CN106903838A - The conjunction and its processing method of stainless steel and plastics - Google Patents
The conjunction and its processing method of stainless steel and plastics Download PDFInfo
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- CN106903838A CN106903838A CN201710029374.XA CN201710029374A CN106903838A CN 106903838 A CN106903838 A CN 106903838A CN 201710029374 A CN201710029374 A CN 201710029374A CN 106903838 A CN106903838 A CN 106903838A
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- Prior art keywords
- stainless steel
- oxide
- film
- acid
- plastics
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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
- 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
Abstract
The invention discloses a kind of stainless steel and the conjunction and its processing method of plastics.The conjunction of the stainless steel and plastics includes stainless steel substrate, cellular pore is formed with the surface of the stainless steel substrate, by 110 450 degrees Celsius, the high temperature oxidation process of 120 10 minutes, oxide-film is formed with the surface of the cellular pore, the volume content of oxygen is 75% 100% in the atmosphere of high temperature oxidation process, the oxide-film at least includes two kinds in ferriferous oxide, chromated oxide or nickel oxide, plastic material is injection molded with the stainless steel substrate, the plastic material is embedded in the cellular pore.A technique effect of the invention is that the oxide-film has good effect of heat insulation, improves the combination power between stainless steel substrate and plastic material.
Description
Technical field
The present invention relates to materials processing technology field, in particular it relates to the conjunction of a kind of stainless steel and plastics and its add
Work method.
Background technology
With the gradually development of material technology, increasing product constitutes product in the form of metal and plastics are compound
Structure.This structure design can realize abundant functional effect.For example, need product outward appearance present metallicity and it is interior
In the case that portion's structure needs to reduce weight, material-saving cost, it is possible to the design being combined with plastics using metal.
The conventional composite mode of metal and plastics including adhesive bonds, buckle engage or rivet interlacement etc. mode.But
It is that traditional complex method has that compound reliability is low, need to increase the defects such as the mechanism that is fixedly connected.With the development of technology,
Have also appeared in the prior art by plastic injection metal surface complex method.When the injection molding of plastics is carried out, with gold
Category material as base material, by the direct injection moulding of plastics on the metal material.But, the combination power between metal and plastics
It is limited, there is the risk for coming off between the two, compound reliability is difficult to improve.
Therefore, it is necessary to be improved with the combination process of plastic material to metal, the structure reliability of Material cladding is improved
Property, or the structure of product that simplification is made, reduction increases additional component on product.
The content of the invention
It is an object of the present invention to provide a kind of stainless steel and the compound new solution of plastics.
According to the first aspect of the invention, there is provided the conjunction of a kind of stainless steel and plastics, the conjunction is included not
Rust steel substrate, is formed with cellular pore, by 110-450 degrees Celsius, 120-10 minutes on the surface of the stainless steel substrate
High temperature oxidation process, oxide-film is formed with the surface of the cellular pore, oxygen in the atmosphere of high temperature oxidation process
Volume content is 75%-100%, and the oxide-film at least includes two kinds in ferriferous oxide, chromated oxide or nickel oxide, institute
State and plastic material is injection molded with stainless steel substrate, the plastic material is embedded in the cellular pore.
Alternatively, the oxide-film at least includes ferriferous oxide and chromated oxide.
Alternatively, in the atmosphere of the high temperature oxidation process oxygen volume content >=90%.
Alternatively, the temperature range of the high temperature oxidation process is 200-300 degrees Celsius, and process time is 90-30 minutes.
Alternatively, the plastic material is by polyphenylene sulfide, poly terephthalic acid butanol resin, polyamide, poly- carbonic acid
At least one material in ester and polyolefin is made.
Alternatively, the average pore size scope of the cellular pore is 10-150nm, and the cellular pore is from stainless steel
The mean depth scope that the surface of base material extends inward is 10-200nm.
Alternatively, the thickness range of the oxide-film is 1-20nm.It is further alternative, the thickness range of the oxide-film
It is 10-20nm.
Alternatively, the adsorption of the oxide-film has profit hole agent, and profit hole agent is terephthalic acid (TPA), ethylenediamine tetrem
In acid, p-nitrophenyl sulfonic acid, water-soluble amino acids, ethylenediamine, triethanolamine, ammoniacal liquor, chloroethanes, epoxychloropropane at least one
Kind.
Alternatively, doped with packing material in the plastic material, the packing material is nylon fiber, carbon fiber, glass
At least one in glass fiber, aromatic polyamide fibre, calcium carbonate, magnesium carbonate, silica and clay, the packing material
The scope of shared mass percent is 5-40wt% in the plastic material.
