WO2018129873A1 - 不锈钢和塑料的结合件及其加工方法 - Google Patents

不锈钢和塑料的结合件及其加工方法 Download PDF

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Publication number
WO2018129873A1
WO2018129873A1 PCT/CN2017/090632 CN2017090632W WO2018129873A1 WO 2018129873 A1 WO2018129873 A1 WO 2018129873A1 CN 2017090632 W CN2017090632 W CN 2017090632W WO 2018129873 A1 WO2018129873 A1 WO 2018129873A1
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Prior art keywords
stainless steel
acid
plastic
oxide film
steel substrate
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PCT/CN2017/090632
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English (en)
French (fr)
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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Goertek Inc
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Goertek Inc
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    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
    • C23C22/47—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates containing also phosphates
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment

Definitions

  • the invention relates to the technical field of material processing, in particular to a joint of stainless steel and plastic and a processing method thereof.
  • metal and plastic composite forms to form the product structure.
  • This structural design can achieve rich functional effects. For example, in the case where the appearance of the product is required to exhibit metal features and the internal structure needs to be reduced in weight and material cost, a metal-plastic composite design can be used.
  • a joint of stainless steel and plastic includes a stainless steel substrate having a honeycomb-shaped pore formed on a surface thereof, and is subjected to passivation treatment of an organic oxidizing solution, and an oxide film is formed on a surface of the honeycomb pore, the oxide film At least two of iron oxide, chromium oxide or nickel oxide are injection molded on the stainless steel substrate, the plastic material being embedded in the honeycomb pores.
  • the organic oxidizing solution is acetic acid, phytic acid, oxalic acid, lactic acid, citric acid, peracetic acid, tannic acid, tartaric acid, ammonia triacetic acid, pyrophosphoric acid, formic acid, ethylenediaminetetraacetic acid, poly horse At least one of acid, polyacrylic acid, hydroxy fork diphosphate, and ethylenediamine methylphosphoric acid.
  • the organic oxidizing solution has a pH of 1-5.
  • the oxide film comprises iron oxide and chromium oxide.
  • the passivation treatment uses an organic oxidizing solution which is a mixed solution of citric acid having a mass fraction of 5-20% and hydrogen peroxide having a mass fraction of 5-30%.
  • the organic oxidizing solution used in the passivation treatment is a mixed solution of a mass fraction of 0.1-5% potassium chloride and a mass fraction of 30-80% acetic acid.
  • the honeycomb pores have an average pore diameter ranging from 10 to 150 nm, and the honeycomb pores extend from the surface of the stainless steel substrate to an inner depth ranging from 10 to 200 nm, and the thickness range of the oxide film It is 1-20 nm.
  • the oxide film has a thickness ranging from 10 to 20 nm.
  • a surface pore adsorbing agent is adsorbed on the surface of the oxide film, and the pore-piercing agent is terephthalic acid, ethylenediaminetetraacetic acid, p-nitrobenzenesulfonic acid, water-soluble amino acid, ethylenediamine, triethanolamine. At least one of ammonia water, ethyl chloride, and epichlorohydrin.
  • the plastic material is doped with a filler material
  • the filler material is at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silicon dioxide, and clay.
  • the percentage of the filler material in the plastic material ranges from 5 to 40 wt.%.
  • the invention also provides a method for processing a combination of stainless steel and plastic, providing a stainless steel substrate; forming a honeycomb pore on the surface of the stainless steel substrate; and passivating the stainless steel substrate with an organic oxidizing solution, Forming an oxide film on a surface of the stainless steel substrate, the oxide film comprising at least two of iron oxide, chromium oxide or nickel oxide;
  • the surface of the material is injection molded with a plastic material, and a part of the structure of the plastic material is embedded in the honeycomb pores to form an integrated combination of stainless steel and plastic.
  • the oxide film comprises a special oxide and a chromium oxide.
  • the organic oxidizing solution is a mixed solution of citric acid having a mass fraction of 5-20% and hydrogen peroxide having a mass fraction of 5-30%;
  • the organic oxidizing solution is a mixed solution of a mass fraction of 0.1-5% potassium chloride and a mass fraction of 30-80% acetic acid.
  • the passivation treatment has a temperature of 10-60 degrees Celsius and the passivation treatment time is 2-30 minutes.
  • the stainless steel substrate is subjected to a boring treatment, and the stainless steel substrate is immersed in the porogen, the porphyrin is terephthalic acid, ethylenediaminetetraacetic acid, p-nitrobenzene At least one of a sulfonic acid, a water-soluble amino acid, ethylenediamine, triethanolamine, aqueous ammonia, ethyl chloride or epichlorohydrin.
  • the inventors of the present invention have found that in the prior art, although there are technical solutions for injection-molding some metal materials with plastic materials, there is no improvement in the prior art for the composite manner of stainless steel and plastic materials. A technical solution with high reliability. For the existing compounding scheme, the processed materials used are harmful to the human body and the environment. 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.
  • FIG. 1 is a schematic view showing the structure of a joint of stainless steel and plastic provided by the present invention.
  • FIG. 2 is a schematic view showing the topographical features of the honeycomb pores provided in an embodiment of the present invention.
  • FIG. 3 is a schematic view showing the surface structure of a stainless steel substrate provided by the present invention.
