WO2018129870A1 - Stainless steel and plastic combined member, and processing method therefor - Google Patents

Stainless steel and plastic combined member, and processing method therefor Download PDF

Info

Publication number
WO2018129870A1
WO2018129870A1 PCT/CN2017/090621 CN2017090621W WO2018129870A1 WO 2018129870 A1 WO2018129870 A1 WO 2018129870A1 CN 2017090621 W CN2017090621 W CN 2017090621W WO 2018129870 A1 WO2018129870 A1 WO 2018129870A1
Authority
WO
WIPO (PCT)
Prior art keywords
stainless steel
acid
steel substrate
plastic
oxide film
Prior art date
Application number
PCT/CN2017/090621
Other languages
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
Original Assignee
歌尔股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 歌尔股份有限公司 filed Critical 歌尔股份有限公司
Publication of WO2018129870A1 publication Critical patent/WO2018129870A1/en

Links

Images

Classifications

    • 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
    • B29C45/14778—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 the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14795—Porous or permeable material, e.g. foam
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32

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 comprises a stainless steel substrate having a honeycomb-shaped pore formed on the surface of the stainless steel substrate, and an electrochemical passivation treatment, an oxide film is formed on the surface of the honeycomb pore, the electrochemical passivation treatment
  • the processing condition is a voltage of 0.5-6 V, and the passivation time is 1-30 minutes.
  • the oxide film includes at least two of iron oxide, chromium oxide or nickel oxide, and the stainless steel substrate is injection molded. A plastic material embedded in the honeycomb pores.
  • the solution used in the electrochemical passivation treatment is at least one of nitric acid, sulfuric acid, nitrous acid, hypochlorous acid, citric acid, phosphoric acid, chromic acid, permanganic acid and salts thereof.
  • the plastic material is made of at least one of a polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin.
  • 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.
  • 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, comprising: providing a stainless steel substrate; forming a honeycomb pore on the surface of the stainless steel substrate; and electrochemically passivating the stainless steel substrate
  • the surface of the stainless steel substrate forms an oxide film
  • the processing condition of the electrochemical passivation treatment is a voltage of 0.5-6 V
  • the passivation time is 1-30 minutes
  • the oxide film includes at least iron oxide and chromium oxide.
  • plastic material is injection molded on the surface of the stainless steel substrate, and a partial structure of the plastic material is embedded in the honeycomb pores to form an integrated combination of stainless steel and plastic.
  • the electrochemical passivation treatment uses a passivation solution having a volume fraction of 5-30% nitric acid, and the electrochemical passivation treatment uses a constant voltage of 0.6-3V.
  • the electrochemical passivation solution has a temperature of 20-40 degrees Celsius and a passivation time of 10-20 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-nitro At least one of benzenesulfonic acid, water-soluble amino acid, ethylenediamine, triethanolamine, aqueous ammonia, ethyl chloride, and 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 electrochemical passivation treatment.
  • the stainless steel substrate 1 may be placed in a passivation liquid, and the stainless steel substrate 1 is taken out from the passivation liquid after being energized for a certain period of time, and the electrochemical 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, time, energization voltage, and type of the passivation solution of the electrochemical passivation treatment.
  • the electrochemical treatment of the present invention has a treatment range of 0.5-6 V and a passivation time of 1-30 minutes.
  • the joint of the stainless steel and the plastic provided by the invention has the following technical effects.
  • the honeycomb pores further enhance the bonding force between the stainless steel substrate and the plastic material.
  • the oxide film formed by the passivation treatment is grown in situ from the surface of the stainless steel substrate.
  • 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 present invention can control the passivation liquid, the treatment temperature, the treatment time, the electrification voltage and the like used in the electrochemical 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 solution used in the electrochemical treatment may be at least one of nitric acid, sulfuric acid, nitrous acid, hypochlorous acid, citric acid, phosphoric acid, chromic acid, permanganic acid, and salts thereof. It is also possible to mix a plurality of solutions.
  • Fe, Cr, Ni, and O elements are mainly present in the oxide film at a surface of 12 nm from the surface layer of the stainless steel substrate.
  • the element content is mainly Fe, Cr, O, and Ni is a little.
  • the thickness of the oxide film is 12 nm or more, which is larger than the natural oxide film of 2-4.8 nm thick 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 honeycomb porous stainless steel substrate prepared by the present technical scheme is optionally embedded in an injection molding die by electrochemical passivation of a volume fraction of 5-30% nitric acid and a constant voltage of 0.6-3 V.
  • 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 29.5 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 of the present invention is a process in which an applied voltage drives the stainless steel to form an oxide film in the passivation region, and the oxide film formed by polarization is thicker.
  • the thickness of the formed oxide film reaches 14.3 nm.
  • the electrochemical passivation is also anodized, and the anode passivation process preferentially corrodes the passivated active metal. Therefore, after electrochemical passivation, stainless steel is mainly composed of chromium oxide and iron oxide.
  • 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 electrochemical passivation film layer is thicker and has higher hardness. Better insulation and corrosion resistance, significantly increasing the bonding between stainless steel and plastic.
  • 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 electrochemical 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 electrochemical passivation treatment uses a passivation solution having a volume fraction of 5-30% nitric acid, and the electrochemical passivation treatment uses a constant voltage of 0.6-3V.
  • the electrochemical passivation treatment used in the present invention applies a voltage to a stainless steel substrate, and is made of a stainless steel substrate.
  • the anode electrochemically reacts its surface with an oxidizing passivation medium to form a dense passivation film. Due to the forced driving of the applied potential, the chemical reaction on the surface of the stainless steel substrate is more efficient, and it is more compact and more effective than the ordinary acid-washed oxide film.
  • the above is a specific manner of electrochemical passivation treatment provided by the present invention.
  • the invention adopts constant potential electrochemical passivation, has simple equipment and process, has clear electrode state in the polarization process, has small influence factors, and is passivated. Can play a good passivation oxide film forming effect.
  • the oxide film prepared by the invention has higher reliability, and the pitting potential of the stainless steel substrate can reach 1000 mV (25 ° C, 3 wt.% NaCl). the above.
  • the concentration of the acid solution used is relatively low, the use is safe, and the impact on the human body and the environment is small, which is in line with the technological 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 plastic material may also be doped with a filler material, which is nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, and second. At least one of silicon oxide and clay, the filler material occupies a mass percentage in the plastic material ranging 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 invention also provides a method for processing a combination of stainless steel and plastic, firstly, providing a stainless steel substrate, forming a honeycomb pore on the surface of the stainless steel substrate; and then electrochemically passivating the stainless steel substrate Forming an oxide film on the surface of the stainless steel substrate, the oxide film including at least two of iron oxide, chromium oxide or nickel oxide, and the processing condition of the electrochemical passivation treatment is 0.5-6V The voltage and the passivation time are 1-30 minutes. Finally, the plastic material is injection molded on the surface of the stainless steel substrate, and 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 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, then placed in a neutralizing solution for about 60 s, and then washed 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 passivation solution used in the electrochemical passivation treatment is nitric acid having a volume fraction of 10-20%, and the electrochemical passivation treatment adopts a constant voltage of 0.8-1.5V. .
  • An electrode is attached to the stainless steel substrate that acts as an anode in an electrochemical reaction.
  • the treatment temperature is 30 degrees Celsius and the treatment time is 15 minutes.
  • the oxide film obtained by the invention has higher reliability, and the pitting potential of the stainless steel substrate can reach 1000 mV or more.
  • the concentration of nitric acid used is relatively low, the use is safe, and the impact on the human body and the environment is small, which is in line with the technological development trend of sustainable development.
  • the stainless steel substrate may be subjected to a boring treatment, which can improve the surface characteristics of the oxide film, so that the plastic material can be better filled into the honeycomb in the subsequent injection molding process.
  • a boring treatment which can improve the surface characteristics of the oxide film, so that the plastic material can be better filled into the honeycomb in the subsequent injection molding process.
  • the 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.

