stainless steel substrate 1, for example, it may have a different inclination angle from the surface of the stainless steel substrate 1.
  • the recessed structure 11 has an average depth H of 0.1 to 30 ⁇ m, and the recessed structure 11 has an average width W of 0.2 to 15 ⁇ m.
  • the recess structure 11 includes a first recess structure having a slope with respect to a surface of the stainless steel substrate 1. The slope of the first recessed structure with respect to the surface of the stainless steel substrate 1 may have different values.
  • the recessed structure 11 may further include a second recessed structure perpendicular to the surface of the stainless steel substrate 1. As such, the recessed structure 11 including the first recessed junction and the second recessed structure has different inclination angles with respect to the surface of the stainless steel substrate 1.
  • the recessed structure 11 formed by the etching of the etching solution has a great relationship with the chromium-depleted region in the structure of the stainless steel substrate 1.
  • the stainless steel substrate 1 is subjected to heat treatment between 400 and 900 °C.
  • the stainless steel substrate 1 is heated between 400 and 900 degrees Celsius, or slowly cooled through the temperature of this interval, intergranular segregation occurs, which exacerbates the precipitation and precipitation of carbides in the crystal defects, in the crystal grains. Severe chromium-depleted areas are rapidly formed on both sides and near crystal defects.
  • Theoretical analysis and experimental verification show that, taking the grain boundary as an example, when the heat treatment temperature of stainless steel is lower than 400 degrees Celsius, it is difficult to form chromium carbide on the grain boundary, and it is difficult to form a chromium-depleted region near the grain boundary.
  • the heat treatment temperature is higher than 900 degrees Celsius, the diffusion capacity of chromium is enhanced, and the chromium in the crystal grains can diffuse to the grain boundary, and the chromium-depleted region is not formed due to the precipitation of chromium carbide.
  • a region where the corrosion and corrosion resistance are cross-distributed is formed on the stainless steel substrate 1.
  • a chromium-depleted region is a solute atom, an impurity, and a second equal enrichment region, which can form a living-passive micro-galvanic structure, and then corrode and corrode in a corrosive region through erosion of a specific corrosive medium.
  • the stainless steel substrate 1 is injection molded with a plastic 2, and a part of the structure of the plastic 2 is embedded in the recessed structure 11 to form the joint. Since the recessed structure 11 has different inclination angles with respect to the surface of the stainless steel substrate 1, a part of the structure in the plastic 2 can be embedded into the inside of the recessed structure 11 at different inclination angles. Alternatively, the recessed structure 11 may be formed only on the stainless steel substrate 1 where the plastic 2 needs to be injection molded. Alternatively, the recessed structure 11 may be formed on the entire surface of the stainless steel substrate 1.
  • the combination of stainless steel and plastic provided by the invention has the following technical effects. Firstly, by heat treatment of stainless steel, that is, sensitization treatment, intergranular segregation is generated, which exacerbates precipitation of carbides in crystal defects, in the crystal grains. Severe chromium-depleted areas are formed on both sides and crystal defects, which are corrosive areas. After etching by the etching solution, a plurality of micron-sized recessed structures 11 are formed in the easily corrodible region. Since the recessed structure 11 and the surface of the stainless steel substrate 1 have different inclination angles, when the plastic 2 is injection molded onto the surface of the stainless steel substrate 1, a part of the structure in the plastic 2 can be inclined at different angles.
  • the plastic 2 can be embedded in the recessed structure 11 on the surface of the stainless steel substrate 1 like the root of the plant, and the bonding force is large, and the plastic 2 is not easily peeled off during stretching or shearing.
  • Fig. 4 is a schematic cross-sectional view showing the combination of the stainless steel substrate 1 and the plastic 2 in this embodiment.
  • the micro-scale recessed structure 11 formed by etching is larger and deeper, and the plastic 2 can be better filled in the recessed structure 11 without the activation of the porogen.
  • the joint fractured portion is in the middle of the plastic 2, and the joint surface of the plastic 2 and the stainless steel substrate 1 is not cracked, thereby demonstrating the between the stainless steel substrate 1 and the plastic 2 in the present invention. Has a strong binding force.
  • the stainless steel substrate 1 has regions of different structures, such as a chromium-depleted region, such as high-potential substances such as solid solution atoms, second phase, and impurities, or crystal defects such as grain boundaries and twins. It is a high-energy, lively area. Impregnated in the corrosive solution of this scheme, the above areas preferentially corrode and fall off, while other areas only cause slight corrosion, which greatly reduces the consumption of corrosive liquid.
  • the recessed structure 11 can be formed by one dipping.
  • a corrosion extension can be added on the basis of the first etching.
  • the recessed structure 11. After that, direct injection molding eliminates the need for additional processing. Therefore, the technical solution of the present invention is simplified in the hole forming process, and the scrap rate of the joint member is reduced.
  • the injection molded plastic of the present invention is suitable for most plastics, including thermoplastic resins such as polyphenylene sulfide resin (PPS), polybutylene terephthalate resin (PBT), polyamide (PA), polycarbonate. (PC), polyolefin, polystyrene.
  • thermoplastic resins such as polyphenylene sulfide resin (PPS), polybutylene terephthalate resin (PBT), polyamide (PA), polycarbonate. (PC), polyolefin, polystyrene.
  • PPS polyphenylene sulfide resin
  • PBT polybutylene terephthalate resin
  • PA polyamide
  • PC polycarbonate.
  • polyolefin polystyrene
  • Plastics in injection molding require heat generated by an exothermic reaction to retard solidification in the pores.
  • the size of the micron-sized recessed structure 11 in the present invention is large, and a good filling can be obtained without the exothermic reaction of the plastic and the pore-piercing agent, thereby expanding the selection range of the plastic.
  • the temperature of the heat treatment is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours.
  • heat treatment of the stainless steel substrate 1 for a certain period of time within this temperature range can rapidly form a severe chromium-depleted region.
  • the cross section of the recessed structure 11 in a direction perpendicular to the surface of the stainless steel substrate 1 includes at least one of an inverted triangle, an arcuate shape, a U shape, and a quadrangular shape.
  • the plastic 2 is easily inserted into the recessed structure 11 during injection molding.
  • the extending direction and the distribution form of the recessed structure 11 may be different in that the recessed structure 11 obtained by etching can generate an adsorption force to the plastic 2 embedded in the injection molding.
  • the recess structure 11 may include at least one of a strip structure, a fold structure, and a curved structure.
  • the inner recessed space formed by the recessed structure should ensure good coherence and no abrupt change in the direction of extension. In this way, it is more convenient to embed the plastic 2 into the recessed structure 11.
  • the intergranular corrosion on the stainless steel substrate 1 is performed along the edges of the crystal grains, and thus the projection of the recessed structure 11 on the surface of the stainless steel substrate 1 may include a closed pattern.
  • the closed pattern may be a closed figure of a rectangle, a ring or other irregular shape surrounding the die.
  • Figure 2 and Figure 3. It should be noted that the closed pattern may be formed by at least one of a plurality of strip structures, a fold structure, and a curved structure.
  • the projection of the recessed structure 11 on the surface of the stainless steel substrate 1 may also include an open pattern. As shown in Figure 3,
  • the recessed structure 11 may be a strip structure or the like having an average length L of more than 0.2 ⁇ m.
  • the surface of the recessed structure 11 is formed with an oxide film layer having a thickness of 1 to 20 nm.
  • the oxide film layer includes at least two of iron oxide, chromium oxide, and nickel oxide. Compared with the stainless steel substrate 1, the thermal conductivity of the oxide film is low, and the heat loss of the plastic 2 can be reduced during injection molding, and the time for solidification and crystallization of the plastic 2 is delayed, so that the plastic 2 can be more fully filled in the recessed structure 11 The bottom of the recessed structure 11 can also achieve better filling.
  • the thermal conductivity of stainless steel is 16.3 W / m ⁇ K
  • the thermal conductivity of ferric oxide is 5.1 W / m ⁇ K
  • the thermal conductivity of ferrous oxide is 15.0 W / m ⁇ K
  • oxidation The thermal conductivity of chromium is about 10 W/m ⁇ K.
  • the formation mode of the oxide film layer is not limited, and may include high temperature oxidation, chemical passivation, and electrochemical passivation. In either case, the final effect is to form a dense, thermally insulating oxide film on the stainless steel surface.
  • the linear expansion coefficient of the plastic 2 should be as close as possible to the stainless steel substrate 1 to facilitate the curing of the injection molding. Since the linear expansion coefficient of PPS or PBT materials commonly used for injection molding is about 6-8 ⁇ 10 -5 /°C, and the linear expansion coefficient of stainless steel is 1.5 ⁇ 10 -5 /°C, the difference is large. Therefore, it is necessary to modify the main component resin material to significantly lower the linear expansion coefficient of the composition.
  • the plastic 2 comprises a thermoplastic resin and a filling material.