  • the present invention provides a combination of stainless steel and plastic that includes a stainless steel substrate and an injection molded plastic.
  • a honeycomb-like pore 11 is formed on the surface of the stainless steel substrate 1, and the honeycomb-shaped pores 11 have a nano-scale pore structure.
  • the honeycomb pores 11 may be formed only in a region on the stainless steel substrate 1 where the plastic material 2 needs to be injection molded.
  • the honeycomb pores 11 may be formed on the entire surface of the stainless steel substrate 1.
  • an oxide film 12 is formed on the surface of the honeycomb pores 11, and as shown in Fig. 3, the oxide film 12 is formed by passivation treatment of an organic oxidizing solution.
  • the stainless steel substrate 1 may be placed in an organic oxidizing solution, and after the passivation for a certain period of time, the stainless steel substrate 1 is taken out from the organic oxidizing solution, and the passivation treatment forms oxidation at least on the surface of the honeycomb pores 11.
  • the oxide film 12 includes at least two of iron oxide, chromium oxide, or nickel oxide. The thickness and composition of the oxide film can be adjusted by adjusting the temperature and time of the passivation treatment. In the preferred real In the embodiment, the oxide film includes iron oxide and chromium oxide.
  • the joint of stainless steel and plastic provided by the invention has the following technical effects.
  • the combination of the stainless steel substrate and the plastic material is further improved on the basis of the fine holes.
  • the oxide film formed by the passivation treatment is grown in situ from the surface of the stainless steel substrate, and the oxide film has a stronger bonding force with the stainless steel substrate. Therefore, the stainless steel substrate and the plastic material are not easily separated and damaged during the drawing or shearing process.
  • the oxide film grown by in-situ oxidation has a distinct and stronger bonding force with respect to the oxide layer formed by impregnation and drying using an acid solution or a salt solution containing metal ions.
  • the oxide film of the present invention is more physically and chemically bonded to a stainless steel substrate.
  • the oxide film of the present invention has a denser structure and stronger corrosion resistance than the above-mentioned conventional oxide film. This structural feature ensures the reliability of plastic material injection on the oxide film, and prevents corrosion cracking, mechanical fracture, and the like. .
  • the organic oxidizing acid has stronger activity on iron than chromium, and can remove free iron and its oxide on the surface of the stainless steel, thereby enriching a large amount of chromium on the surface of the stainless steel, and in the solution.
  • the oxygen reaction combines to form a low thermal conductivity chromium oxide. Therefore, the oxide film component after passivation of the scheme is mainly composed of chromium oxide, and the presence of oxide of nickel having a large thermal conductivity is suppressed.
  • the present invention can adjust the organic oxidizing solution, the treatment temperature and the treatment time used in the passivation treatment, and the material of the oxide film can be mainly iron oxide, chromium oxide or nickel oxide.
  • the above three oxides have a heat transfer coefficient smaller than that of the stainless steel substrate, and the oxide film is equivalent to the stainless steel substrate covered with a heat insulating layer.
  • the oxide film can reduce the heat loss of the plastic material and reduce the heat of the plastic material from being lost from one side of the stainless steel substrate. This effect delays the time for solidification and crystallization of the plastic material, so that the plastic material can be more fully filled in the honeycomb pores, and the bottom of the honeycomb pores can also be well filled. In this way, the stainless steel substrate and the plastic material can exhibit better airtightness and the connection reliability is higher.
  • the junction According to XPS analysis, at 12 nm from the surface layer of the stainless steel substrate, Fe, Cr, Ni, and O elements are mainly present in the oxide film. Among them, the element content is mainly Cr and O, and Fe and Ni are a little. It can be seen that the thickness of the oxide film is 12 nm or more, which is larger than the natural oxide film of 2-4.8 nm of stainless steel, and mainly consists of chromium oxide and iron oxide having a small thermal conductivity, and exhibits a good heat insulating effect.
  • 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
  • the thermal conductivity of chromium oxide is about 10 W/m ⁇ K.
  • the honeycomb porous stainless steel sheet prepared by the technical scheme is passivated by a mixed solution of 5-20% by mass of citric acid and 5-30% by mass of hydrogen peroxide, and then embedded in an injection molding die.
  • a plastic material mixed with PBT + 30 wt% glass fiber was injected at an injection temperature of 300 ° C, and finally injection-molded to obtain a joint of stainless steel and plastic.
  • the area of the plastic and stainless steel joint was 0.5 cm 2 and was drawn and stretched on a tensile tester to obtain an average shear breaking force of 30.6 MPa. This has a significant increase in the cutting strength compared to the conventional conventional scheme.
  • the conventional oxide film is mainly a natural oxide film of iron, or a manganese oxide, a zinc phosphorus oxide or the like.
  • This oxide film has a large thermal conductivity and cannot function as a heat insulator.
  • the oxide film which is naturally generated slowly is not only thinner in thickness, but also loose in structure, and the natural oxide film does not have sufficient corrosion resistance, resulting in corrosion damage of the bonded body. Therefore, the passivation treatment step of the present invention can have a good technical effect, and the oxide film formed by oxidation in the organic oxidizing solution has a thick thickness, a high hardness, a strong corrosion resistance, and a significant increase between the plastic and the plastic. The combination of strength.