Abstract

A stainless steel and plastic combined member, and a processing method therefor. The stainless steel and plastic combined member comprises a stainless steel substrate (1). Honeycomb pores (11) are formed on the surface of the stainless steel substrate (1). An oxide film (12) is formed on the surface having the honeycomb pores (11) by means of electrochemical passivation. The treatment conditions for the electrochemical passivation are that the voltage is 0.5-6 V and the passivation time is 1-30 minutes. The oxide film (12) at least comprises two of an iron oxide, a chromic oxide, and a nickel oxide. A plastic material (2) is formed on the stainless steel substrate (1) by means of injection molding. The plastic material (2) is embedded into the honeycomb pores (11). The oxide film (12) has a good heat insulation effect and improves the combining force between the stainless steel substrate (1) and the plastic material (2).

Description

不锈钢和塑料的结合件及其加工方法Combination of stainless steel and plastic and processing method thereof 技术领域Technical field
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。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.
背景技术Background technique
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。With the gradual development of materials technology, more and more products use 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.
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。Traditional combinations of metal and plastic include adhesive bonding, snap-fit or rivet attachment. However, the conventional composite method has defects such as low composite reliability and a need to increase the fixed connection mechanism. With the development of technology, a composite method of injection molding plastic on a metal surface has appeared in the prior art. In the plastic injection molding process, the plastic is directly injection molded on the metal material using the metal material as a substrate. However, the bonding force between metal and plastic is limited, there is a risk of falling off between the two, and the composite reliability is difficult to improve.
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。On the other hand, in order to enable plastics to be injection molded and fixed on metal, it is often necessary to chemically treat the metal, and the materials used in the chemical treatment are harmful to the human body, pollute the environment, and have high cost.
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。Therefore, it is necessary to improve the composite process of metal and plastic materials, improve the structural reliability of the material composite, or reduce the harm of the processed materials to the human body.
发明内容Summary of the invention
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。It is an object of the present invention to provide a new technical solution for the composite of stainless steel and plastic.
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，经过电化学钝化处理，所述蜂窝状细孔的表面上形成有氧化膜，所述电化学钝化处理的处理条件为0.5-6V的电压，钝化时间为1-30分钟，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。According to a first aspect of the present invention, a joint of stainless steel and plastic is provided, The bonding member comprises a stainless steel substrate having a honeycomb-shaped pore formed on the surface of the stainless steel substrate, and an electrochemical passivation treatment, an oxide film is formed on the surface of the honeycomb pore, the electrochemical passivation treatment The processing condition is a voltage of 0.5-6 V, and the passivation time is 1-30 minutes. The oxide film includes at least two of iron oxide, chromium oxide or nickel oxide, and the stainless steel substrate is injection molded. A plastic material embedded in the honeycomb pores.
可选地，所述电化学钝化处理采用的溶液为硝酸、硫酸、亚硝酸、次氯酸、柠檬酸、磷酸、铬酸、高锰酸及其盐中的至少一种。Optionally, the solution used in the electrochemical passivation treatment is at least one of nitric acid, sulfuric acid, nitrous acid, hypochlorous acid, citric acid, phosphoric acid, chromic acid, permanganic acid and salts thereof.
可选地，所述塑料材料由聚苯硫醚树脂、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。Alternatively, the plastic material is made of at least one of a polyphenylene sulfide resin, a polybutylene terephthalate resin, a polyamide, a polycarbonate, and a polyolefin.
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。Optionally, 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.
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。Optionally, 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.
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.％。Optionally, the plastic material is doped with a filler material, and 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.%.
本发明还提供了一种不锈钢和塑料的结合体的加工方法，包括：提供不锈钢基材；在不锈钢基材的表面形成蜂窝状细孔；对所述不锈钢基材进行电化学钝化处理，在所述不锈钢基材的表面形成氧化膜，所述电化学钝化处理的处理条件为0.5-6V的电压，钝化时间为1-30分钟，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。The invention also provides a method for processing a combination of stainless steel and plastic, comprising: providing a stainless steel substrate; forming a honeycomb pore on the surface of the stainless steel substrate; and electrochemically passivating the stainless steel substrate The surface of the stainless steel substrate forms an oxide film, the processing condition of the electrochemical passivation treatment is a voltage of 0.5-6 V, and the passivation time is 1-30 minutes, and the oxide film includes at least iron oxide and chromium oxide. Or two of the nickel oxides; plastic material is injection molded on the surface of the stainless steel substrate, and a partial structure of the plastic material is embedded in the honeycomb pores to form an integrated combination of stainless steel and plastic.