  • the thermoplastic resin may include a polyolefin polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, a polyolefin, or the like.
  • the mass percentage of the filler material in the plastic 2 may be 5-40%.
  • the filler material may include at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, and clay.
  • the filler material improves the main component resin material of the plastic 2, and can significantly reduce the linear expansion coefficient of the plastic 2, thereby approaching the linear expansion coefficient of the stainless steel.
  • a method of processing stainless steel and plastic joints includes:
  • a stainless steel substrate 1 is provided to facilitate injection molding of the plastic 2 onto the surface of the stainless steel substrate 1.
  • commonly used stainless steels include austenitic stainless steel and martensitic stainless steel, and the chromium content in the structure is greater than 12%.
  • the chromium atom has a small diffusion rate in stainless steel and is easy to form a chromium-depleted region.
  • the main reason for the strong corrosion resistance of stainless steel is that the chromium element is oxidized to form a dense oxide film, which improves the corrosion resistance of the material. Therefore, a large number of areas of corrosion-prone areas such as chromium-depleted areas are followed by stainless steel. Etching provides a good basis for organization.
  • the present technical solution is not applicable to steel materials, but is applicable to all stainless steels.
  • the stainless steel substrate 1 is subjected to heat treatment between 400 and 900 degrees Celsius.
  • precipitation of carbides at the crystal defect sites is aggravated, and severe chromium-depleted regions are formed on both sides of the crystal grains and crystal defects. Since the corrosion rate between the chromium-depleted region and other regions is inconsistent, that is, the corrosion rate of the chromium-depleted region is greater than that of other regions, a region where the corrosion and corrosion resistance are cross-distributed is formed on the stainless steel substrate 1.
  • the temperature of the heat treatment is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours.
  • heat treatment of the stainless steel substrate 1 for a certain period of time within this temperature range can rapidly form a severe chromium-depleted region.
  • the interior of the recessed structure 11 is more consistent, and the plastic 2 is more easily embedded in the interior thereof.
  • the stainless steel substrate 1 is subjected to an etching solution etching treatment to form a micron-sized recessed structure 11. 2, 3, and 4 show surface topography features etched by the present technical solution.
  • the recessed structure 11 has an average depth H of 0.1-30 microns and an average width W of 0.2-15 microns.
  • the recessed structure 11 includes a first recessed structure having a slope with respect to the stainless steel substrate 1.
  • the slope of the first recessed structure with respect to the surface of the stainless steel substrate 1 may have different values.
  • the recessed structure 11 may further include a second recessed structure perpendicular to the surface of the stainless steel substrate 1.
  • the recessed structure 11 including the first recessed junction and the second recessed structure has different inclination angles with respect to the surface of the stainless steel substrate 1. It is possible to cause a part of the structure in the plastic 2 to be embedded in the recessed structure 11 like the root of the plant with a greater bonding force therebetween.
  • the key to the corrosion of stainless steel to form the recessed structure 11 is the inconsistency of the corrosion rate between the chromium-depleted area and other areas, that is, the corrosion rate of the chromium-depleted area is greater than that of other areas. Therefore, the type and composition of the etching liquid not only determine whether or not the recessed structure 11 can be formed, but also determines the size of the recessed structure 11. Therefore, several sets of etching liquids are preferred in the present scheme to constitute a weak oxidizing medium, which is more advantageous for the formation of the micro-scale recessed structure 11.
  • the etching solution comprises at least one of nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, oxalic acid, acetic acid, hydrofluoric acid, maleic acid, phthalic acid, oxalic acid solution and a salt solution thereof.
  • the etching solution comprises: 5-30% oxalic acid At least a combination of a solution with a chloride or sulfate, a combination of 1-60% nitric acid and chloride or oxide, 10-30% nitric acid, and 5-15% metal nitrate and 2-10% sulfate
  • a solution with a chloride or sulfate a combination of 1-60% nitric acid and chloride or oxide
  • 10-30% nitric acid and 5-15% metal nitrate and 2-10% sulfate
  • the temperature during the etching of the etching solution is 20-90 degrees Celsius and the duration is 1-50 minutes.
  • the size, shape, and the like of the desired recessed structure 11 can be obtained.
  • the stainless steel substrate 1 may be subjected to degreasing and degreasing treatment prior to etching.
  • the stainless steel substrate 1 can be immersed in a cleaning agent of 35-80 degrees Celsius for ultrasonic treatment for 60-600 seconds. After that, rinse with pure water.
  • the cleaning agent may be an acid, a base or an organic solvent of 100 to 300 g/L or the like.
  • the surface of the stainless steel substrate 1 may be processed to form an oxide film layer.
  • the oxide film layer may have a thickness of 1 to 20 nm.
  • the oxide film layer may include at least two of iron oxide, chromium oxide, and nickel oxide.
  • the heat loss of the plastic 2 can be reduced during the injection molding, and the time for solidification and crystallization of the plastic 2 can be delayed, so that the plastic 2 can be more fully filled in the recessed structure 11, and the bottom of the recessed structure 11 can also be better.
  • the padding It should be noted that the formation mode of the oxide film layer is not limited, and may include high temperature oxidation, chemical passivation, and electrochemical passivation. In either case, the final effect is to form a dense, thermally insulating oxide film on the stainless steel surface.
  • plastic 2 is injection molded onto the surface of the stainless steel substrate 1, and a part of the structure in the plastic 2 is embedded in the recessed structure 11 to form a joint of stainless steel and plastic.
  • the plastic 2 comprises a thermoplastic resin and a filling material.
  • the thermoplastic resin may include at least one of a polyolefin polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin.
  • the mass percentage of the filler material in the plastic 2 may be 5-40%.
  • the filler material may include at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, and clay.
  • the filler material improves the main component resin material of the plastic 2, and can significantly reduce the linear expansion coefficient of the plastic 2, thereby approaching the linear expansion coefficient of the stainless steel.
  • the stainless steel is first exposed to a temperature of 700 degrees Celsius.
  • the steel substrate 1 is subjected to heat treatment; the stainless steel substrate 1 is etched by a combined etching solution of 10-30% nitric acid and 5-15% metal nitrate and 2-10% sulfate, and the etching temperature is 60 degrees Celsius;
  • a plastic material mixed with PBT + 30 wt% glass fibers was injected onto the surface of the stainless steel substrate 1 to finally obtain a joint of stainless steel and plastic.

Abstract

A combined piece of stainless steel and plastic and a processing method therefor. The combined piece comprises: a stainless steel substrate (1), and after undergoing heat processing at 400-900 degrees Celsius and then being etched by means of an etching solution, a plurality of recessed structures (11) are formed on a surface of the stainless steel substrate, the average depth of the recessed structures being 0.1-30 microns, while the average width of the recessed structures (11) is 0.2-15 microns; the stainless steel substrate (1) is injection-molded with plastic (2), and a part of the structure of the plastic (2) is embedded within the recessed structures (11). The stainless steel substrate (1) undergoes heat processing at 400-900 degrees Celsius to form a severely chromium-depleted area, and is then etched by means of the etching solution to form the plurality of micron-sized recessed structures (11) on the chromium-depleted area; after injection molding, the stability of the combined piece is increased, said piece is more air tight, the process procedure is shortened, and production costs are reduced, while the present invention is more suitable for large-scale production, has no special material requirements for injection molding plastic, and has a wider application range.

Description

一种不锈钢和塑料的结合件及其加工方法Combined piece of stainless steel and plastic and processing method thereof 技术领域Technical field
本发明涉及产品复合技术领域，更具体地，本发明涉及一种不锈钢和塑料的结合件及其加工方法。The invention relates to the field of product compounding technology, and more particularly to a joint of stainless steel and plastic and a processing method thereof.
背景技术Background technique
随着电子行业的快速发展，越来越多电子产品的外壳采用金属和塑料结合后形成的复合产品，以达到外观金属表现，内部塑料的目的。With the rapid development of the electronics industry, more and more electronic products are made of a composite product formed by combining metal and plastic to achieve the purpose of appearance metal and internal plastic.
目前，在金属和塑料注塑结合的方法中，一般在金属基材的表面通过多道处理工序加工形成纳米级小孔，该纳米级小孔一般垂直于金属基材。具体的，可先在金属基材表面处理形成微米级大孔，再进一步腐蚀形成纳米级小孔。且为达到较佳的填充效果，往往又要在细孔壁上披覆一层润孔剂或氧化膜。最后，将塑料直接压入具有若干纳米级小孔的金属基材表面。但是，此种方法仅能在铝合金上大规模应用，不能应用与不锈钢等其他金属或合金中。这是因为纳米级小孔在其他大多数金属或者合金中并不容易获得，或通过该方法获得的小孔的尺寸、分布不具有使得金属具有牢固结合塑料的效果。At present, in the method of metal-plastic injection molding, generally, nano-scale pores are formed by processing in a plurality of processing steps on the surface of the metal substrate, and the nano-sized pores are generally perpendicular to the metal substrate. Specifically, the micro-scale macropores can be formed on the surface of the metal substrate, and further etched to form nano-sized pores. In order to achieve a better filling effect, it is often necessary to coat a pore wall with a layer of a pore-orating agent or an oxide film. Finally, the plastic is pressed directly into the surface of the metal substrate having several nanometer-sized pores. However, this method can only be applied on a large scale on aluminum alloys and cannot be applied to other metals or alloys such as stainless steel. This is because nano-sized pores are not readily available in most other metals or alloys, or the size and distribution of the pores obtained by this method do not have the effect of making the metal firmly bonded to the plastic.