  • the bonding member provided by the present invention has the above-described technical effects, in the present invention, the pore diameter of the honeycomb pores can be appropriately reduced, and the bonding force between the stainless steel substrate and the plastic material can be ensured.
  • the corresponding pore forming process is also simplified, thereby resulting in simplification of the process flow and reduction in time cost.
  • Figure 2 shows the morphology of the honeycomb pores on the surface of the stainless steel substrate after passivation treatment, and the honeycomb pores are evenly distributed.
  • 3 shows the oxide film 12 on the surface of the honeycomb pores 11 and the honeycomb pores 11.
  • the organic oxidizing solution may be acetic acid, phytic acid, oxalic acid, lactic acid, citric acid, peracetic acid, tannic acid, tartaric acid, ammonia triacetic acid, pyrophosphoric acid, formic acid, ethylenediamine.
  • acetic acid phytic acid, oxalic acid, lactic acid, citric acid, peracetic acid, tannic acid, tartaric acid, ammonia triacetic acid, pyrophosphoric acid, formic acid, ethylenediamine.
  • the pH of the organic oxidizing solution can be controlled between 1-5.
  • the organic oxidizing solution used for passivating the stainless steel substrate may be a mixed solution of citric acid having a mass fraction of 5-20% and hydrogen peroxide having a mass fraction of 5-30%.
  • the organic oxidizing solution used for the passivation treatment may be a mixed solution of a mass fraction of 0.1-5% potassium chloride and a mass fraction of 30-80% acetic acid.
  • organic oxidizing solution used in the present invention can perform good passivation.
  • organic acids such as citric acid, acetic acid and phytic acid do not dissolve heavy metal ions such as chromium and nickel during chemical passivation, but oxidize them into oxides to form a passivation film.
  • the discharged wastewater is free of heavy metal pollution. It is directly absorbed and degraded by plants and organisms.
  • the organic oxidizing solution used in the technical solution is environmentally friendly solution such as organic acid, which causes less damage to the human body and has less impact on the environment, and is in line with the development trend of sustainable development.
  • the plastic material may be made of at least one of a polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin. These materials can be combined to form a high-hardness crystalline resin composition in which the composition can be crystallized and solidified in the honeycomb pores after cooling.
  • the honeycomb pores may have an average pore diameter ranging from 10 to 150 nm, and the honeycomb pores may extend from the surface of the stainless steel substrate to an inner depth ranging from 10 to 200 nm.
  • the above structural features can be adjusted by controlling the pore forming process.
  • the honeycomb pores have an average pore size of 60 nm.
  • the oxide film may have a thickness ranging from 1 to 20 nm, and the thickness of the oxide film may be adjusted by adjusting the temperature of the passivation treatment, the time, the composition of the organic oxidizing solution, and the like.
  • the thickness of the oxide film is controlled to be between 10 and 20 nm.
  • the surface of the oxide film may further adsorb a pore-piercing agent, which is terephthalic acid, ethylenediaminetetraacetic acid, p-nitrobenzenesulfonic acid, water-soluble amino acid, ethylenediamine, and three B At least one of an alcohol amine, ammonia water, ethyl chloride, and epichlorohydrin.
  • the pore-penetrating agent can improve the surface characteristics of the oxide film, so that the plastic material can smoothly flow into the honeycomb pores during the injection molding process.
  • the plastic material may also be doped with a filler material, which is at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silicon dioxide, and clay.
  • a filler material which is at least one of nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, silicon dioxide, and clay.
  • the percentage of the filler material in the plastic material ranges from 5 to 40% by weight.
  • the filler material may be doped in the plastic material prior to the injection molding process.
  • the coefficient of linear expansion of stainless steel is 1.5 ⁇ 10 -5 /°C, while the coefficient of linear expansion of plastic materials is 6-8 ⁇ 10 -5 /°C.
  • the coefficient of linear expansion between stainless steel and plastic materials is not conducive to the curing of plastic materials. process. Therefore, it is necessary to modify the plastic material to reduce the coefficient of linear expansion of the plastic material.
  • the glass fiber material has a linear expansion coefficient of only 3.8 ⁇ 10 -5 / ° C, and a material such as glass fiber can be blended in the plastic material so that the linear expansion coefficient of the plastic material composition is as close as possible to the stainless steel.
  • the present invention also provides a method for processing a combination of stainless steel and plastic.
  • a stainless steel substrate is provided to form honeycomb pores on the surface of the stainless steel substrate; and then the stainless steel substrate is subjected to an organic oxidizing solution.
  • Passivation treatment forming an oxide film on the surface of the stainless steel substrate, the oxide film comprising at least two of iron oxide, chromium oxide or nickel oxide; finally, molding plastic on the surface of the stainless steel substrate
  • the material is such that a partial structure of the plastic material is embedded in the honeycomb pores to form an integrated combination of stainless steel and plastic.
  • the combination of stainless steel and plastic provided by the present invention can be prepared by the processing method provided by the present invention.
  • the step of pretreatment may also be included prior to the hole forming process of the stainless steel substrate.
  • the degreasing and degreasing treatment of the stainless steel substrate may be performed in advance.
  • the stainless steel substrate was soaked in a stainless steel cleaning agent at 35-80 ° C for 60-600 s, and then washed in pure water having a conductivity of less than 20 us/cm for 60 s.