可选地，所述电化学钝化处理采用的钝化液为体积分数5-30％的硝酸，所述电化学钝化处理采用0.6-3V的恒定电压。 Optionally, the electrochemical passivation treatment uses a passivation solution having a volume fraction of 5-30% nitric acid, and the electrochemical passivation treatment uses a constant voltage of 0.6-3V.
可选地，所述电化学钝化溶液温度20-40摄氏度，钝化时间为10-20分钟。Optionally, the electrochemical passivation solution has a temperature of 20-40 degrees Celsius and a passivation time of 10-20 minutes.
可选地，在电化学钝化后，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。Optionally, after the electrochemical passivation, 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-nitro At least one of benzenesulfonic acid, water-soluble amino acid, ethylenediamine, triethanolamine, aqueous ammonia, ethyl chloride, and epichlorohydrin.
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。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.
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是本发明提供的不锈钢和塑料的结合件的结构示意图。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a joint of stainless steel and plastic provided by the present invention.
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。2 is a schematic view showing the topographical features of the honeycomb pores provided in an embodiment of the present invention.
图3是本发明提供的不锈钢基材的表面结构示意图。3 is a schematic view showing the surface structure of a stainless steel substrate provided by 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 at least one exemplary embodiment is merely illustrative and is in no way Any limitations to the invention and its application or use.
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, and therefore, once an item is defined in one figure, it is not required to be further discussed in the 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是经过电化学钝化处理形成的。可以将所述不锈钢基材1放置在钝化液中，通电反应一定时间后将不锈钢基材1从钝化液中取出，电化学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。通过对电化学钝化处理的温度、时间、通电电压以及钝化液的种类进行调控，可以调节氧化膜的厚度和成分。本发明的电化学处理的处理范围为0.5-6V的电压，钝化时间为1-30分钟。The present invention provides a combination of stainless steel and plastic that includes a stainless steel substrate and an injection molded plastic. As shown in FIG. 1, 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. Alternatively, 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. Alternatively, the honeycomb pores 11 may be formed on the entire surface of the stainless steel substrate 1. Specifically, 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 electrochemical passivation treatment. The stainless steel substrate 1 may be placed in a passivation liquid, and the stainless steel substrate 1 is taken out from the passivation liquid after being energized for a certain period of time, and the electrochemical passivation treatment forms oxidation at least on the surface of the honeycomb pores 11. Membrane 12. 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, time, energization voltage, and type of the passivation solution of the electrochemical passivation treatment. The electrochemical treatment of the present invention has a treatment range of 0.5-6 V and a passivation time of 1-30 minutes.
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，经过电化学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。The joint of the stainless steel and the plastic provided by the invention has the following technical effects. First, the volume of the oxide film formed by the electrochemical passivation treatment is expanded, and the surface forms a fine uneven surface, which increases the surface roughness of the honeycomb pores. The honeycomb pores further enhance the bonding force between the stainless steel substrate and the plastic material.
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。Second, the oxide film formed by the passivation treatment is grown in situ from the surface of the stainless steel substrate. 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. In particular, 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. Moreover, 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. .
进一步地，本发明通过对电化学钝化处理采用的钝化液、处理温度、处理时间、通电电压等进行调控，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。Further, the present invention can control the passivation liquid, the treatment temperature, the treatment time, the electrification voltage and the like used in the electrochemical 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. When the injection molding process is performed, 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.
所述电化学处理采用的溶液可以为硝酸、硫酸、亚硝酸、次氯酸、柠檬酸、磷酸、铬酸、高锰酸及其盐中的至少一种。也可以将多种溶液混合。The solution used in the electrochemical treatment may be at least one of nitric acid, sulfuric acid, nitrous acid, hypochlorous acid, citric acid, phosphoric acid, chromic acid, permanganic acid, and salts thereof. It is also possible to mix a plurality of solutions.