因此，在不锈钢上若采用该种纳米注塑方法结合塑料，结合后形成的复合产品存在工艺不稳定、可靠性差等诸多问题。因而有必要对现有不锈钢和塑料复合产品及其加工方法进行改进。Therefore, if the nano-injection method is combined with plastic on stainless steel, the composite product formed after the combination has many problems such as unstable process and poor reliability. Therefore, it is necessary to improve the existing stainless steel and plastic composite products and their processing methods.
发明内容Summary of the invention
有鉴于此，本发明的一个目的是提供一种不锈钢和塑料的结合件及其加工方法的新技术方案。In view of this, it is an object of the present invention to provide a new technical solution for a joint of stainless steel and plastic and a method of processing the same.
根据本发明的第一方面，提供了一种不锈钢和塑料的结合件。该结合件包括不锈钢基材，经400-900摄氏度的热处理再通过腐蚀液蚀刻后，在 所述不锈钢基材的表面形成有若干凹陷结构，所述凹陷结构的平均深度为0.1-30微米，所述凹陷结构的平均宽度为0.2-15微米，所述不锈钢基材上注射成型有塑料，所述塑料中的部分结构嵌入在所述凹陷结构内。According to a first aspect of the invention, a combination of stainless steel and plastic is provided. The bonding member comprises a stainless steel substrate, which is subjected to a heat treatment at 400-900 degrees Celsius and then etched by an etching solution. The surface of the stainless steel substrate is formed with a plurality of recessed structures, the recessed structure has an average depth of 0.1-30 micrometers, the recessed structure has an average width of 0.2-15 micrometers, and the stainless steel substrate is injection molded with plastic. A portion of the structure in the plastic is embedded within the recessed structure.
可选地，所述热处理的温度为600-800摄氏度，所述热处理的时间为2-5小时。Alternatively, the heat treatment temperature is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours.
可选地，所述凹陷结构的平均长度大于0.2微米。Optionally, the recessed structure has an average length greater than 0.2 microns.
可选地，所述凹陷结构包括条形结构、折形结构、曲形结构中的至少一种。Optionally, the recess structure comprises at least one of a strip structure, a fold structure, and a curved structure.
可选地，所述凹陷结构在所述不锈钢基材表面上的投影包括封闭的图形。Optionally, the projection of the recessed structure on the surface of the stainless steel substrate comprises a closed pattern.
可选地，所述凹陷结构在垂直于所述不锈钢基材表面的方向上的截面形状包括倒三角形、弓形、U形、四边形中的至少一种。Optionally, the cross-sectional shape of the recessed structure in a direction perpendicular to the surface of the stainless steel substrate comprises at least one of an inverted triangle, an arc, a U, and a quad.
可选地，所述腐蚀液包括：硝酸、磷酸、硫酸、亚硫酸、盐酸、草酸、醋酸、氢氟酸、马来酸、苯二酸、乙二酸溶液及其盐溶液中的至少一种。Optionally, the etching solution comprises at least one of nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, oxalic acid, acetic acid, hydrofluoric acid, maleic acid, phthalic acid, oxalic acid solution and a salt solution thereof. .
可选地，所述腐蚀液包括：5-30％草酸溶液与氯化盐或硫酸盐的组合、1-60％硝酸与氯化物或氧化物的组合、10-30％硝酸和5-15％金属硝酸盐和2-10％硫酸盐的组合中的至少一种。Optionally, the etching solution comprises: a combination of 5-30% oxalic acid solution and a chloride or sulfate, a combination of 1-60% nitric acid and chloride or oxide, 10-30% nitric acid and 5-15% At least one of a combination of a metal nitrate and a 2-10% sulfate.
可选地，所述蚀刻处理的温度为20-90摄氏度，时间为1-50分钟。Optionally, the etching treatment has a temperature of 20-90 degrees Celsius and a time of 1-50 minutes.
可选地，在所述凹陷结构的表面形成有氧化膜层，所述氧化膜层的厚度为1-20纳米。Optionally, an oxide film layer is formed on a surface of the recess structure, and the oxide film layer has a thickness of 1-20 nm.
可选地，所述氧化膜层至少包括铁氧化物、铬氧化物和镍氧化物中的两种。Optionally, the oxide film layer includes at least two of iron oxide, chromium oxide, and nickel oxide.
可选地，所述塑料包括热塑性树脂和填充材料，所述填充材料在所述塑料中的质量百分比为5-40％，所述填充材料包括尼龙纤维、碳纤维、玻璃纤维、芳香族聚酰胺纤维、碳酸钙、碳酸镁、二氧化硅及黏土中的至少一种。Optionally, the plastic comprises a thermoplastic resin and a filler material, the filler material is 5-40% by mass in the plastic, and the filler material comprises nylon fiber, carbon fiber, glass fiber, and aramid fiber. At least one of calcium carbonate, magnesium carbonate, silica, and clay.
可选地，所述热塑性树脂至少包括聚苯硫醚树脂、聚对苯二甲酸丁醇树脂、聚酰胺、聚碳酸酯和聚烯烃中的至少一种。Optionally, the thermoplastic resin comprises at least one of a polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin.
根据本发明的第二方面，提供了一种不锈钢和塑料结合件的加工方 法。该加工方法包括：提供不锈钢基材；经400-900摄氏度的热处理再进行腐蚀液蚀刻处理，在所述不锈钢基材的表面形成若干平均深度为0.1-30微米、平均宽度为0.2-15微米的凹陷结构；将塑料注塑到所述不锈钢基材的表面，使所述塑料中的部分结构嵌入至所述凹陷结构内，以形成不锈钢和塑料的结合件。According to a second aspect of the present invention, there is provided a process for processing a joint of stainless steel and plastic law. The processing method comprises: providing a stainless steel substrate; performing a heat treatment at 400-900 degrees Celsius and performing an etching solution etching process, and forming a plurality of average depths of 0.1-30 micrometers and an average width of 0.2-15 micrometers on the surface of the stainless steel substrate. a recessed structure; plastic is injection molded onto the surface of the stainless steel substrate such that a portion of the structure in the plastic is embedded into the recessed structure to form a joint of stainless steel and plastic.
可选地，所述热处理的温度为600-800摄氏度，所述热处理的时间为2-5小时。Alternatively, the heat treatment temperature is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours.
可选地，所述腐蚀液包括：硝酸、磷酸、硫酸、亚硫酸、盐酸、草酸、醋酸、氢氟酸、马来酸、苯二酸、乙二酸溶液及其盐溶液中的至少一种。Optionally, the etching solution comprises at least one of nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, oxalic acid, acetic acid, hydrofluoric acid, maleic acid, phthalic acid, oxalic acid solution and a salt solution thereof. .
可选地，所述腐蚀液包括：5-30％草酸溶液与氯化盐或硫酸盐的组合、1-60％硝酸与氯化物或氧化物的组合、10-30％硝酸和5-15％金属硝酸盐和2-10％硫酸盐的组合的至少一种。Optionally, the etching solution comprises: a combination of 5-30% oxalic acid solution and a chloride or sulfate, a combination of 1-60% nitric acid and chloride or oxide, 10-30% nitric acid and 5-15% At least one of a combination of a metal nitrate and a 2-10% sulfate.
可选地，所述腐蚀液蚀刻过程中的温度为20-90摄氏度，时间为1-50分钟。Optionally, the temperature during the etching of the etching solution is 20-90 degrees Celsius and the time is 1-50 minutes.
可选地，在所述不锈钢基材的表面形成所述凹陷结构后，在所述不锈钢基材的表面还形成有氧化膜层，所述氧化膜层的厚度为1-20纳米。Alternatively, after the recessed structure is formed on the surface of the stainless steel substrate, an oxide film layer is further formed on the surface of the stainless steel substrate, and the oxide film layer has a thickness of 1 to 20 nm.
可选地，所述氧化膜层至少包括铁氧化物、铬氧化物和镍氧化物中的两种。Optionally, the oxide film layer includes at least two of iron oxide, chromium oxide, and nickel oxide.