  • the stainless steel cleaning agent is an acid, a base or an organic solvent of 100 to 300 g/L.
  • the surface layer of the stainless steel substrate can also be subjected to de-natural oxide treatment.
  • the degreased stainless steel substrate is immersed in a 40-80 ° C removal solution for about 60 s, and then placed in neutralization.
  • the solution is treated for about 60 s in the liquid and then rinsed in pure water.
  • the membrane removing solution is an alkaline solution of 5-10 vol.% sodium hydroxide or potassium hydroxide, and the neutralizing liquid is 100-300 g/L of dilute nitric acid and sulfuric acid liquid and neutralizing alkali residue on the stainless steel substrate. Solution. Its main purpose is to remove the natural oxide film formed on the surface of the stainless steel substrate, and to eliminate the adverse effect of the uneven oxide film on the etching process.
  • the organic oxidizing solution may be a mixed solution of citric acid having a mass fraction of 5-20% and hydrogen peroxide having a mass fraction of 5-30%.
  • the organic oxidizing solution may be a mixed solution of a mass fraction of 0.1-5% potassium chloride and a mass fraction of 30-80% acetic acid.
  • the above are two organic oxidizing solutions exemplified in the present invention which are suitable for the method of the present invention. Other solutions may be used as the organic oxidizing solution according to actual performance requirements of the product, and the present invention does not limit.
  • the organic oxidizing solution can perform good oxidation passivation, and has little harm to the human body and the environment, and is in line with the development trend of sustainable development.
  • the passivation treatment temperature is 10-60 degrees Celsius, and the passivation treatment time is 2-30 minutes. This processing condition ensures that the formed oxide film is dense and has a sufficient thickness.
  • the stainless steel substrate may be subjected to a hole-removing treatment, which can improve the surface characteristics of the oxide film, so that the plastic material can be better filled into the honeycomb-like fine in the subsequent injection molding process.
  • a hole-removing treatment may immerse the stainless steel substrate in a pore-treating agent, which is terephthalic acid, ethylenediaminetetraacetic acid, p-nitrobenzenesulfonic acid, water-soluble amino acid, ethylenediamine, triethanolamine. At least one of ammonia water, ethyl chloride, and epichlorohydrin.
