WO2018129871A1 - 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
WO2018129871A1
WO2018129871A1 PCT/CN2017/090623 CN2017090623W WO2018129871A1 WO 2018129871 A1 WO2018129871 A1 WO 2018129871A1 CN 2017090623 W CN2017090623 W CN 2017090623W WO 2018129871 A1 WO2018129871 A1 WO 2018129871A1
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Prior art keywords
stainless steel
acid
steel substrate
oxide film
plastic
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Ceased
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PCT/CN2017/090623
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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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    • 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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • C23C8/14—Oxidising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/06—Etching of iron or steel
    • 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
    • B29C2045/14803—Porous or permeable material, e.g. foam the injected material entering minute pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning

Definitions

  • the invention relates to the 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 comprising a stainless steel substrate having a honeycomb-shaped pore formed on a surface thereof, after 110-450 degrees Celsius, 120 -10 minutes of high temperature oxidation treatment, the honeycomb pores of the table
  • An oxide film is formed on the surface, and the volume content of oxygen in the atmosphere of the high temperature oxidation treatment is 75% to 100%, and the oxide film includes at least two of iron oxide, chromium oxide or nickel oxide.
  • the material is injection molded with a plastic material embedded in the honeycomb pores.
  • the oxide film comprises at least iron oxide and chromium oxide.
  • the volume content of oxygen in the high temperature oxidation treatment atmosphere is ⁇ 90%.
  • the high temperature oxidation treatment has a temperature in the range of 200-300 degrees Celsius and a treatment time of 90-30 minutes.
  • 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 the inside with an average depth ranging from 10 to 200 nm.
  • the oxide film has a thickness ranging from 1 to 20 nm. Further optionally, 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% by weight.
  • the invention also provides a method for processing a combination of stainless steel and plastic, providing a stainless steel substrate; etching the stainless steel substrate to form a honeycomb pore on the surface of the stainless steel substrate; and performing high temperature on the stainless steel substrate
  • An oxidation treatment an oxide film is formed on a surface of the stainless steel substrate, the oxide film includes iron oxide, and includes at least one of a chromium oxide or a nickel oxide, and the high temperature oxidation treatment has a temperature range of 110- 450 degrees Celsius, processing time is 120-10 minutes, the volume content of oxygen in the high temperature oxidation treatment atmosphere ranges from 75% to 100%; plastic material is injection molded on the surface of the stainless steel substrate, so that part of the structure of the plastic material is embedded in the In the honeycomb pores, an integrated combination of stainless steel and plastic is formed.
  • the oxide film comprises at least iron oxide and chromium oxide.
  • the volume content of oxygen in the high temperature oxidation treatment atmosphere is ⁇ 90%.
  • the high temperature oxidation treatment has a temperature in the range of 200-300 ° C and a treatment time of 90-30 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 etching process is chemical etching
  • the stainless steel substrate is immersed in a chemical etching solution of 30-90 degrees Celsius for 10-120 minutes
  • the chemical etching solution is sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, boric acid, formic acid.
  • the etching process is electrochemical etching
  • the stainless steel substrate is used as an anode
  • the region where the honeycomb pores are to be formed is electrochemically etched
  • the electrochemical etching voltage ranges from 5 to 60 V, and the duration is 10-100 minutes.
  • 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. 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 the oxide film 12 is formed by high temperature oxidation treatment.
  • the stainless steel substrate 1 may be placed in a heat treatment apparatus and heat-treated at a temperature of 110-450 degrees Celsius for 120-10 minutes, and specifically, may be heat-treated for 120-90 minutes in a temperature range of 110-200 degrees Celsius.
  • Heat treatment in a temperature range of 200-300 degrees Celsius for 90-30 minutes in a temperature range of 300-450 degrees Celsius The heat treatment is performed for 30 to 10 minutes to form the oxide film 12 on at least the surface of the honeycomb pores 11.
  • the heat treatment for 90-30 minutes in a temperature range of 200-300 degrees Celsius produces a good quality of the oxide film.
  • the above specific temperature and time setting is only exemplary. Generally, an ideal oxide film is obtained, and the temperature and time generally tend to be inversely proportional, but this is not inevitable.
  • the oxide film 12 mainly includes at least two of iron oxide, chromium oxide or nickel oxide, and may include, for example, iron oxide and chromium oxide, or may include iron oxide, chromium oxide, nickel oxide, and the like. .