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Fe、Cr、O为主，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厚的自然氧化膜，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。In one embodiment of the present invention, by adjusting the conditions of the passivation treatment, in combination with XPS analysis, Fe, Cr, Ni, and O elements are mainly present in the oxide film at a surface of 12 nm from the surface layer of the stainless steel substrate. Among them, the element content is mainly Fe, Cr, O, and Ni is 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 thick of stainless steel, and mainly consists of chromium oxide and iron oxide having a small thermal conductivity, and exhibits a good heat insulating effect.
经本技术方案制备的蜂窝状多孔不锈钢基材，可选地，由体积分数5-30％的硝酸，0.6-3V的恒定电压的电化学钝化后，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29.5MPa。这相比于现有常规方案的切断强度有大幅度的提升。The honeycomb porous stainless steel substrate prepared by the present technical scheme is optionally embedded in an injection molding die by electrochemical passivation of a volume fraction of 5-30% nitric acid and a constant voltage of 0.6-3 V. 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 29.5 MPa. This has a significant increase in the cutting strength compared to the conventional conventional scheme.
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是外加电压驱使不锈钢在钝化区形成氧化膜的过程，极化形成的氧化膜厚度更厚。例如，SUS304不锈钢在稀硝酸溶液中钝化20min后，形成的氧化膜厚度达到14.3nm。同时依据《金属腐蚀手册》可知，电化学钝化亦是阳极钝化，阳极钝化过程优先腐蚀钝化活泼性金属。因此，电化学钝化后不锈钢主要以铬氧化物和铁的氧化物为主。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。另外，由于外加极化电压的驱动，不仅加快了不锈钢钝化反应速率，缩短了化学钝化处理时间，而且极化电位选择性地钝化了活泼元素铬，膜层中形成更多的低导热系数的铬氧化物。因此，本技术方案中电化学钝化膜层较厚、硬度较高。隔热性更好，耐腐蚀性较强，显著增加不锈钢与塑料间的结合力。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. Moreover, 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 of the present invention is a process in which an applied voltage drives the stainless steel to form an oxide film in the passivation region, and the oxide film formed by polarization is thicker. For example, after passivation of SUS304 stainless steel in a dilute nitric acid solution for 20 min, the thickness of the formed oxide film reaches 14.3 nm. At the same time, according to the "metal corrosion manual", the electrochemical passivation is also anodized, and the anode passivation process preferentially corrodes the passivated active metal. Therefore, after electrochemical passivation, stainless steel is mainly composed of chromium oxide and iron oxide. Among them, 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, The thermal conductivity of chromium oxide is about 10 W/m·K. In addition, due to the driving of the applied polarization voltage, not only the rate of passivation of the stainless steel is accelerated, but also the chemical passivation treatment time is shortened, and the polarization potential selectively deactivates the active element chromium, and more low heat conduction is formed in the film layer. Coefficient of chromium oxide. Therefore, in the technical solution, the electrochemical passivation film layer is thicker and has higher hardness. Better insulation and corrosion resistance, significantly increasing the bonding between stainless steel and plastic.
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示出了经过电化学钝化处理后，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。On the other hand, since 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. By reducing the pore size of the honeycomb pores, the corresponding pore forming process is also simplified, thereby resulting in simplification of the process flow and reduction in time cost. After the pore size of the honeycomb pores is lowered, the pores are more evenly distributed and the pore quality is higher. Figure 2 shows the morphology of the honeycomb pores on the surface of the stainless steel substrate after electrochemical 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.
可选地，在一种实施方式中，所述电化学钝化处理采用的钝化液为体积分数5-30％的硝酸，所述电化学钝化处理采用0.6-3V的恒定电压。本发明采用的电化学钝化处理对不锈钢基材施加电压，以不锈钢基材作为 阳极，使其表面与氧化性的钝化液介质发生电化学反应形成致密的钝化膜。由于存在外加电位的强制驱动，不锈钢基材表面的化学反应更为高效，相比于普通酸洗氧化膜更为致密，更为有效。以上是本发明提供的一种电化学钝化处理的具体方式，本发明采用恒电位电化学钝化，在设备、工艺简单，在极化过程中电极状态明确，影响因素小，且钝化处理能够起到良好的钝化氧化成膜效果。同时，相较于采用浓硝酸、重铬酸等进行化学钝化处理，本发明制得的氧化膜可靠性更高，不锈钢基材的点蚀电位能够达到1000mV(25℃、3wt.％NaCl)以上。而且，采用的酸液的浓度相对更低，使用安全，对人体、环境的影响较小，符合可持续性发展的技术发展趋势。Optionally, in one embodiment, the electrochemical passivation treatment uses a passivation solution having a volume fraction of 5-30% nitric acid, and the electrochemical passivation treatment uses a constant voltage of 0.6-3V. The electrochemical passivation treatment used in the present invention applies a voltage to a stainless steel substrate, and is made of a stainless steel substrate. The anode electrochemically reacts its surface with an oxidizing passivation medium to form a dense passivation film. Due to the forced driving of the applied potential, the chemical reaction on the surface of the stainless steel substrate is more efficient, and it is more compact and more effective than the ordinary acid-washed oxide film. The above is a specific manner of electrochemical passivation treatment provided by the present invention. The invention adopts constant potential electrochemical passivation, has simple equipment and process, has clear electrode state in the polarization process, has small influence factors, and is passivated. Can play a good passivation oxide film forming effect. At the same time, compared with the chemical passivation treatment using concentrated nitric acid, dichromic acid, etc., the oxide film prepared by the invention has higher reliability, and the pitting potential of the stainless steel substrate can reach 1000 mV (25 ° C, 3 wt.% NaCl). the above. Moreover, the concentration of the acid solution used is relatively low, the use is safe, and the impact on the human body and the environment is small, which is in line with the technological development trend of sustainable development.