  • the stainless steel substrate After the stainless steel substrate is taken out from the porogen, it can be dried naturally or washed.
  • the pore-penetrating agent uniformly attached to the oxide layer can physically and chemically react with the plastic material in the injection molding process, so that the plastic material accelerates into the honeycomb-like pores, and the bonding force between the plastic and the stainless steel member is remarkably improved.
  • the present invention can employ an etching treatment.
  • the stainless steel substrate is immersed in a chemical etching solution at 30-90 degrees Celsius for 10 to 120 minutes by chemical etching, and the chemical etching solution is sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, boric acid, formic acid, propionic acid. , butyric acid, alginic acid, oxalic acid, citric acid and caprolactam At least one of them.
  • electrochemical etching may be employed, wherein the stainless steel substrate is used as an anode to electrochemically etch a region where the honeycomb pores are to be formed, and the electrochemical etching voltage ranges from 5 to 60 V for a duration of 10 to 100 minutes. .

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

一种不锈钢和塑料的结合件，包括不锈钢基材(1)，不锈钢基材(1)的表面上形成有蜂窝状细孔(11)，经过有机氧化性溶液的钝化处理，蜂窝状细孔(11)的表面上形成有氧化膜(12)，氧化膜(12)至少包括铁氧化物、铬氧化物或镍氧化物中的两种，不锈钢基材(1)上注塑成型有塑料材料(2)，塑料材料(2)嵌入蜂窝状细孔(11)中。还公开了一种不锈钢和塑料的结合体的加工方法。

Description

不锈钢和塑料的结合件及其加工方法 技术领域
本发明涉及材料加工技术领域，具体地，涉及一种不锈钢和塑料的结合件及其加工方法。
背景技术
随着材料技术的逐渐发展，越来越多的产品采用金属和塑料复合的形式构成产品结构。这种结构设计可以实现丰富的功能效果。例如，在需要产品的外观呈现金属特征而内部结构需要降低重量、节省材料成本的情况下，就可以采用金属与塑料复合的设计。
金属与塑料的传统复合方式包括粘接剂粘合、卡扣卡合或者铆钉连接等方式。但是，传统的复合方式存在复合可靠性低、需增加固定连接的机构等缺陷。随着技术的发展，现有技术中还出现了将塑料注塑在金属表面的复合方式。在进行塑料的注塑加工时，以金属材料作为基材，将塑料直接注塑成型在金属材料上。但是，金属和塑料之间的结合作用力有限，两者之间存在脱落的风险，复合可靠性难以提高。
另一方面，为了使塑料能够注塑固定在金属上，往往需要对金属进行化学处理，化学处理所使用的物料对人体有危害、污染环境，且成本较高。
因此，有必要对金属与塑料材料的复合工艺进行改进，提高材料复合的结构可靠性，或者减小加工物料对人体的危害。
发明内容
本发明的一个目的是提供一种不锈钢和塑料复合的新技术方案。
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，所述 结合件包括不锈钢基材，所述不锈钢基材的表面上形成有蜂窝状细孔，经过有机氧化性溶液的钝化处理，所述蜂窝状细孔的表面上形成有氧化膜，所述氧化膜至少包括铁氧化物、铬氧化物或镍氧化物中的两种，所述不锈钢基材上注塑成型有塑料材料，所述塑料材料嵌入所述蜂窝状细孔中。
可选地，所述有机氧化性溶液为醋酸、植酸、草酸、乳酸、柠檬酸、过氧乙酸、单宁酸、酒石酸、氨三乙酸、焦磷酸、甲酸、乙二胺四乙酸、聚马来酸、聚丙烯酸、羟基叉二磷酸、乙二胺甲叉磷酸中的至少一种。
可选地，所述有机氧化性溶液的PH＝1-5。
可选地，所述氧化膜包括铁氧化物和铬氧化物。
可选地，所述钝化处理采用的有机氧化性溶液为质量分数5-20％的柠檬酸与质量分数5-30％的双氧水的混合溶液。
可选地，所述钝化处理采用的有机氧化性溶液为质量分数0.1-5％氯化钾和质量分数30-80％的醋酸的混合溶液。
可选地，所述蜂窝状细孔的平均孔径范围为10-150nm，所述蜂窝状细孔从不锈钢基材的表面向内部延伸的平均深度范围为10-200nm，所述氧化膜的厚度范围为1-20nm。
可选地，所述氧化膜的厚度范围为10-20nm。