  • the thickness and composition of the oxide film can be adjusted by adjusting the temperature and time of the heat treatment, and the above specific temperature and time are preferred embodiments of the present invention to achieve the technical effect.
  • the volume content of oxygen in the atmosphere of the high temperature oxidation treatment in the present invention is from 75% to 100%, that is, in a high oxygen content atmosphere.
  • the high temperature oxidation treatment for forming the oxide film is preferably carried out in an atmosphere having a volume content of oxygen of ⁇ 90%, and further may be carried out in an atmosphere of pure oxygen.
  • the treatment in the above oxygen-containing atmosphere can effectively control the material and thickness of the oxide film 12, and the surface characteristics of the formed oxide film 12 are also more advantageous for bonding with the plastic material 2.
  • a plastic material 2 is injection-molded on the surface of the stainless steel substrate 1, and the plastic material 2 is injection molded on a region of the stainless steel substrate 1 having the honeycomb pores 11. On the contact surface of the plastic material 2 with the stainless steel substrate 1, a plastic material 2 is embedded in the honeycomb pores 11.
  • 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 high temperature oxidation treatment is formed by in-situ oxidative growth from the surface of the stainless steel substrate.
  • the oxide film is dense and thick, 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.
  • an oxide film grown by in-situ oxidation is used relative to the use
  • the oxide layer formed by impregnation and drying of an acid solution or a salt solution containing metal ions has a distinct and stronger binding force.
  • This oxide film is more physically and chemically bonded to the 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 temperature, time, and atmosphere of the high temperature oxidation treatment to make the material of the oxide film 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 oxygen content in the atmosphere of the high temperature oxidation treatment is from 75% to 100%, that is, the oxygen pressure is high.
  • iron is sufficiently oxidized to form mainly ferric oxide, and the content of ferrous oxide is very low.
  • the thermal conductivity of ferric oxide is much smaller than that of ferrous oxide, which can provide better insulation.
  • 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 10 W/m ⁇ K. about.
  • the atmosphere of high oxygen pressure can also shorten the time of high temperature oxidation treatment.
  • 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 conventional oxide film of the steel material is mainly a natural oxide film of iron, or a manganese oxide, a zinc phosphorus oxide, etc., and the oxide film has a large thermal conductivity and cannot function as a heat insulator.
  • the stainless steel material after chemical etching is preferentially corroded by the active element of chromium, so the natural oxide film of stainless steel also includes a loose, extremely thin chromium oxide.
  • This oxide layer is susceptible to damage from external environments and mechanical contact. If the plastic material is directly injected into the oxide layer, other metal atoms such as metal iron will continuously precipitate to form loose oxygen. Film.
  • This oxide film not only does not function as a heat insulator, but also does not have an anti-corrosion effect, which affects the bonding reliability of the plastic material.
  • the formed oxide film is dense and thick, and mainly contains Fe, Cr, Ni, O elements, wherein the Ni element content Lower. Therefore, the oxide film mainly has a small thermal conductivity of iron oxide and chromium oxide, and exhibits superior heat insulation effect.
  • 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.
  • the pores are more evenly distributed and the pore quality is higher.
  • Fig. 2 shows the morphology of the honeycomb pores on the surface of the stainless steel substrate after high-temperature oxidation treatment, and the honeycomb pores are uniformly distributed.
  • 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 50-100 nm.
  • the thickness of the oxide film may range from 1 to 20 nm, and the thickness of the oxide film may be adjusted by adjusting conditions such as temperature, time, and atmosphere of the high temperature oxidation treatment. Further, by verifying, the honeycomb is verified.
  • the average pore size of the pores is 50-100 nm, and when the thickness of the oxide film ranges from 10 to 20 nm, the corrosion resistance and crack prevention effect of the plastic material and the stainless steel are optimal.
  • 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 porogen can improve oxygen
  • the surface characteristics of the film enable the plastic material to smoothly flow into the honeycomb pores during the injection molding process.
  • the oxide film of the present invention is formed by a high temperature oxidation treatment which can enhance the adsorption of the pore former on the oxide film. Moreover, the adsorption and filling effects of the plastic material during injection molding can also be improved, and the plastic material can be more fully and reliably adsorbed into the honeycomb pores.