可选地，所述塑料包括热塑性树脂和填充材料，所述填充材料在所述塑料中的质量百分比为5-40％，所述填充材料包括尼龙纤维、碳纤维、玻璃纤维、芳香族聚酰胺纤维、碳酸钙、碳酸镁、二氧化硅及黏土中的至少一种。Optionally, the plastic comprises a thermoplastic resin and a filler material, the filler material is 5-40% by mass in the plastic, and the filler material comprises nylon fiber, carbon fiber, glass fiber, and aramid fiber. At least one of calcium carbonate, magnesium carbonate, silica, and clay.
可选地，所述热塑性树脂包括聚苯硫醚树脂、聚对苯二甲酸丁醇树脂、聚酰胺、聚碳酸酯和聚烯烃中的至少一种。Optionally, the thermoplastic resin comprises at least one of a polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin.
本发明的发明人发现，在不锈钢上采用现有技术中常用的纳米注塑方法结合塑料，通过纳米级小孔注塑结合后形成的复合产品存在工艺不稳定、可靠性差等诸多问题。The inventors of the present invention have found that the nano-injection method commonly used in the prior art is combined with plastic on stainless steel, and the composite product formed by nano-scale small-hole injection molding has many problems such as unstable process and poor reliability.
本发明中的不锈钢基材进行400-900摄氏度的热处理，也即敏化处理，加剧了碳铬化合物在晶体缺陷部位的析出、沉淀，能在不锈钢基材上 形成严重的贫铬区域，再经由腐蚀液蚀刻后在贫铬区域形成若干微米级的凹陷结构。不锈钢基材与塑料通过该凹陷结构注塑结合后的结合力更大。缩短了工艺流程，降低了生产成本，更适合大规模生产。且对于注塑塑料没有特殊材质要求，适用范围更广。The stainless steel substrate in the present invention is subjected to heat treatment at 400-900 degrees Celsius, that is, sensitization treatment, which exacerbates precipitation and precipitation of carbon chromium compounds in crystal defects, and can be on a stainless steel substrate. A severe chromium-depleted region is formed, which is etched through the etching solution to form a plurality of micron-sized recessed structures in the chromium-depleted region. The bonding force of the stainless steel substrate and the plastic after injection molding by the recessed structure is greater. The process flow is shortened, the production cost is reduced, and it is more suitable for mass production. There is no special material requirement for injection molding plastics, and the scope of application is wider.
因此，本发明所要实现的技术任务或者所要解决的技术问题是本领域技术人员从未想到的或者没有预期到的，故本发明是一种新的技术方案。Therefore, the technical task to be achieved by the present invention or the technical problem to be solved is not thought of or expected by those skilled in the art, so the present invention is a new technical solution.
通过以下参照附图对本发明的示例性实施例的详细描述，本发明的其它特征及其优点将会变得清楚。Other features and advantages of the present invention will become apparent from the Detailed Description of the <RTIgt;
附图说明DRAWINGS
被结合在说明书中并构成说明书的一部分的附图示出了本发明的实施例，并且连同其说明一起用于解释本发明的原理。The accompanying drawings, which are incorporated in FIG
图1是本发明实施例中提供的不锈钢和塑料的结合件的结构示意图；1 is a schematic structural view of a joint of stainless steel and plastic provided in an embodiment of the present invention;
图2是本发明实施例中提供的不锈钢基材上的凹陷结构的示意图；2 is a schematic view showing a recessed structure on a stainless steel substrate provided in an embodiment of the present invention;
图3是本发明实施例中提供的不锈钢基材上的凹陷结构的示意图；3 is a schematic view showing a recessed structure on a stainless steel substrate provided in an embodiment of the present invention;
图4是本发明实施例中不锈钢和塑料结合后的截面示意图。Fig. 4 is a schematic cross-sectional view showing the combination of stainless steel and plastic in the embodiment of the present invention.
具体实施方式detailed description
现在将参照附图来详细描述本发明的各种示例性实施例。应注意到：除非另外具体说明，否则在这些实施例中阐述的部件和步骤的相对布置、数字表达式和数值不限制本发明的范围。Various exemplary embodiments of the present invention will now be described in detail with reference to the drawings. It should be noted that the relative arrangement of the components and steps, numerical expressions and numerical values set forth in the embodiments are not intended to limit the scope of the invention unless otherwise specified.
以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。The following description of the at least one exemplary embodiment is merely illustrative and is in no way
对于相关领域普通技术人员已知的技术、方法和设备可能不作详细讨论，但在适当情况下，所述技术、方法和设备应当被视为说明书的一部分。Techniques, methods and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but the techniques, methods and apparatus should be considered as part of the specification, where appropriate.
在这里示出和讨论的所有例子中，任何具体值应被解释为仅仅是示例性的，而不是作为限制。因此，示例性实施例的其它例子可以具有不同的值。In all of the examples shown and discussed herein, any specific values are to be construed as illustrative only and not as a limitation. Thus, other examples of the exemplary embodiments may have different values.
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一 旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步讨论。It should be noted that similar reference numerals and letters indicate similar items in the following figures, therefore, one Once an item is defined in a drawing, it is not required to be further discussed in subsequent figures.
本发明提供了一种不锈钢和塑料的结合件，该结合件包括不锈钢基材和塑料。如图1至图4所示，不锈钢基材1经过400-900摄氏度的热处理，也即敏化处理，加剧了碳化物在晶体缺陷部位的析出、沉淀，能在不锈钢基材1上形成严重的贫铬区域。再经由腐蚀液蚀刻后在贫铬区域形成若干微米级的凹陷结构11，所述凹陷结构11为微米级的蚀痕。获得的凹陷结构11与所述不锈钢基材1的表面之间具有倾斜角度，例如其与所述不锈钢基材1的表面之间可以具有不同的倾斜角度。所述凹陷结构11的平均深度H为0.1-30微米，所述凹陷结构11的平均宽度W为0.2-15微米。具体地，所述凹陷结构11包括与所述不锈钢基材1表面存在斜率的第一凹陷结构。所述第一凹陷结构相对于所述不锈钢基材1的表面的斜率可以具有不同的数值。所述凹陷结构11还可以包括垂直于所述不锈钢基材1表面的第二凹陷结构。如此，包括所述第一凹陷结和所述第二凹陷结构的凹陷结构11相对于不锈钢基材1的表面具有不同的倾斜角度。The present invention provides a joint of stainless steel and plastic that includes a stainless steel substrate and plastic. As shown in FIG. 1 to FIG. 4, the stainless steel substrate 1 is subjected to heat treatment at 400-900 degrees Celsius, that is, sensitization treatment, which exacerbates the precipitation and precipitation of carbides in the crystal defect portion, and can form a serious on the stainless steel substrate 1. Chromium-poor area. After etching through the etching solution, a plurality of micron-sized recessed structures 11 are formed in the chromium-depleted region, and the recessed structures 11 are micron-scale etch marks. The obtained recessed structure 11 has an inclined angle with the surface of the stainless steel substrate 1, for example, it may have a different inclination angle from the surface of the stainless steel substrate 1. The recessed structure 11 has an average depth H of 0.1 to 30 μm, and the recessed structure 11 has an average width W of 0.2 to 15 μm. Specifically, the recess structure 11 includes a first recess structure having a slope with respect to a surface of the stainless steel substrate 1. The slope of the first recessed structure with respect to the surface of the stainless steel substrate 1 may have different values. The recessed structure 11 may further include a second recessed structure perpendicular to the surface of the stainless steel substrate 1. As such, the recessed structure 11 including the first recessed junction and the second recessed structure has different inclination angles with respect to the surface of the stainless steel substrate 1.
经过腐蚀液蚀刻后形成的凹陷结构11与不锈钢基材1组织中的贫铬区域有很大的关系。本发明中，在400-900摄氏度之间，对所述不锈钢基材1进行加热处理。当所述不锈钢基材1在400-900摄氏度之间加热时，或者缓慢冷却通过这个区间的温度时，会产生晶间偏析，加剧了碳化物在晶体缺陷部位的析出、沉淀，在晶粒的两侧、晶体缺陷附近处快速形成严重的贫铬区域。且经理论分析及实验验证表明：以晶界为例，不锈钢热处理温度低于400摄氏度时，晶界上难以形成碳化铬，晶界附近也难以形成贫铬区。而当热处理温度高于900摄氏度时，铬的扩散能力增强，晶粒内的铬能够扩散至晶界，不会因碳化铬的析出而形成贫铬区。The recessed structure 11 formed by the etching of the etching solution has a great relationship with the chromium-depleted region in the structure of the stainless steel substrate 1. In the present invention, the stainless steel substrate 1 is subjected to heat treatment between 400 and 900 °C. When the stainless steel substrate 1 is heated between 400 and 900 degrees Celsius, or slowly cooled through the temperature of this interval, intergranular segregation occurs, which exacerbates the precipitation and precipitation of carbides in the crystal defects, in the crystal grains. Severe chromium-depleted areas are rapidly formed on both sides and near crystal defects. Theoretical analysis and experimental verification show that, taking the grain boundary as an example, when the heat treatment temperature of stainless steel is lower than 400 degrees Celsius, it is difficult to form chromium carbide on the grain boundary, and it is difficult to form a chromium-depleted region near the grain boundary. When the heat treatment temperature is higher than 900 degrees Celsius, the diffusion capacity of chromium is enhanced, and the chromium in the crystal grains can diffuse to the grain boundary, and the chromium-depleted region is not formed due to the precipitation of chromium carbide.