可选地，所述氧化膜的表面吸附有润孔剂，所述润孔剂为对苯二甲酸、乙二胺四乙酸、对硝基苯磺酸、水溶性氨基酸、乙二胺、三乙醇胺、氨水、氯乙烷、环氧氯丙烷中的至少一种。
可选地，所述塑料材料中掺杂有填充材料，所述填充材料为尼龙纤维、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，所述填充材料在所述塑料材料中所占质量百分比的范围为5-40wt.％。
本发明还提供了一种不锈钢和塑料的结合体的加工方法，提供不锈钢基材；在不锈钢基材的表面形成蜂窝状细孔；用有机氧化性溶液对所述不锈钢基材进行钝化处理，在所述不锈钢基材的表面形成氧化膜，所述氧化膜至少包括铁氧化物、铬氧化物或镍氧化物中的两种；在所述不锈钢基 材的表面注塑塑料材料，使塑料材料的部分结构嵌在所述蜂窝状细孔中，形成不锈钢与塑料的一体化结合体。
可选地，所述氧化膜包括特氧化物和铬氧化物。
可选地，所述有机氧化性溶液为质量分数5-20％的柠檬酸与质量分数5-30％的双氧水的混合溶液；
或者，所述有机氧化性溶液为质量分数0.1-5％氯化钾和质量分数30-80％的醋酸的混合溶液。
可选地，所述钝化处理的温度为10-60摄氏度，钝化处理的时间为2-30分钟。
可选地，在钝化处理后，对不锈钢基材进行润孔处理，将不锈钢基材浸入润孔剂中，所述润孔剂为对苯二甲酸、乙二胺四乙酸、对硝基苯磺酸、水溶性氨基酸、乙二胺、三乙醇胺、氨水、氯乙烷、环氧氯丙烷中至少一种。
本发明的发明人发现，在现有技术中，虽然出现了将一些金属材料与塑料材料注塑复合的技术方案，但是，对于不锈钢与塑料材料的复合方式，现有技术中并没有出现改进的、复合可靠性高的技术方案。对于现有的复合方案，采用的加工物料对人体和环境都有危害。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。
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。
附图说明
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。
图1是本发明提供的不锈钢和塑料的结合件的结构示意图。
图2是本发明一种实施方式中提供的蜂窝状细孔的形貌特征示意图。
图3是本发明提供的不锈钢基材的表面结构示意图。
具体实施方式
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。
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。
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。
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。
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。
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注塑塑料。如图1所示，所述不锈钢基材1的表面上形成有蜂窝状细孔11，所述蜂窝状细孔11为纳米级的孔洞结构。可选地，所述蜂窝状细孔11可以只形成在不锈钢基材1上需要注塑塑料材料2的区域。或者，也可以在不锈钢基材1的全部表面形成蜂窝状细孔11。特别地，所述蜂窝状细孔11的表面上形成有氧化膜12，如图3所示，所述氧化膜12是经过有机氧化性溶液的钝化处理形成的。可以将所述不锈钢基材1放置在有机氧化性溶液中，钝化一定时间后将不锈钢基材1从有机氧化性溶液中取出，钝化处理会至少在蜂窝状细孔11的表面上形成氧化膜12。所述氧化膜12至少包括铁氧化物、铬氧化物或镍氧化物中的两种。通过对钝化处理的温度和时间进行调控，可以调节氧化膜的厚度和成分。在优选的实 施方式中，所述氧化膜包括铁氧化物和铬氧化物。
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，经过钝化处理形成的氧化膜体积发生膨胀，表面形成细微的凹凸面，增加了蜂窝状细孔的表面粗糙度，在蜂窝状细孔的基础上进一步提高了不锈钢基材与塑料材料的结合作用力。
第二，钝化处理形成的氧化膜是从不锈钢基材的表面原位氧化生长而成，所述氧化膜与不锈钢基材之间具有更强的结合力。因此，结合件整体在拉拔或者剪切过程中，不锈钢基材与塑料材料不易分离、损坏。特别地，原位氧化生长而成的氧化膜相对于使用含有金属离子的酸溶液或盐溶液浸渍、烘干形成的氧化层具有明显的、更强的结合作用力。本发明的氧化膜与不锈钢基材的物理化学结合性更强。而且，本发明的氧化膜与上述传统氧化膜相比，结构更密实，耐腐蚀性更强，这种结构特点保证了塑料材料注塑在氧化膜上的可靠性，防止腐蚀开裂、力学断裂等情况。
第三，有机氧化性溶液在钝化过程中，有机氧化性酸对铁的活性比铬要强，能够去除不锈钢表面的游离铁及其氧化物，从而在不锈钢表面富集大量的铬，与溶液中氧反应结合形成低导热系数的三氧化二铬。因此，该方案钝化后的氧化膜组份主要以三氧化二铬为主，而抑制了较大导热系数的镍的氧化物的存在。
进一步地，本发明通过对钝化处理采用的有机氧化性溶液、处理温度、处理时间进行调控，可以使氧化膜的材料主要为铁氧化物、铬氧化物或镍氧化物。上述三种氧化物的热传导系数均小于不锈钢基材，所述氧化膜相当于所述不锈钢基材上覆盖了一层隔热层。在进行注塑工艺时，所述氧化膜能够减少塑料材料的热量散失，减少塑料材料的热量从不锈钢基材的一侧散失。这一效果延缓了塑料材料凝固、结晶的时间，使塑料材料能够更充分的填充在蜂窝状细孔内，蜂窝状细孔的底部也能够获得较好的填充。这样，不锈钢基材与塑料材料之间能够呈现更好的气密性，并且连接可靠性更高。