  • the main reason is that the high temperature oxidation process, the oxide interface which has been generated with the oxygen atom of molecular oxygen reduction reaction occurs, forming a large amount of O 2 - active ion. The formation and aggregation of such active ions on the surface of the oxide film is more conducive to the subsequent adsorption of humectants and plastics. This technical effect does not exist on the natural oxide film or the oxide film formed by acid-base oxidation in the prior art, and is a technical effect unmatched by the conventional oxide film.
  • 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, and the stainless steel substrate is etched to form honeycomb pores on the surface of the stainless steel substrate;
  • the stainless steel substrate is subjected to a high temperature oxidation treatment to form 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, for example, iron oxide and chromium may be contained.
  • the oxide may contain iron oxide, chromium oxide, nickel oxide, and the like.
  • the high temperature oxidation treatment has a temperature range of 110-450 degrees Celsius, a treatment time of 120-10 minutes, and a volume content of oxygen in a high temperature oxidation treatment atmosphere.
  • the range is from 75% to 100%; finally, a 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 high temperature oxidation treatment is performed by heat treatment for 90 to 30 minutes in a temperature range of 200 to 300 degrees Celsius, and the quality of the oxide film formed is good. Further, the high-temperature oxidation treatment is preferably carried out in an atmosphere having a volume content of oxygen of ⁇ 90%, and further can be carried out in an atmosphere of pure oxygen.
  • the step of pretreatment may also be included prior to etching 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, 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 etching treatment of the stainless steel substrate may be performed by chemical etching or electrochemical etching.
  • the present invention does not limit this, and a specific etching treatment may be selected according to the structure and performance requirements of the honeycomb pores.
  • the stainless steel substrate may be immersed in a chemical etching solution of 30-90 degrees Celsius for 10-120 minutes, and the chemical etching solution is sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, boric acid, formic acid, propionic acid, butyric acid, At least one of alginic acid, oxalic acid, citric acid, and caprolactam.
  • the entire etching process to form a hole may include a plurality of different chemical etching steps to control the pore-forming effect of the pore size, distribution, and the like of the honeycomb pores.
  • the stainless steel substrate can be used as an anode to form a honeycomb shape. Electrochemical etching occurs in the pore region, and the electrochemical etching voltage ranges from 5 to 60 V for a duration of 10-100 minutes.
  • etching and electrochemical etching respectively, in different steps of the entire etching process.
  • This etching method can obtain richer pore-forming control effects.
  • chemical etching can be used to form pores with larger pore diameters, and then electrochemical etching etching is used to form honeycomb pores having smaller pore diameters.