由于贫铬区域与其他区域之间腐蚀率的不一致，也就是贫铬区域的腐蚀速率要大于其他区域，因而在不锈钢基材1上就形成了易腐蚀与耐腐蚀交叉分布的区域。具体的，此类贫铬区域是溶质原子、杂质、第二相等富集区域，能够形成活态-钝态的微电偶结构，再经由特定的腐蚀介质的侵蚀，易腐蚀的区域腐蚀、脱落，形成所述凹陷结构11。 Since the corrosion rate between the chromium-depleted region and other regions is inconsistent, that is, the corrosion rate of the chromium-depleted region is greater than that of other regions, a region where the corrosion and corrosion resistance are cross-distributed is formed on the stainless steel substrate 1. Specifically, such a chromium-depleted region is a solute atom, an impurity, and a second equal enrichment region, which can form a living-passive micro-galvanic structure, and then corrode and corrode in a corrosive region through erosion of a specific corrosive medium. Forming the recessed structure 11.
所述不锈钢基材1上注射成型有塑料2，所述塑料2中的部分结构嵌入在所述凹陷结构11内以形成所述结合件。由于所述凹陷结构11相对于不锈钢基材1的表面具有不同的倾斜角度，因而所述塑料2中的部分结构能够以不同的倾斜角度嵌入至所述凹陷结构11的内部。可选地，所述凹陷结构11可以只形成在不锈钢基材1上需要注塑塑料2的区域。或者，也可以在不锈钢基材1的全部表面形成所述凹陷结构11。The stainless steel substrate 1 is injection molded with a plastic 2, and a part of the structure of the plastic 2 is embedded in the recessed structure 11 to form the joint. Since the recessed structure 11 has different inclination angles with respect to the surface of the stainless steel substrate 1, a part of the structure in the plastic 2 can be embedded into the inside of the recessed structure 11 at different inclination angles. Alternatively, the recessed structure 11 may be formed only on the stainless steel substrate 1 where the plastic 2 needs to be injection molded. Alternatively, the recessed structure 11 may be formed on the entire surface of the stainless steel substrate 1.
本发明提供的不锈钢和塑料的结合件具有如下技术效果，首先，通过对不锈钢进行热处理，也即敏化处理，产生晶间偏析，加剧了碳化物在晶体缺陷部位的沉淀析出，在晶粒的两侧、晶体缺陷处形成严重的贫铬区域，为易腐蚀区域。通过腐蚀液蚀刻后，在易腐蚀区域形成若干微米级的凹陷结构11。由于所述凹陷结构11与所述不锈钢基材1的表面之间具有不同倾斜角度，在将塑料2注塑到所述不锈钢基材1的表面时，塑料2中的部分结构能够以不同的倾斜角度嵌入至所述凹陷结构11内，以形成塑料与不锈钢的结合件。且所述凹陷结构11的连贯性好，填充至所述凹陷结构11内的塑料2的连贯性也较好。因此，塑料2能够像植物的根部一样嵌入在不锈钢基材1表面的凹陷结构11内，结合力大，在拉伸或剪切过程中塑料2不易脱落。The combination of stainless steel and plastic provided by the invention has the following technical effects. Firstly, by heat treatment of stainless steel, that is, sensitization treatment, intergranular segregation is generated, which exacerbates precipitation of carbides in crystal defects, in the crystal grains. Severe chromium-depleted areas are formed on both sides and crystal defects, which are corrosive areas. After etching by the etching solution, a plurality of micron-sized recessed structures 11 are formed in the easily corrodible region. Since the recessed structure 11 and the surface of the stainless steel substrate 1 have different inclination angles, when the plastic 2 is injection molded onto the surface of the stainless steel substrate 1, a part of the structure in the plastic 2 can be inclined at different angles. Embedded in the recessed structure 11 to form a joint of plastic and stainless steel. Moreover, the continuity of the recessed structure 11 is good, and the continuity of the plastic 2 filled into the recessed structure 11 is also good. Therefore, the plastic 2 can be embedded in the recessed structure 11 on the surface of the stainless steel substrate 1 like the root of the plant, and the bonding force is large, and the plastic 2 is not easily peeled off during stretching or shearing.
图4示出了本实施例中不锈钢基材1和塑料2结合后的一种截面示意图。本例中，蚀刻形成的微米级凹陷结构11较大较深，无需润孔剂的活化，塑料2即可在凹陷结构11内获得较好的填充。且经过牵引拉伸实验后，结合件断裂部位在塑料2中部，而塑料2与不锈钢基材1的结合面并未出现裂纹，由此证明了本发明中的不锈钢基材1和塑料2之间具有较强的结合力。Fig. 4 is a schematic cross-sectional view showing the combination of the stainless steel substrate 1 and the plastic 2 in this embodiment. In this example, the micro-scale recessed structure 11 formed by etching is larger and deeper, and the plastic 2 can be better filled in the recessed structure 11 without the activation of the porogen. After the tensile tensile test, the joint fractured portion is in the middle of the plastic 2, and the joint surface of the plastic 2 and the stainless steel substrate 1 is not cracked, thereby demonstrating the between the stainless steel substrate 1 and the plastic 2 in the present invention. Has a strong binding force.
第二、不锈钢基材1中存在组织各异的区域，例如贫铬区域，此类区域存在固溶原子、第二相及杂质等高电位物质，或者以晶界、孪晶等晶体缺陷，均是能量高、较活泼的区域。浸渍于本方案的腐蚀液，上述区域优先发生腐蚀、脱落，而其他区域仅发生轻微的腐蚀，大大降低了腐蚀液的消耗。例如针对于奥氏体不锈钢，采用一次浸渍即可形成所述凹陷结构11。而针对于其他不锈钢，在第一次蚀刻基础上再添加一次腐蚀扩展即可形成 所述凹陷结构11。之后，直接注塑成型，无需进行其他加工工序。因此，本技术方案成孔工艺流程简化，降低结合件的废品率。Second, the stainless steel substrate 1 has regions of different structures, such as a chromium-depleted region, such as high-potential substances such as solid solution atoms, second phase, and impurities, or crystal defects such as grain boundaries and twins. It is a high-energy, lively area. Impregnated in the corrosive solution of this scheme, the above areas preferentially corrode and fall off, while other areas only cause slight corrosion, which greatly reduces the consumption of corrosive liquid. For example, for austenitic stainless steel, the recessed structure 11 can be formed by one dipping. For other stainless steels, a corrosion extension can be added on the basis of the first etching. The recessed structure 11. After that, direct injection molding eliminates the need for additional processing. Therefore, the technical solution of the present invention is simplified in the hole forming process, and the scrap rate of the joint member is reduced.
第三、本发明中的注塑塑料适用于大多数塑料，包括热塑性树脂，例如聚苯硫醚树脂(PPS)、聚对苯二甲酸丁醇树脂(PBT)、聚酰胺(PA)、聚碳酸酯(PC)、聚烯烃，聚苯乙烯。而现有技术中形成的细小盲孔，塑料在盲孔内的流动性不佳，需要借助于润孔剂与PPS或者PBT材料的物理和化学反应，因此，常规技术方案塑料类别多局限于PPS或者PBT材料，仅此两类塑料含有大量的羧基，与润孔剂中阳离子发生放热反应。注塑中塑料需借助于放热反应产生的热量，延缓在细孔内的固化。而本发明中的微米级凹陷结构11的尺寸较大，无需塑料与润孔剂的放热反应即可获得较好的填充，由此扩大了塑料的选用范围。Third, the injection molded plastic of the present invention is suitable for most plastics, including thermoplastic resins such as polyphenylene sulfide resin (PPS), polybutylene terephthalate resin (PBT), polyamide (PA), polycarbonate. (PC), polyolefin, polystyrene. However, the small blind holes formed in the prior art have poor fluidity in the blind holes, and physical and chemical reactions with the PPS or PBT materials are required by means of the pore-treating agent. Therefore, the conventional technical solutions are mostly limited to PPS. Or PBT materials, only these two types of plastics contain a large amount of carboxyl groups, and an exothermic reaction with the cations in the pore former. Plastics in injection molding require heat generated by an exothermic reaction to retard solidification in the pores. However, the size of the micron-sized recessed structure 11 in the present invention is large, and a good filling can be obtained without the exothermic reaction of the plastic and the pore-piercing agent, thereby expanding the selection range of the plastic.