在本发明的一种实施方式中，通过对钝化处理的条件进行调控，结 合XPS分析，在距不锈钢基材的表层12nm处，氧化膜中主要存在Fe、Cr、Ni、O元素。其中，元素含量主要以Cr、O为主，Fe、Ni少许。可见，氧化膜的厚度为12nm以上，要大于不锈钢的2-4.8nm的自然氧化膜，且主要以导热系数较小的铬氧化物、铁氧化物为主，呈现出良好的隔热效果。其中，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。
经本技术方案制备的蜂窝状多孔不锈钢钢片，由质量分数5-20％的柠檬酸与质量分数5-30％的双氧水的混合溶液钝化后，嵌入到注射成型模中。在注射温度为300℃下注射由PBT+30wt％玻璃纤维混合的塑料材料，最终注射成型得到不锈钢和塑料的结合件。塑料与不锈钢结合件的面积为0.5cm2,在拉伸试验机上牵引拉伸，得到其平均剪切断裂力为30.6MPa。这相比于现有常规方案的切断强度有大幅度的提升。
传统的氧化膜，主要是铁的自然氧化膜，或者是锰氧化物、锌磷氧化物等。这种氧化膜的导热性较大，无法起到隔热的作用。而且，自然缓慢生成的氧化膜不仅厚度较薄，结构疏松，而且自然氧化膜没有足够的耐腐蚀性，导致结合体会发生腐蚀破坏。因此，本发明所述的钝化处理步骤能够起到良好的技术效果，浸渍于有机氧化性溶液中氧化形成的氧化膜厚度较厚、硬度较高、耐腐蚀性较强，显著增加与塑料间的结合力。
另一方面，由于本发明提供的结合件具有上述技术效果，所以在本发明中，可以适当减小蜂窝状细孔的孔径，仍能保证不锈钢基材与塑料材料之间的结合作用力。降低蜂窝状细孔的孔径，相应的成孔工艺也得到简化，由此带来工艺流程的简化和时间成本的降低。蜂窝状细孔的孔径降低后，孔洞的分布更均匀，成孔质量更高。图2示出了经过钝化处理后，不锈钢基材表面的蜂窝状细孔的形貌，蜂窝状细孔分布均匀。图3示出了蜂窝状细孔11以及蜂窝状细孔11表面的氧化膜12。
可选地，所述有机氧化性溶液为可以为醋酸、植酸、草酸、乳酸、柠檬酸、过氧乙酸、单宁酸、酒石酸、氨三乙酸、焦磷酸、甲酸、乙二胺 四乙酸、聚马来酸、聚丙烯酸、羟基叉二磷酸、乙二胺甲叉磷酸中的至少一种。有机氧化性溶液的PH值可以控制在1-5之间。
在一种实施方式中，用于对不锈钢基材进行钝化处理的有机氧化性溶液可以为质量分数5-20％的柠檬酸与质量分数5-30％的双氧水的混合溶液。或者可选地，在另一种实施方式中，用于钝化处理的有机氧化性溶液可以为质量分数0.1-5％氯化钾和质量分数30-80％的醋酸的混合溶液。
以上是本发明提供的两种有机氧化性溶液的具体成分，本发明采用的有机氧化性溶液能够起到良好的钝化作用。同时，柠檬酸、醋酸、植酸等有机酸在化学钝化过程中不溶解铬、镍等重金属离子，而是把他们氧化成氧化物而形成钝化膜，排放的废水无重金属的污染，可被植物、生物直接吸收降解。且相比于浓硝酸、浓硫酸、铬酸等代表的传统钝化液，不存在浓硝酸使用中存在的酸雾及二氧化氮；浓硫酸的强烈的脱水性、助燃性；铬酸的腐蚀性、强氧化性和致癌性。因此，技术方案所采用的有机氧化性溶液以有机酸等环境友好型溶液，对人体造成的伤害小，对环境的影响较小，符合可持续性发展的技术发展趋势。
可选地，所述塑料材料可以由聚苯硫醚树脂、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材料制成。这些材料可以组合形成高硬度的结晶性树脂组合物，在注塑工艺中，组合物冷却后可以在蜂窝状细孔中结晶凝固。
可选地，所述蜂窝状细孔的平均孔径范围可以为10-150nm，所述蜂窝状细孔从不锈钢基材的表面向内部延伸的平均深度范围为10-200nm。可以通过对成孔工艺的调控对上述结构特征进行调节。可选地，所述蜂窝状细孔的平均孔径大小为60nm。
可选地，所述氧化膜的厚度范围可以为1-20nm，可以通过对钝化处理的温度、时间、有机氧化性溶液的成分等条件进行调控，从而调节氧化膜的厚度。优选地，所述氧化膜的厚度控制在10-20nm之间。
特别地，所述氧化膜的表面还可以吸附有润孔剂，所述润孔剂为对苯二甲酸、乙二胺四乙酸、对硝基苯磺酸、水溶性氨基酸、乙二胺、三乙 醇胺、氨水、氯乙烷、环氧氯丙烷中的至少一种。所述润孔剂能够改善氧化膜的表面特征，使得进行注塑成型工艺时，塑料材料能够顺畅的流动到蜂窝状细孔中。
特别地，所述塑料材料中还可以掺杂有填充材料，所述填充材料为尼龙纤维、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，所述填充材料在所述塑料材料中所占质量百分比的范围为5-40wt％。所述填充材料可以在进行注塑加工工艺之前掺杂填充在塑料材料中。
不锈钢的线膨胀系数为1.5×10-5/℃，而塑料材料的线膨胀系数在6-8×10-5/℃，不锈钢与塑料材料间相差较大的线膨胀系数不利于塑料材料的固化过程。因此，有必要对于塑料材料加以改性以降低塑料材料的线膨胀系数。例如，玻璃纤维材料的线膨胀系数仅为3.8×10-5/℃，可以将玻璃纤维等材料掺在在塑料材料中，使塑料材料组合物的线膨胀系数与不锈钢尽可能的接近。
本发明还提供了一种不锈钢和塑料的结合体的加工方法，首先，提供不锈钢基材，在不锈钢基材的表面形成蜂窝状细孔；然后，采用有机氧化性溶液对所述不锈钢基材进行钝化处理，在所述不锈钢基材的表面形成氧化膜，所述氧化膜至少包括铁氧化物、铬氧化物或镍氧化物中的两种；最后，在所述不锈钢基材的表面注塑塑料材料，使塑料材料的部分结构嵌在所述蜂窝状细孔中，形成不锈钢与塑料的一体化结合体。通过本发明提供的加工方法，能够制备本发明提供的不锈钢和塑料的结合体。
在对不锈钢基材进行成孔加工之前，还可以包括预处理的步骤。可选地，可以预先进行不锈钢基材的除油脱脂处理。将不锈钢基材浸泡于35-80℃的不锈钢清洗剂中超声处理60-600s，随后置于电导率小于20us/cm的纯水中清洗60s。所述不锈钢清洗剂为100-300g/L的酸、碱或有机溶剂等。