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。Alternatively, 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.
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。Alternatively, 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. Alternatively, the honeycomb pores have an average pore size of 60 nm.
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。Alternatively, 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.
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。In particular, 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 At least one of ethanolamine, ammonia, 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.
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。In particular, the plastic material may also be doped with a filler material, which is nylon fiber, carbon fiber, glass fiber, aramid fiber, calcium carbonate, magnesium carbonate, and second. At least one of silicon oxide and clay, the filler material occupies a mass percentage in the plastic material ranging from 5 to 40% by weight. The filler material may be doped in the plastic material prior to the injection molding process.
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。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. For example, 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.
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，对所述不锈钢基材进行电化学钝化处理，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，所述电化学钝化处理的处理条件为0.5-6V的电压，钝化时间为1-30分钟；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。The invention also provides a method for processing a combination of stainless steel and plastic, firstly, providing a stainless steel substrate, forming a honeycomb pore on the surface of the stainless steel substrate; and then electrochemically passivating the stainless steel substrate Forming an oxide film on the surface of the stainless steel substrate, the oxide film including at least two of iron oxide, chromium oxide or nickel oxide, and the processing condition of the electrochemical passivation treatment is 0.5-6V The voltage and the passivation time are 1-30 minutes. Finally, the plastic material is injection molded on the surface of the stainless steel substrate, and 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.
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。The step of pretreatment may also be included prior to the hole forming process of the stainless steel substrate. Alternatively, 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.
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。 Alternatively, 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, then placed in a neutralizing solution for about 60 s, and then washed 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.
在本发明的一种可选的实施方式中，所述电化学钝化处理采用的钝化液为体积分数10-20％的硝酸，所述电化学钝化处理采用0.8-1.5V的恒定电压。电极连接在所述不锈钢基材上，所述不锈钢基材在电化学反应中作为阳极。优选地，处理温度为30摄氏度，处理时间为15分钟。以上是本发明例举出的一种适用于本发明所述方法的电化学钝化处理具体方式，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钝化液，也可以采用不同的电压，本发明不对此进行限制。相较于采用浓硝酸、重铬酸等进行氧化处理，本发明制得的氧化膜可靠性更高，不锈钢基材的点蚀电位能够达到1000mV以上。而且，采用的硝酸浓度相对更低，使用安全，对人体、环境的影响较小，符合可持续性发展的技术发展趋势。In an optional embodiment of the present invention, the passivation solution used in the electrochemical passivation treatment is nitric acid having a volume fraction of 10-20%, and the electrochemical passivation treatment adopts a constant voltage of 0.8-1.5V. . An electrode is attached to the stainless steel substrate that acts as an anode in an electrochemical reaction. Preferably, the treatment temperature is 30 degrees Celsius and the treatment time is 15 minutes. The above is a specific manner of the electrochemical passivation treatment which is exemplified in the present invention, and can be used as the passivation liquid according to actual performance requirements of the product. Different voltages are used, and the invention does not limit this. Compared with the oxidation treatment using concentrated nitric acid, dichromic acid or the like, the oxide film obtained by the invention has higher reliability, and the pitting potential of the stainless steel substrate can reach 1000 mV or more. Moreover, the concentration of nitric acid used is relatively low, the use is safe, and the impact on the human body and the environment is small, which is in line with the technological development trend of sustainable development.
特别地，在电化学钝化处理后，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。In particular, after the electrochemical passivation treatment, the stainless steel substrate may be subjected to a boring treatment, which can improve the surface characteristics of the oxide film, so that the plastic material can be better filled into the honeycomb in the subsequent injection molding process. In the pores, a form in which the plastic material is solidified and embedded in the honeycomb pores is formed. The 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. 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.
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 (10)