  • 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-like fine 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-like fine 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.
  • 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.

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Abstract

一种不锈钢和塑料的结合件及其加工方法，该不锈钢和塑料的结合件包括不锈钢基材（1），该不锈钢基材（1）的表面上形成有蜂窝状细孔（11），经过110-450摄氏度、120-10分钟的高温氧化处理，该蜂窝状细孔（11）的表面上形成有氧化膜（12），高温氧化处理的气氛中氧气的体积含量为75％-100％，该氧化膜（12）至少包括铁氧化物、铬氧化物或镍氧化物中的两种，该不锈钢基材（1）上注塑成型有塑料材料（2），该塑料材料（2）嵌入蜂窝状细孔（11）中。该氧化膜具有良好的隔热效果，提高了不锈钢基材（1）和塑料材料（2）之间的结合作用力。

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。
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，或者简化制成的产品的结构，减少在产品上增加附加部件。
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110-450摄氏度、120-10分钟的高温氧化处理，所述蜂窝状细孔的表 面上形成有氧化膜，高温氧化处理的气氛中氧气的体积含量为75％-100％，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，所述氧化膜至少包括铁氧化物和铬氧化物。
可选地，所述高温氧化处理的气氛中氧气的体积含量≥90％。
可选地，所述高温氧化处理的温度范围为200-300摄氏度，处理时间为90-30分钟。
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。
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。
可选地，所述氧化膜的厚度范围为1-20nm。进一步可选的，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；对不锈钢基材进行蚀刻处理，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高温氧化处理，在所述不锈钢基材的表面形成氧化膜，所述氧化膜包括铁氧化物，并且包括铬氧化物或镍氧化物中的至少一种，所述高温氧化处理的温度范围为110-450摄氏度，处理时间为120-10分钟，高温氧化处理的气氛中氧气的体积含量范围为75％-100％；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，所述氧化膜至少包括铁氧化物和铬氧化物。
可选的，所述高温氧化处理的气氛中氧气的体积含量≥90％。
可选的，所述高温氧化处理的温度范围为200-300℃，处理时间为90-30分钟。
可选地，在高温氧化处理后，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。
可选地，所述蚀刻处理为化学蚀刻，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。
可选地，所述蚀刻处理为电化学蚀刻，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。
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。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，所述氧化膜12是经过高温氧化处理形成的。可以将所述不锈钢基材1放置在热处理设备中，在110-450摄氏度的温度中热处理120-10分钟，具体的，可以是在温度范围为110-200摄氏度的条件中热处理120-90分钟，在温度范围为200-300摄氏度的条件中热处理90-30分钟，在温度范围为300-450摄氏度的条件中 热处理30-10分钟，从而至少在蜂窝状细孔11的表面上形成氧化膜12。优选的，在温度范围为200-300摄氏度的条件中热处理90-30分钟的方案，生成氧化膜的质量较好。上述具体温度与时间的设定仅是示例性的，通常要获得理想状态的氧化膜，温度与时间一般呈反比趋势，但是这并不是必然的，根据具体情况需要，对氧化膜的质量要求降低的情况下，温度与时间可以不需要在这种趋势下设定，例如，在110摄氏度的情况下，仅加热10-30分钟。所述氧化膜12主要包括铁氧化物、铬氧化物或镍氧化物中的至少两种，例如可以包含铁氧化物和铬氧化物，或者可以包含铁氧化物、铬氧化物和镍氧化物等。通过对热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，上述具体的温度和时间是本发明为达到技术效果的优选的实施方式。
特别地，本发明中高温氧化处理的气氛中氧气的体积含量在75％-100％，也即是在高含氧量的气氛中进行。在本发明的优选的实施方式中，形成氧化膜的高温氧化处理优选在氧气的体积含量≥90％的气氛下进行，进一步的可以在纯氧的气氛下进行。在上述含氧量的气氛中进行处理，能够有效的控制氧化膜12的材料和厚度，形成的氧化膜12的表面特征也更有利于与塑料材料2的结合。所述不锈钢基材1的表面上注塑成型有塑料材料2，塑料材料2注塑在不锈钢基材1上具有蜂窝状细孔11的区域。在所述塑料材料2与不锈钢基材1接触面上，塑料材料2嵌入所述蜂窝状细孔11中。
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，经过高温氧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，高温氧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，氧化膜致密、厚度较厚，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。这种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。
进一步地，本发明通过对高温氧化处理的温度、时间、气氛进行调控，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。特别地，由于高温氧化处理的气氛中氧气含量在75％-100％，即氧气压较高。在高氧气压的气氛中，铁元素充分氧化，主要形成三氧化二铁，氧化亚铁的含量很低。三氧化二铁的导热率远小于氧化亚铁，能够起到更好的隔热效果。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。另外，由于铬元素活泼于铁元素，在高氧气压加高温的气氛中，加快了金属反应速率，氧化铬薄膜更加致密，在400℃的情况下，氧化铬的导热系数为10W/m·K左右。而且，高氧气压的气氛也能够缩短高温氧化处理的时间。
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。