可选地，还可以对不锈钢基材的表层进行去自然氧化物处理。将除油脂后的不锈钢基材置于40-80℃除膜液中浸渍60s左右，随后置于中和 液中处理60s左右，而后置于纯水中清洗。所述除膜液为5-10vol.％氢氧化钠、氢氧化钾等碱性溶液，所述中和液为100-300g/L的稀硝酸和硫酸液中和不锈钢基材上残留的碱性溶液。其主要目的在于去除不锈钢基材表面形成的自然氧化膜，排除不均匀氧化膜对蚀刻过程的不利影响。
在本发明的一种可选的实施方式中，所述有机氧化性溶液可以为质量分数5-20％的柠檬酸与质量分数5-30％的双氧水的混合溶液。在另一种实施方式中，所述有机氧化性溶液可以为质量分数0.1-5％氯化钾和质量分数30-80％的醋酸的混合溶液。以上是本发明例举出的两种适用于本发明所述方法的有机氧化性溶液，根据实际对产品的性能的要求，还可以采用其它溶液作为所述有机氧化性溶液，本发明不对此进行限制。所述有机氧化性溶液能够起到良好的氧化钝化作用，而且对人体和环境的危害小，符合可持续发展的技术发展趋势。
可选地，对于采用上述两种有机氧化性溶液，所述钝化处理的温度10-60摄氏度，钝化处理的时间为2-30分钟。该处理条件保证了生成的氧化膜致密、具有足够的厚度。
特别地，在钝化处理后，还可以对所述不锈钢基材进行润孔处理，该处理可以改善氧化膜的表面特性，使后续注塑加工中塑料材料能够更好的填充到所述蜂窝状细孔中，形成塑料材料凝固后嵌于蜂窝状细孔中的形态。所述润孔处理可以将不锈钢基材浸入润孔剂中，所述润孔剂为对苯二甲酸、乙二胺四乙酸、对硝基苯磺酸、水溶性氨基酸、乙二胺、三乙醇胺、氨水、氯乙烷、环氧氯丙烷中至少一种。将不锈钢基材从润孔剂中取出后，可以自然晾干也可以清洗烘干。均匀附着在氧化层上的润孔剂可以与注塑过程中的塑料材料发生物理和化学反应，使得塑料材料加速充满蜂窝状细孔内，显著提高塑胶与不锈钢件的结合力。
对于在不锈钢基材的表面形成蜂窝状细孔的工艺，本发明可以采用刻蚀处理的方式。可选地，采用化学刻蚀，将不锈钢基材置于30-90摄氏度的化学蚀刻液中浸渍10-120分钟，化学蚀刻液为硫酸、硝酸、磷酸、氢氟酸、硼酸、甲酸、丙酸、丁酸、褐藻酸、草酸、柠檬酸和己内酰胺中 的至少一种。或者，可以采用电化学刻蚀，以所述不锈钢基材为阳极，使待形成蜂窝状细孔的区域发生电化学腐蚀，电化学蚀刻的电压范围为5-60V，持续时间为10-100分钟。
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。

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，所述不锈钢基材的表面上形成有蜂窝状细孔，经过有机氧化性溶液的钝化处理，所述蜂窝状细孔的表面上形成有氧化膜，所述氧化膜至少包括铁氧化物、铬氧化物或镍氧化物中的两种，所述不锈钢基材上注塑成型有塑料材料，所述塑料材料嵌入所述蜂窝状细孔中。
  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,所述有机氧化性溶液为醋酸、植酸、草酸、乳酸、柠檬酸、过氧乙酸、单宁酸、酒石酸、氨三乙酸、焦磷酸、甲酸、乙二胺四乙酸、聚马来酸、聚丙烯酸、羟基叉二磷酸、乙二胺甲叉磷酸中的至少一种。
  3. 根据权利要求1或2所述的不锈钢和塑料的结合件，其特征在于，所述有机氧化性溶液的PH＝1-5。
  4. 根据权利要求1-3任意之一所述的不锈钢和塑料的结合件，其特征在于，所述氧化膜包括铁氧化物和铬氧化物。
  5. 根据权利要求1-4任意之一所述的不锈钢和塑料的结合件，其特征在于，所述有机氧化性溶液为质量分数5-20％的柠檬酸与质量分数5-30％的双氧水的混合溶液。
  6. 根据权利要求1-5任意之一所述的不锈钢和塑料的结合件，其特征在于，所述有机氧化性溶液为质量分数30-80％的醋酸和质量分数0.1-5％氯化钾的混合溶液。
  7. 根据权利要求1-6任意之一所述的不锈钢和塑料的结合件，其特征在于，所述氧化膜的厚度范围为1-20nm。
  8. 根据权利要求1-7任意之一所述的不锈钢和塑料的结合件，其特征在于，所述氧化膜的表面吸附有润孔剂，所述润孔剂为对苯二甲酸、乙二胺四乙酸、对硝基苯磺酸、水溶性氨基酸、乙二胺、三乙醇胺、氨水、氯乙烷、环氧氯丙烷中的至少一种。
  9. 根据权利要求1-8任意之一所述的不锈钢和塑料的结合件，其特 征在于，所述塑料材料中掺杂有填充材料，所述填充材料为尼龙纤维、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，所述填充材料在所述塑料材料中所占质量百分比的范围为5-40wt.％。
  10. 一种不锈钢和塑料的结合体的加工方法，其特征在于，提供不锈钢基材；在不锈钢基材的表面形成蜂窝状细孔；用有机氧化性溶液对所述不锈钢基材进行钝化处理，在所述不锈钢基材的表面形成氧化膜，所述氧化膜至少包括铁氧化物、铬氧化物或镍氧化物中的两种；在所述不锈钢基材的表面注塑塑料材料，使塑料材料的部分结构嵌在所述蜂窝状细孔中，形成不锈钢与塑料的一体化结合体。
  11. 根据权利要求10所述的加工方法，其特征在于，所述氧化膜包括铁氧化物和铬氧化物。
  12. 根据权利要求10或11所述的加工方法，其特征在于，所述有机氧化性溶液为质量分数5-20％的柠檬酸与质量分数5-30％的双氧水的混合溶液。
  13. 根据权利要求10-12任意之一所述的加工方法，其特征在于，所述有机氧化性溶液为质量分数30-80％的醋酸和质量分数0.1-5％氯化钾的混合溶液。
  14. 根据权利要求10-13任意之一所述的加工方法，其特征在于，所述钝化处理的温度为10-60摄氏度，钝化处理的时间为2-30分钟。
  15. 根据权利要求10-14任意之一所述的加工方法，其特征在于，在钝化处理后，对不锈钢基材进行润孔处理，将不锈钢基材浸入润孔剂中，所述润孔剂为对苯二甲酸、乙二胺四乙酸、对硝基苯磺酸、水溶性氨基酸、乙二胺、三乙醇胺、氨水、氯乙烷、环氧氯丙烷中至少一种。
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