  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，经过电化学钝化处理，所述蜂窝状细孔的表面上形成有氧化膜，所述电化学钝化处理的处理条件为0.5-6V的电压，钝化时间为1-30分钟，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。A joint member of stainless steel and plastic, characterized in that the joint member comprises a stainless steel substrate, and the surface of the stainless steel substrate is formed with honeycomb pores, which are electrochemically passivated, the honeycomb pores An oxide film is formed on the surface, the processing condition of the electrochemical passivation treatment is a voltage of 0.5-6 V, and the passivation time is 1-30 minutes, and the oxide film includes at least iron oxide, chromium oxide or nickel oxide. In the two types, the stainless steel substrate is injection molded with a plastic material embedded in the honeycomb pores.
  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，所述电化学钝化处理采用的溶液为硝酸、硫酸、亚硝酸、次氯酸、柠檬酸、磷酸、铬酸、高锰酸及其盐中的至少一种。The combination of stainless steel and plastic according to claim 1, wherein the electrochemical passivation treatment uses nitric acid, sulfuric acid, nitrous acid, hypochlorous acid, citric acid, phosphoric acid, chromic acid, and high manganese. At least one of an acid and a salt thereof.
  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，所述塑料材料由聚苯硫醚树脂、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。A combination of stainless steel and plastic according to claim 1 or 2, wherein the plastic material is composed of polyphenylene sulfide resin, polybutylene terephthalate resin, polyamide, polycarbonate and polyolefin. Made of at least one material.
  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。The combination of stainless steel and plastic according to any one of claims 1 to 3, wherein the honeycomb pores have an average pore diameter ranging from 10 to 150 nm, and the honeycomb pores are from the surface of the stainless steel substrate. The average depth extending to the inside ranges from 10 to 200 nm, and the thickness of the oxide film ranges from 1 to 20 nm.
  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。The joint of stainless steel and plastic according to any one of claims 1 to 4, characterized in that the surface of the oxide film is adsorbed with a pore former, and the pore former is terephthalic acid or ethylenediamine. At least one of acetic acid, p-nitrobenzenesulfonic acid, water-soluble amino acid, ethylenediamine, triethanolamine, aqueous ammonia, ethyl chloride, and epichlorohydrin.
  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％。The combination of stainless steel and plastic according to any one of claims 1 to 5, characterized in that the plastic material is doped with a filler material, which is nylon fiber, carbon fiber, glass fiber, aromatic poly At least one of amide fibers, calcium carbonate, magnesium carbonate, silica, and clay, the filler material occupies a mass percentage in the plastic material ranging from 5 to 40% by weight.
  7. 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；对所述不锈钢基材进行电化学钝化处理，在所述不锈钢基材的表面形成氧化膜，所述电化学钝化处理的处理条件为0.5-6V的电压，钝化时间为1-30分钟，所述氧化膜包括铁氧化物、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。A method for processing a combination of stainless steel and plastic, characterized in that stainless steel is provided a steel substrate; forming a honeycomb pore on a surface of the stainless steel substrate; performing an electrochemical passivation treatment on the stainless steel substrate to form an oxide film on a surface of the stainless steel substrate, and the electrochemical passivation treatment The condition is a voltage of 0.5-6 V, the passivation time is 1-30 minutes, and the oxide film includes two of iron oxide, chromium oxide or nickel oxide; plastic material is injection molded on the surface of the stainless steel substrate, A partial structure of the plastic material is embedded in the honeycomb pores to form an integrated combination of stainless steel and plastic.
  8. 根据权利要求7所述的方法，其特征在于，所述电化学钝化处理采用的钝化液为体积分数5-30％的硝酸，所述电化学钝化处理采用0.6-3V的恒定电压。The method according to claim 7, wherein the passivation solution used in the electrochemical passivation treatment is nitric acid having a volume fraction of 5-30%, and the electrochemical passivation treatment uses a constant voltage of 0.6-3V.
  9. 根据权利要求7或8所述的方法，其特征在于，所述电化学钝化溶液温度20-40摄氏度，钝化时间为10-20分钟。The method according to claim 7 or 8, wherein the electrochemical passivation solution has a temperature of 20-40 degrees Celsius and a passivation time of 10-20 minutes.
  10. 根据权利要求7-9任意之一所述的方法，其特征在于，在电化学钝化后，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。 The method according to any one of claims 7 to 9, wherein after the electrochemical passivation, the stainless steel substrate is subjected to a boring treatment, and the stainless steel substrate is immersed in the porogen, and the boring agent is At least one of terephthalic acid, ethylenediaminetetraacetic acid, p-nitrobenzenesulfonic acid, water-soluble amino acid, ethylenediamine, triethanolamine, aqueous ammonia, ethyl chloride, and epichlorohydrin.
PCT/CN2017/090621 2017-01-16 2017-06-28 Stainless steel and plastic combined member, and processing method therefor WO2018129870A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710028878.XA CN106917129B (en) 2017-01-16 2017-01-16 The engaging member and its processing method of stainless steel and plastics
CN201710028878.X 2017-01-16