优选地，所述热处理的温度为600-800摄氏度，所述热处理的时间为2-5小时。如此，在此温度区间范围内对所述不锈钢基材1一定时间的热处理能够快速形成严重的贫铬区域。Preferably, the temperature of the heat treatment is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours. Thus, heat treatment of the stainless steel substrate 1 for a certain period of time within this temperature range can rapidly form a severe chromium-depleted region.
优选地，所述凹陷结构11在垂直于所述不锈钢基材1表面的方向上的截面至少包括倒三角形、弓形、U形、四边形中的至少一种。如此，注塑时，塑料2便于嵌入至此种凹陷结构11内。Preferably, the cross section of the recessed structure 11 in a direction perpendicular to the surface of the stainless steel substrate 1 includes at least one of an inverted triangle, an arcuate shape, a U shape, and a quadrangular shape. Thus, the plastic 2 is easily inserted into the recessed structure 11 during injection molding.
所述凹陷结构11的延伸方向以及分布形态可以有不同方式，只要通过腐蚀得到的凹陷结构11能对注塑嵌入的塑料2产生吸附力即可。优选地，所述凹陷结构11可包括条形结构、折形结构、曲形结构中的至少一种。在其中的任意一种结构中的凹陷结构中，其形成的内部凹陷空间应保证连贯性较好，延伸方向不发生突变。如此，更加便于将塑料2嵌入至所述凹陷结构11内。The extending direction and the distribution form of the recessed structure 11 may be different in that the recessed structure 11 obtained by etching can generate an adsorption force to the plastic 2 embedded in the injection molding. Preferably, the recess structure 11 may include at least one of a strip structure, a fold structure, and a curved structure. In the recessed structure in any of the structures, the inner recessed space formed by the recessed structure should ensure good coherence and no abrupt change in the direction of extension. In this way, it is more convenient to embed the plastic 2 into the recessed structure 11.
不锈钢基材1上的晶间腐蚀是沿着晶粒的边缘进行的，因而所述凹陷结构11在所述不锈钢基材1表面上的投影可包括封闭的图形。例如所述封闭的图形可以是围绕晶粒的长方形、环形或者其他不规则形状的封闭图形。例如图2、图3所示。需要说明的是，所述封闭的图形可以由上述若干条形结构、折形结构、曲形结构中的至少一种连接形成。所述凹陷结构11在所述不锈钢基材1表面上的投影也可以包括开放的图形。如图3所示，所 述凹陷结构11可以是平均长度L大于0.2微米的条形结构等。The intergranular corrosion on the stainless steel substrate 1 is performed along the edges of the crystal grains, and thus the projection of the recessed structure 11 on the surface of the stainless steel substrate 1 may include a closed pattern. For example, the closed pattern may be a closed figure of a rectangle, a ring or other irregular shape surrounding the die. For example, Figure 2 and Figure 3. It should be noted that the closed pattern may be formed by at least one of a plurality of strip structures, a fold structure, and a curved structure. The projection of the recessed structure 11 on the surface of the stainless steel substrate 1 may also include an open pattern. As shown in Figure 3, The recessed structure 11 may be a strip structure or the like having an average length L of more than 0.2 μm.
优选地，所述凹陷结构11的表面形成有氧化膜层，所述氧化膜层的厚度为1-20纳米。进一步地，所述氧化膜层至少包括铁氧化物、铬氧化物和镍氧化物中的两种。相比于不锈钢基材1，氧化膜的导热系数较低，注塑时能减少塑料2的热量散失，延缓了塑料2凝固、结晶的时间，使塑料2能够更充分的填充在所述凹陷结构11内，所述凹陷结构11的底部也能够获得较好的填充。例如在400℃的情况下，不锈钢的导热系数为16.3W/m·K，三氧化二铁的导热系数为5.1W/m·K，氧化亚铁的导热系数为15.0W/m·K，氧化铬的导热系数为10W/m·K左右。Preferably, the surface of the recessed structure 11 is formed with an oxide film layer having a thickness of 1 to 20 nm. Further, the oxide film layer includes at least two of iron oxide, chromium oxide, and nickel oxide. Compared with the stainless steel substrate 1, the thermal conductivity of the oxide film is low, and the heat loss of the plastic 2 can be reduced during injection molding, and the time for solidification and crystallization of the plastic 2 is delayed, so that the plastic 2 can be more fully filled in the recessed structure 11 The bottom of the recessed structure 11 can also achieve better filling. For example, in the case of 400 ° C, the thermal conductivity of stainless steel is 16.3 W / m · K, the thermal conductivity of ferric oxide is 5.1 W / m · K, the thermal conductivity of ferrous oxide is 15.0 W / m · K, oxidation The thermal conductivity of chromium is about 10 W/m·K.
需要说明的是，氧化膜层的形成方式并不受到局限，可以包括高温氧化、化学钝化、电化学钝化方式。无论何种方式其最终效果是在不锈钢表面形成一层致密的、隔热性的氧化膜。It should be noted that the formation mode of the oxide film layer is not limited, and may include high temperature oxidation, chemical passivation, and electrochemical passivation. In either case, the final effect is to form a dense, thermally insulating oxide film on the stainless steel surface.
所述塑料2的线形膨胀系数应与不锈钢基材1尽可能的接近，以利于注塑的固化。由于常用于注塑的PPS或者PBT材料的线膨胀系数在6-8×10-5/℃左右，而不锈钢的线膨胀系数为1.5×10-5/℃，相差较大。因此，有必要对于主成分树脂材料加以改性，显著降低组合物的线膨胀系数。The linear expansion coefficient of the plastic 2 should be as close as possible to the stainless steel substrate 1 to facilitate the curing of the injection molding. Since the linear expansion coefficient of PPS or PBT materials commonly used for injection molding is about 6-8×10 -5 /°C, and the linear expansion coefficient of stainless steel is 1.5×10 -5 /°C, the difference is large. Therefore, it is necessary to modify the main component resin material to significantly lower the linear expansion coefficient of the composition.
优选地，所述塑料2包括是热塑性树脂和填充材料。例如所述热塑性树脂可以包括聚烯烃聚苯硫醚树脂、聚对苯二甲酸丁醇树脂、聚酰胺、聚碳酸酯、聚烯烃等。所述填充材料在所述塑料2中的质量百分比可以为5-40％。所述填充材料可包括尼龙纤维、碳纤维、玻璃纤维、芳香族聚酰胺纤维、碳酸钙、碳酸镁、二氧化硅及黏土中的至少一种。如此，所述填充材料对所述塑料2的主成分树脂材料加以改进，能够显著降低塑料2的线膨胀系数，从而接近不锈钢的线膨胀系数。Preferably, the plastic 2 comprises a thermoplastic resin and a filling material. For example, the thermoplastic resin may include a polyolefin polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, a polyolefin, or the like. The mass percentage of the filler material in the plastic 2 may be 5-40%. The filler material may include at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, and clay. Thus, the filler material improves the main component resin material of the plastic 2, and can significantly reduce the linear expansion coefficient of the plastic 2, thereby approaching the linear expansion coefficient of the stainless steel.
本发明中，不锈钢和塑料结合件的一种加工方法包括：In the present invention, a method of processing stainless steel and plastic joints includes:
首先，提供不锈钢基材1，以便于将塑料2注塑到不锈钢基材1的表面。目前，常用的不锈钢包括奥氏体不锈钢和马氏体不锈钢，组织中铬元素质量分数大于12％。铬原子在不锈钢中扩散速度小，易形成贫铬区域。而不锈钢具有较强耐腐蚀性的主要原因在于铬元素氧化形成致密的氧化膜，提高材料耐蚀性。因此，大量的贫铬区域等易腐蚀区域为不锈钢后续 蚀刻提供了良好的组织基础。由此，本技术方案并不适用钢铁材料，但是适用于全部的不锈钢。First, a stainless steel substrate 1 is provided to facilitate injection molding of the plastic 2 onto the surface of the stainless steel substrate 1. At present, commonly used stainless steels include austenitic stainless steel and martensitic stainless steel, and the chromium content in the structure is greater than 12%. The chromium atom has a small diffusion rate in stainless steel and is easy to form a chromium-depleted region. The main reason for the strong corrosion resistance of stainless steel is that the chromium element is oxidized to form a dense oxide film, which improves the corrosion resistance of the material. Therefore, a large number of areas of corrosion-prone areas such as chromium-depleted areas are followed by stainless steel. Etching provides a good basis for organization. Thus, the present technical solution is not applicable to steel materials, but is applicable to all stainless steels.
之后，在400-900摄氏度之间，对所述不锈钢基材1进行加热处理。如此，加剧了碳化物在晶体缺陷部位的沉淀析出，在晶粒的两侧、晶体缺陷处形成严重的贫铬区域。由于贫铬区域与其他区域之间腐蚀率的不一致，也就是贫铬区域的腐蚀速率要大于其他区域，因而在不锈钢基材1上就形成了易腐蚀与耐腐蚀交叉分布的区域。Thereafter, the stainless steel substrate 1 is subjected to heat treatment between 400 and 900 degrees Celsius. In this way, precipitation of carbides at the crystal defect sites is aggravated, and severe chromium-depleted regions are formed on both sides of the crystal grains and crystal defects. Since the corrosion rate between the chromium-depleted region and other regions is inconsistent, that is, the corrosion rate of the chromium-depleted region is greater than that of other regions, a region where the corrosion and corrosion resistance are cross-distributed is formed on the stainless steel substrate 1.