钢铁材料的常规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。其中，对于不锈钢材料来说，化学蚀刻后的不锈钢材料，由于铬元素活泼于铁元素优先被腐蚀，因此不锈钢的自然氧化膜还包括稀松的、极薄的铬氧化物。这种氧化物层易受到外界环境及机械接触的破坏。如果直接将塑料材料注塑在这种氧化物层上，金属铁等其它金属原子会不断析出，形成疏松的氧 化膜。这种氧化膜不但不能起到隔热的作用，而且也不具有防腐蚀的作用，对塑料材料的结合可靠性造成影响。
在本发明的一种实施方式中，通过对高温氧化处理的条件进行调控，结合能谱分析，形成的氧化膜致密且较厚，其中主要存在Fe、Cr、Ni、O元素，其中Ni元素含量较低。所以，氧化膜主要以较小导热系数铁氧化物和铬氧化物为主，呈现出更优的隔热效果。
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示出了经过高温氧化处理后，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。
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50-100nm。
可选地，所述氧化膜的厚度范围可以为1-20nm，可以通过对高温氧化处理的温度、时间、气氛等条件进行调控，从而调节氧化膜的厚度，进一步的，通过验证，所述蜂窝状细孔的平均孔径大小为50-100nm，且氧化膜的厚度范围在10-20nm时，塑料材料与不锈钢的耐腐蚀、防开裂效果最优。
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。
另外，本发明所述的氧化膜通过高温氧化处理形成，这种处理方式能够提高润孔剂在氧化膜上的吸附。并且，也能够提高塑料材料在注塑时的吸附、填充效果，使塑料材料更充分、可靠的吸附嵌入所述蜂窝状细孔中。主要原因在于，高温氧化处理过程中，已经生成的氧化物与氧原子的界面发生氧分子还原反应，形成大量的O2 -活性离子。该类活性离子在氧化膜表面的生成和聚集更有利于后续的湿润剂及塑胶的吸附。这一技术效果在现有技术中的自然氧化膜或者经酸碱氧化形成的氧化膜上并不存在，是常规氧化膜无法比拟的技术效果。
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，对不锈钢基材进行蚀刻处理，以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高温氧化处理，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，例如可以包含铁氧化物和铬氧化物，或者可以包含铁氧化物、铬氧化物和镍氧化物等。所述高温氧化处理的温度范围为110-450摄氏度，处理时间为120-10分钟，高温氧化处理的气氛中氧气的体积含量 范围为75％-100％；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。
在本发明的优选的实施方式中，高温氧化处理是在温度范围为200-300摄氏度的条件中热处理90-30分钟，生成氧化膜的质量较好。并且高温氧化处理优选在氧气的体积含量≥90％的气氛下进行，进一步的可以在纯氧的气氛下进行。
在对不锈钢基材进行蚀刻处理之前，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。
对不锈钢基材进行的蚀刻处理成孔加工可以采用化学蚀刻也可以采用电化学蚀刻，本发明不对此进行限制，可以根据对蜂窝状细孔的结构、性能要求，选择具体的蚀刻处理。
对于化学蚀刻，可以将不锈钢基材置于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。可选地，整个蚀刻处理成孔的过程可以包括多次不同的化学蚀刻步骤，以调控蜂窝状细孔的孔径、分布情况等成孔效果。
对于电化学蚀刻，可以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。
特别地，也可以在整个蚀刻处理的不同步骤中分别采用化学蚀刻和电化学蚀刻。这种蚀刻方式可以得到更丰富的成孔调控效果，例如，可以先采用化学蚀刻形成孔径较大的孔洞，之后再用电化学蚀刻定向腐蚀形成孔径较小的蜂窝状细孔。
特别地，在高温氧化处理后，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。
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110-450摄氏度、120-10分钟的高温氧化处理，所述蜂窝状细孔的表面上形成有氧化膜，高温氧化处理的气氛中氧气的体积含量为75％-100％，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，所述氧化膜至少包括铁氧化物和铬氧化物。
  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，所述高温氧化处理的气氛中氧气的体积含量≥90％。
  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，所述高温氧化处理的温度范围为200-300摄氏度，处理时间为90-30分钟。
  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。
  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，所述氧化膜的厚度范围为1-20nm。
  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。
  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％。
  9. 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；对不锈钢基材进行蚀刻处理，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高温氧化处理，在所述不锈钢基材的表面形成氧化膜，所述氧化膜包括铁氧化物，并且包括铬氧化物或镍氧化物中的至少一种，所述高温氧化处理的温度范围为110-450摄氏度，处理时间为120-10分钟，高温氧化处理的气氛中氧气的体积含量范围为75％-100％；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。
  10. 根据权利要求9所述的加工方法，其特征在于，所述氧化膜至少包括铁氧化物和铬氧化物。
  11. 根据权利要求9或10所述的加工方法，其特征在于，所述高温氧化处理的气氛中氧气的体积含量≥90％。
  12. 根据权利要求9-11任意之一所述的加工方法，其特征在于，所述高温氧化处理的温度范围为200-300℃，处理时间为90-30分钟。
  13. 根据权利要求9-12任意之一所述的加工方法，其特征在于，在高温氧化处理后，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。
  14. 根据权利要求9-13任意之一所述的加工方法，其特征在于，所述蚀刻处理为化学蚀刻，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。
  15. 根据权利要求9-14任意之一所述的加工方法，其特征在于，所述蚀刻处理为电化学蚀刻，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。
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