Publications (1)

Publication Number Publication Date
WO2018129870A1 true WO2018129870A1 (en) 2018-07-19

Family

ID=59453979

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/090621 WO2018129870A1 (en) 2017-01-16 2017-06-28 Stainless steel and plastic combined member, and processing method therefor

Country Status (2)

Country Link
CN (1) CN106917129B (en)
WO (1) WO2018129870A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112575355A (en) * 2019-09-30 2021-03-30 浙江绍兴苏泊尔生活电器有限公司 Cooking utensil and surface treatment method thereof
CN112609187A (en) * 2020-11-16 2021-04-06 深圳艾利门特科技有限公司 Passivation method for glass and stainless steel packaged workpiece

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106917129B (en) * 2017-01-16 2019-01-04 歌尔股份有限公司 The engaging member and its processing method of stainless steel and plastics
CN109579746A (en) * 2017-09-28 2019-04-05 上海梅山钢铁股份有限公司 A method of detection cold rolling electroplating tin steel plate passivating film
CN109016332B (en) * 2018-07-12 2020-08-25 歌尔股份有限公司 Inorganic nonmetal and plastic combined body and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110008644A1 (en) * 2008-03-17 2011-01-13 Taisei Plas Co., Ltd. Bonded body of galvanized steel sheet and adherend, and manufacturing method thereof
US20110287281A1 (en) * 2009-02-02 2011-11-24 Corona Kogyo Corporation Composite component of clad material and synthetic resin part and manufacturing method of the same
CN102672878A (en) * 2011-03-14 2012-09-19 鸿富锦精密工业（深圳）有限公司 Stainless steel and resin compound and manufacturing method thereof
CN103895151A (en) * 2012-12-28 2014-07-02 比亚迪股份有限公司 Preparation method of stainless steel-resin composite and stainless steel-resin composite prepared by same
CN103895156A (en) * 2014-04-01 2014-07-02 东莞劲胜精密组件股份有限公司 Composite material and preparation method thereof
CN103895161A (en) * 2012-12-28 2014-07-02 比亚迪股份有限公司 Preparation method of stainless steel-resin composite and stainless steel-resin composite prepared by same
CN105196652A (en) * 2014-06-30 2015-12-30 比亚迪股份有限公司 Metal-resin compound and preparation method thereof
CN105908185A (en) * 2016-04-20 2016-08-31 东莞劲胜精密组件股份有限公司 Stainless steel surface treatment method and preparation method of stainless steel plastic composite
CN106917129A (en) * 2017-01-16 2017-07-04 歌尔股份有限公司 The conjunction and its processing method of stainless steel and plastics