优选地，所述加热处理的温度为600-800摄氏度，所述热处理的时间为2-5小时。如此，在此温度区间范围内对所述不锈钢基材1一定时间的热处理能够快速形成严重的贫铬区域。以便在后续处理过程中获得更加符合要求的凹陷结构11，凹陷结构11的内部的连贯性更好，塑料2更易嵌入其内部。Preferably, the temperature of the heat treatment is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours. Thus, heat treatment of the stainless steel substrate 1 for a certain period of time within this temperature range can rapidly form a severe chromium-depleted region. In order to obtain a more desirable recessed structure 11 in the subsequent processing, the interior of the recessed structure 11 is more consistent, and the plastic 2 is more easily embedded in the interior thereof.
之后，对所述不锈钢基材1进行腐蚀液蚀刻处理，以形成微米级的凹陷结构11。图2、图3、图4示出了采用本技术方案所蚀刻的表面形貌特征，所述凹陷结构11的平均深度H为0.1-30微米、平均宽度W为0.2-15微米。Thereafter, the stainless steel substrate 1 is subjected to an etching solution etching treatment to form a micron-sized recessed structure 11. 2, 3, and 4 show surface topography features etched by the present technical solution. The recessed structure 11 has an average depth H of 0.1-30 microns and an average width W of 0.2-15 microns.
所述凹陷结构11包括相对于不锈钢基材1存在斜率的第一凹陷结构。所述第一凹陷结构相对于所述不锈钢基材1的表面的斜率可以具有不同的数值。所述凹陷结构11还可以包括垂直于所述不锈钢基材1表面的第二凹陷结构。如此，包括所述第一凹陷结和所述第二凹陷结构的凹陷结构11相对于不锈钢基材1表面具有不同的倾斜角度。能够使得塑料2中的部分结构像植物的根部一样嵌入在凹陷结构11内，其之间的结合力更大。The recessed structure 11 includes a first recessed structure having a slope with respect to the stainless steel substrate 1. The slope of the first recessed structure with respect to the surface of the stainless steel substrate 1 may have different values. The recessed structure 11 may further include a second recessed structure perpendicular to the surface of the stainless steel substrate 1. As such, the recessed structure 11 including the first recessed junction and the second recessed structure has different inclination angles with respect to the surface of the stainless steel substrate 1. It is possible to cause a part of the structure in the plastic 2 to be embedded in the recessed structure 11 like the root of the plant with a greater bonding force therebetween.
不锈钢能否腐蚀形成凹陷结构11的关键在于贫铬区域与其他区域之间腐蚀率的不一致，也就是贫铬区域的腐蚀速率要大于其他区域。因此，腐蚀液的种类与成分组成不仅决定是否能够形成凹陷结构11，而且也决定凹陷结构11的尺寸。因此，本方案中优选了几组腐蚀液，构成弱氧化性介质，更有利于微米级凹陷结构11的形成。可选地，所述腐蚀液包括：硝酸、磷酸、硫酸、亚硫酸、盐酸、草酸、醋酸、氢氟酸、马来酸、苯二酸、乙二酸溶液及其盐溶液中的至少一种。可选地，所述腐蚀液包括：5-30％草酸 溶液与氯化盐或硫酸盐的组合、1-60％硝酸与氯化物或氧化物的组合、10-30％硝酸和5-15％金属硝酸盐和2-10％硫酸盐的组合中的至少一种The key to the corrosion of stainless steel to form the recessed structure 11 is the inconsistency of the corrosion rate between the chromium-depleted area and other areas, that is, the corrosion rate of the chromium-depleted area is greater than that of other areas. Therefore, the type and composition of the etching liquid not only determine whether or not the recessed structure 11 can be formed, but also determines the size of the recessed structure 11. Therefore, several sets of etching liquids are preferred in the present scheme to constitute a weak oxidizing medium, which is more advantageous for the formation of the micro-scale recessed structure 11. Optionally, the etching solution comprises at least one of nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, oxalic acid, acetic acid, hydrofluoric acid, maleic acid, phthalic acid, oxalic acid solution and a salt solution thereof. . Optionally, the etching solution comprises: 5-30% oxalic acid At least a combination of a solution with a chloride or sulfate, a combination of 1-60% nitric acid and chloride or oxide, 10-30% nitric acid, and 5-15% metal nitrate and 2-10% sulfate One kind
优选地，所述腐蚀液蚀刻过程中的温度为20-90摄氏度，持续时间为1-50分钟。如此，通过控制方法中的多项参数，能够获得需要的凹陷结构11的尺寸，以及形状等。Preferably, the temperature during the etching of the etching solution is 20-90 degrees Celsius and the duration is 1-50 minutes. Thus, by controlling a plurality of parameters in the method, the size, shape, and the like of the desired recessed structure 11 can be obtained.
为了便于对不锈钢基材1的表面进行腐蚀液蚀刻以更好的形成所述凹陷结构11，可选的，在进行腐蚀液蚀刻之前，对不锈钢基材1进行除油脱脂处理。具体的，可以将不锈钢基材1浸泡于35-80摄氏度的清洗剂中进行超声处理60-600秒。之后，进行纯水冲洗。例如，所述清洗剂可以为100-300g/L的酸、碱或者有机溶剂等。In order to facilitate etching of the surface of the stainless steel substrate 1 to better form the recessed structure 11, the stainless steel substrate 1 may be subjected to degreasing and degreasing treatment prior to etching. Specifically, the stainless steel substrate 1 can be immersed in a cleaning agent of 35-80 degrees Celsius for ultrasonic treatment for 60-600 seconds. After that, rinse with pure water. For example, the cleaning agent may be an acid, a base or an organic solvent of 100 to 300 g/L or the like.
可选地，在所述不锈钢基材1的表面形成凹陷结构11之后，在所述所述不锈钢基材1的表面可加工处理形成氧化膜层。所述氧化膜层的厚度可为1-20纳米。进一步地，所述氧化膜层可至少包括铁氧化物、铬氧化物和镍氧化物中的两种。如此，注塑时能减少塑料2的热量散失，延缓了塑料2凝固、结晶的时间，使塑料2能够更充分的填充在所述凹陷结构11内，所述凹陷结构11的底部也能够获得较好的填充。需要说明的是，氧化膜层的形成方式并不受到局限，可以包括高温氧化、化学钝化、电化学钝化方式。无论何种方式其最终效果是在不锈钢表面形成一层致密的、隔热性的氧化膜。Alternatively, after the recessed structure 11 is formed on the surface of the stainless steel substrate 1, the surface of the stainless steel substrate 1 may be processed to form an oxide film layer. The oxide film layer may have a thickness of 1 to 20 nm. Further, the oxide film layer may include at least two of iron oxide, chromium oxide, and nickel oxide. In this way, the heat loss of the plastic 2 can be reduced during the injection molding, and the time for solidification and crystallization of the plastic 2 can be delayed, so that the plastic 2 can be more fully filled in the recessed structure 11, and the bottom of the recessed structure 11 can also be better. The padding. It should be noted that the formation mode of the oxide film layer is not limited, and may include high temperature oxidation, chemical passivation, and electrochemical passivation. In either case, the final effect is to form a dense, thermally insulating oxide film on the stainless steel surface.
最后，将塑料2注塑到所述不锈钢基材1的表面，使所述塑料2中的部分结构嵌入至所述凹陷结构11内，以形成不锈钢和塑料的结合件。优选地，所述塑料2包括热塑性树脂和填充材料。所述热塑性树脂可以包括聚烯烃聚苯硫醚树脂、聚对苯二甲酸丁醇树脂、聚酰胺、聚碳酸酯、聚烯烃中的至少一种。所述填充材料在所述塑料2中的质量百分比可以为5-40％。所述填充材料可包括尼龙纤维、碳纤维、玻璃纤维、芳香族聚酰胺纤维、碳酸钙、碳酸镁、二氧化硅及黏土中的至少一种。如此，所述填充材料对所述塑料2的主成分树脂材料加以改进，能够显著降低塑料2的线膨胀系数，从而接近不锈钢的线膨胀系数。Finally, plastic 2 is injection molded onto the surface of the stainless steel substrate 1, and a part of the structure in the plastic 2 is embedded in the recessed structure 11 to form a joint of stainless steel and plastic. Preferably, the plastic 2 comprises a thermoplastic resin and a filling material. The thermoplastic resin may include at least one of a polyolefin polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin. The mass percentage of the filler material in the plastic 2 may be 5-40%. The filler material may include at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silica, and clay. Thus, the filler material improves the main component resin material of the plastic 2, and can significantly reduce the linear expansion coefficient of the plastic 2, thereby approaching the linear expansion coefficient of the stainless steel.
在本发明的一种具体实施方式中，首先在700摄氏度的温度下对不锈 钢基材1进行热处理；再采用10-30％硝酸和5-15％金属硝酸盐和2-10％硫酸盐的组合腐蚀液对不锈钢基材1进行蚀刻，蚀刻处理温度为60摄氏度；而后在300℃的注射温度下，将由PBT+30wt％玻璃纤维混合的塑料材料注射到不锈钢基材1的表面，最终得到不锈钢和塑料的结合件。In a specific embodiment of the invention, the stainless steel is first exposed to a temperature of 700 degrees Celsius. The steel substrate 1 is subjected to heat treatment; the stainless steel substrate 1 is etched by a combined etching solution of 10-30% nitric acid and 5-15% metal nitrate and 2-10% sulfate, and the etching temperature is 60 degrees Celsius; At a injection temperature of 300 ° C, a plastic material mixed with PBT + 30 wt% glass fibers was injected onto the surface of the stainless steel substrate 1 to finally obtain a joint of stainless steel and plastic.
虽然已经通过例子对本发明的一些特定实施例进行了详细说明，但是本领域的技术人员应该理解，以上例子仅是为了进行说明，而不是为了限制本发明的范围。本领域的技术人员应该理解，可在不脱离本发明的范围和精神的情况下，对以上实施例进行修改。本发明的范围由所附权利要求来限定。 While the invention has been described in detail with reference to the preferred embodiments of the present invention, it is understood that It will be appreciated by those skilled in the art that the above embodiments may be modified without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims (15)

  1. 一种不锈钢和塑料的结合件，其特征在于，所述结合件包括不锈钢基材，经400-900摄氏度的热处理再通过腐蚀液蚀刻后，在所述不锈钢基材的表面形成有若干凹陷结构，所述凹陷结构的平均深度为0.1-30微米，所述凹陷结构的平均宽度为0.2-15微米，所述不锈钢基材上注射成型有塑料，所述塑料中的部分结构嵌入在所述凹陷结构内。A joint of stainless steel and plastic, characterized in that the joint member comprises a stainless steel base material, and after being etched by an etching solution by heat treatment at 400-900 degrees Celsius, a plurality of concave structures are formed on the surface of the stainless steel base material. The recessed structure has an average depth of 0.1-30 micrometers, the recessed structure has an average width of 0.2-15 micrometers, and the stainless steel substrate is injection-molded with plastic, and a part of the plastic is embedded in the recessed structure. Inside.
  2. 根据权利要求1所述的不锈钢和塑料的结合件，其特征在于，所述热处理的温度为600-800摄氏度，所述热处理的时间为2-5小时。The combination of stainless steel and plastic according to claim 1, wherein the heat treatment temperature is 600-800 degrees Celsius, and the heat treatment time is 2-5 hours.
  3. 根据权利要求1所述的不锈钢和塑料的结合件，其特征在于，所述凹陷结构的平均长度大于0.2微米。The combination of stainless steel and plastic of claim 1 wherein said recessed structure has an average length greater than 0.2 microns.
  4. 根据权利要求1所述的不锈钢和塑料的结合件，其特征在于，所述凹陷结构包括条形结构、折形结构、曲形结构中的至少一种。The combination of stainless steel and plastic according to claim 1, wherein the recessed structure comprises at least one of a strip structure, a fold structure, and a curved structure.
  5. 根据权利要求1所述的不锈钢和塑料的结合件，其特征在于，所述凹陷结构在所述不锈钢基材表面上的投影包括封闭的图形。The combination of stainless steel and plastic of claim 1 wherein the projection of the recessed structure on the surface of the stainless steel substrate comprises a closed pattern.
  6. 根据权利要求1所述的不锈钢和塑料的结合件，其特征在于，所述凹陷结构在垂直于所述不锈钢基材表面的方向上的截面形状包括倒三角形、弓形、U形、四边形中的至少一种。The joint of stainless steel and plastic according to claim 1, wherein a cross-sectional shape of the recessed structure in a direction perpendicular to a surface of the stainless steel base material comprises at least at least one of an inverted triangle, an arcuate shape, a U-shaped shape, and a quadrangular shape. One.
  7. 根据权利要求1所述的不锈钢和塑料的结合件，其特征在于，在所述凹陷结构的表面形成有氧化膜层，所述氧化膜层的厚度为1-20纳米。The joint of stainless steel and plastic according to claim 1, wherein an oxide film layer is formed on a surface of the recessed structure, and the oxide film layer has a thickness of 1 to 20 nm.
  8. 根据权利要求7所述的不锈钢和塑料的结合件，其特征在于，所述氧化膜层至少包括铁氧化物、铬氧化物和镍氧化物中的两种。The combination of stainless steel and plastic according to claim 7, wherein said oxide film layer comprises at least two of iron oxide, chromium oxide and nickel oxide.
  9. 一种不锈钢和塑料结合件的加工方法，其特征在于，包括：提供不锈钢基材；经400-900摄氏度的热处理再进行腐蚀液蚀刻处理，在所述不锈钢基材的表面形成若干平均深度为0.1-30微米、平均宽度为0.2-15微米的凹陷结构；将塑料注塑到所述不锈钢基材的表面，使所述塑料中的部分结构嵌入至所述凹陷结构内，以形成不锈钢和塑料的结合件。A method for processing a joint of stainless steel and plastic, comprising: providing a stainless steel substrate; performing a heat treatment at 400-900 degrees Celsius and then etching the etching solution to form a certain average depth of 0.1 on the surface of the stainless steel substrate. a recessed structure of -30 microns and an average width of 0.2-15 microns; plastic is injection molded onto the surface of the stainless steel substrate, and a portion of the structure in the plastic is embedded into the recessed structure to form a combination of stainless steel and plastic Pieces.
  10. 根据权利要求9所述的不锈钢和塑料结合件的加工方法，其特征在于，所述热处理的温度为600-800摄氏度，所述热处理的时间为2-5小 时。The method of processing a stainless steel and plastic joint according to claim 9, wherein the heat treatment temperature is 600-800 degrees Celsius, and the heat treatment time is 2-5 small Time.
  11. 根据权利要求9所述的不锈钢和塑料结合件的加工方法，其特征在于，所述腐蚀液包括：硝酸、磷酸、硫酸、亚硫酸、盐酸、草酸、醋酸、氢氟酸、马来酸、苯二酸、乙二酸溶液及其盐溶液中的至少一种。The method for processing a stainless steel and a plastic joint according to claim 9, wherein the etching solution comprises: nitric acid, phosphoric acid, sulfuric acid, sulfurous acid, hydrochloric acid, oxalic acid, acetic acid, hydrofluoric acid, maleic acid, benzene. At least one of a diacid, an oxalic acid solution, and a salt solution thereof.
  12. 根据权利要求9所述的不锈钢和塑料结合件的加工方法，其特征在于，所述腐蚀液包括：5-30％草酸溶液与氯化盐或硫酸盐的组合、1-60％硝酸与氯化物或氧化物的组合、10-30％硝酸和5-15％金属硝酸盐和2-10％硫酸盐的组合的至少一种。The method for processing a stainless steel and plastic joint according to claim 9, wherein the etching solution comprises: a combination of 5-30% oxalic acid solution and a chloride or sulfate, 1-60% nitric acid and chloride Or a combination of oxides, at least one of 10-30% nitric acid and a combination of 5-15% metal nitrate and 2-10% sulfate.
  13. 根据权利要求9所述的不锈钢和塑料结合件的加工方法，其特征在于，所述腐蚀液蚀刻过程中的温度为20-90摄氏度，时间为1-50分钟。The method of processing a stainless steel and plastic joint according to claim 9, wherein the etching temperature in the etching solution is 20-90 degrees Celsius and the time is 1-50 minutes.
  14. 根据权利要求9所述的不锈钢和塑料结合件的加工方法，其特征在于，在所述不锈钢基材的表面形成所述凹陷结构后，在所述不锈钢基材的表面还形成有氧化膜层，所述氧化膜层的厚度为1-20纳米。The method for processing a stainless steel and a plastic joint according to claim 9, wherein after the recessed structure is formed on the surface of the stainless steel substrate, an oxide film layer is further formed on the surface of the stainless steel substrate. The oxide film layer has a thickness of 1 to 20 nm.
  15. 根据权利要求14所述的不锈钢和塑料结合件的加工方法，其特征在于，所述氧化膜层至少包括铁氧化物、铬氧化物和镍氧化物中的两种。 The method of processing a stainless steel and plastic joint according to claim 14, wherein the oxide film layer comprises at least two of iron oxide, chromium oxide and nickel oxide.
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