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103286910B (en) * 2012-02-24 2015-09-30 比亚迪股份有限公司 A kind of metal-resin integrated molding method and a kind of metal-resin composite
CN104309054B (en) * 2013-10-31 2017-04-12 比亚迪股份有限公司 Preparation method of metal-resin composite, and metal-resin composite
CN103993340B (en) * 2014-05-20 2017-05-17 广东长盈精密技术有限公司 Metal sheet as well as metal resin composite and preparation method thereof
CN104313556B (en) * 2014-09-25 2017-05-10 东莞劲胜精密组件股份有限公司 Metal treating agent and composite material and preparation method thereof
CN105587994A (en) * 2014-10-20 2016-05-18 深圳富泰宏精密工业有限公司 Complex preparation method of metal and plastics and complex prepared by the same
CN106257937A (en) * 2016-04-29 2016-12-28 歌尔股份有限公司 A kind of sound-producing device and the preparation method of metal plastic part
CN106217748B (en) * 2016-07-15 2018-12-07 广东劲胜智能集团股份有限公司 A kind of metal and plastic cement integral structure and its manufacturing method
CN106273216B (en) * 2016-08-09 2018-11-02 南京大学 Metal-resin composite and its heat treatment method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110008644A1 (en) * 2008-03-17 2011-01-13 Taisei Plas Co., Ltd. Bonded body of galvanized steel sheet and adherend, and manufacturing method thereof
US20110287281A1 (en) * 2009-02-02 2011-11-24 Corona Kogyo Corporation Composite component of clad material and synthetic resin part and manufacturing method of the same
CN102672878A (en) * 2011-03-14 2012-09-19 鸿富锦精密工业（深圳）有限公司 Stainless steel and resin compound and manufacturing method thereof
CN103895151A (en) * 2012-12-28 2014-07-02 比亚迪股份有限公司 Preparation method of stainless steel-resin composite and stainless steel-resin composite prepared by same
CN103895161A (en) * 2012-12-28 2014-07-02 比亚迪股份有限公司 Preparation method of stainless steel-resin composite and stainless steel-resin composite prepared by same
CN103895156A (en) * 2014-04-01 2014-07-02 东莞劲胜精密组件股份有限公司 Composite material and preparation method thereof
CN105196652A (en) * 2014-06-30 2015-12-30 比亚迪股份有限公司 Metal-resin compound and preparation method thereof
CN105908185A (en) * 2016-04-20 2016-08-31 东莞劲胜精密组件股份有限公司 Stainless steel surface treatment method and preparation method of stainless steel plastic composite
CN106917129A (en) * 2017-01-16 2017-07-04 歌尔股份有限公司 The conjunction and its processing method of stainless steel and plastics

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112575355A (en) * 2019-09-30 2021-03-30 浙江绍兴苏泊尔生活电器有限公司 Cooking utensil and surface treatment method thereof
CN112575355B (en) * 2019-09-30 2023-11-14 浙江绍兴苏泊尔生活电器有限公司 Cooking appliance and surface treatment method thereof
CN112609187A (en) * 2020-11-16 2021-04-06 深圳艾利门特科技有限公司 Passivation method for glass and stainless steel packaged workpiece
CN112609187B (en) * 2020-11-16 2022-10-21 深圳艾利门特科技有限公司 Passivation method for glass and stainless steel packaged workpiece

Also Published As

Publication number Publication date
CN106917129B (en) 2019-01-04
CN106917129A (en) 2017-07-04

Similar Documents

Publication Publication Date Title
WO2018129870A1 (en) Stainless steel and plastic combined member, and processing method therefor
TWI464053B (en) Composite of stainless steel and resin and method for making same
TWI581949B (en) Method of preparing aluminum alloy-resin composite and aluminum alloy-resin composite obtainable by the same
TWI463039B (en) Method of preparing aluminum alloy resin composite and aluminum alloy-resin composite obtainable by the same
CN103882430B (en) Aluminum alloy composite and method of bonding therefor
TWI470122B (en) Aluminum alloy, alluminum alloy-resin composite and methods of preparing the same
TWI481747B (en) Method of preparing aluminum alloy-resin composite and aluminum alloy-resin composite obtainable by the same
JP6387301B2 (en) Aluminum resin bonded body and manufacturing method thereof
CN107709002B (en) Metal resin composite molded body and method for producing same
JP2008162115A (en) Method of manufacturing metal/resin composite material
JP2005342895A (en) Metal/resin compound object and its manufacturing method
CN108000796B (en) Stainless steel and resin composite and preparation method thereof
TW201127992A (en) Aluminum alloy article, aluminum alloy member, and production method therefor
TW201740784A (en) Metal casing with ceramic panel, manufacturing method and application thereof
JPWO2008126812A1 (en) Copper alloy composite and manufacturing method thereof
JP2006027018A (en) Metal/resin composite body and its manufacturing method
JP2012157991A (en) Metal-resin composite and production process thereof
WO2018129871A1 (en) Stainless steel and plastic combined member, and processing method therefor
CN108312419B (en) Surface-treated stainless steel, stainless steel resin complex and preparation method thereof
WO2018129872A1 (en) Stainless steel and plastic combined member, and processing method therefor
CN110524787B (en) Preparation method of copper-based alloy resin composite and copper-based alloy resin composite
KR101568991B1 (en) Aluminium-resin metal composition and method for fabricating the same
WO2018129873A1 (en) Stainless steel and plastic combined member, and processing method therefor
WO2018152998A1 (en) Stainless steel and plastic combined piece and processing method therefor
JP4175174B2 (en) Composite material and manufacturing method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17891832

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17891832

Country of ref document: EP

Kind code of ref document: A1