Present invention also offers a kind of stainless steel and the processing method of the combination of plastics, there is provided stainless steel substrate；To not
Rust steel substrate is etched treatment, and cellular pore is formed on the surface of stainless steel substrate；Height is carried out to the stainless steel substrate
Warm oxidation processes, oxide-film is formed on the surface of the stainless steel substrate, and the oxide-film includes ferriferous oxide, and including chromium
At least one in oxide or nickel oxide, the temperature range of the high temperature oxidation process is 110-450 degrees Celsius, during treatment
Between be 120-10 minute, in the atmosphere of high temperature oxidation process the volume content scope of oxygen be 75%-100%；Described stainless
The surface injection molding plastic material of steel substrate, makes the part-structure of plastic material be embedded in the cellular pore, forms stainless steel
With the integrated combination of plastics.
Alternatively, the oxide-film at least includes ferriferous oxide and chromated oxide.
Optionally, in the atmosphere of the high temperature oxidation process oxygen volume content >=90%.
Optionally, the temperature range of the high temperature oxidation process is 200-300 DEG C, and process time is 90-30 minutes.
Alternatively, after high temperature oxidation process, the treatment of profit hole is carried out to stainless steel substrate, by stainless steel substrate immersion profit hole
In agent, profit hole agent is terephthalic acid (TPA), ethylenediamine tetra-acetic acid, p-nitrophenyl sulfonic acid, water-soluble amino acids, ethylenediamine, three
At least one of monoethanolamine, ammoniacal liquor, chloroethanes, epoxychloropropane.
Alternatively, the etching process is chemical etching, and stainless steel substrate is placed in 30-90 degrees Celsius of chemical etching liquor
Middle dipping 10-120 minutes, chemical etching liquor is sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, boric acid, formic acid, propionic acid, butyric acid, brown alga
At least one in acid, oxalic acid, citric acid and caprolactam.
Alternatively, the etching process is chemical etching, with the stainless steel substrate as anode, is made to be formed cellular
There is electrochemical corrosion in the region of pore, the voltage range of chemical etching is 5-60V, and the duration is 10-100 minutes.
It was found by the inventors of the present invention that in the prior art, although occur in that and note some metal materials and plastic material
The compound technical scheme of modeling, but, for stainless steel and the complex method of plastic material, do not occur improvement in the prior art
, the technical scheme that compound reliability is high.Therefore, the present invention to be realized technical assignment or technical problem to be solved
Be it is that those skilled in the art never expect or it is not expected that, therefore the present invention is a kind of new technical scheme.
By referring to the drawings to the detailed description of exemplary embodiment of the invention, further feature of the invention and its
Advantage will be made apparent from.
Brief description of the drawings
The accompanying drawing for being combined in the description and constituting a part for specification shows embodiments of the invention, and even
It is used to explain principle of the invention together with its explanation.
Fig. 1 is the structural representation of the conjunction of the stainless steel that the present invention is provided and plastics.
Fig. 2 is the shape characteristic schematic diagram of the cellular pore of offer in one embodiment of the present invention.
Fig. 3 is the surface texture schematic diagram of the stainless steel substrate that the present invention is provided.
Specific embodiment
Describe various exemplary embodiments of the invention in detail now with reference to accompanying drawing.It should be noted that：Unless had in addition
Body illustrates that the part and the positioned opposite of step, numerical expression and numerical value for otherwise illustrating in these embodiments do not limit this
The scope of invention.
The description only actually at least one exemplary embodiment is illustrative below, never as to the present invention
And its any limitation applied or use.
May be not discussed in detail for technology, method and apparatus known to person of ordinary skill in the relevant, but suitable
In the case of, the technology, method and apparatus should be considered as a part for specification.
In all examples shown here and discussion, any occurrence should be construed as merely exemplary, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
It should be noted that：Similar label and letter represents similar terms in following accompanying drawing, therefore, once a certain Xiang Yi
It is defined in individual accompanying drawing, then it need not be further discussed in subsequent accompanying drawing.
The invention provides a kind of stainless steel and the conjunction of plastics, the conjunction includes that stainless steel substrate and injection are moulded
Material.As shown in figure 1, being formed with cellular pore 11 on the surface of the stainless steel substrate 1, the cellular pore 11 is nanometer
The pore space structure of level.Alternatively, the cellular pore 11 can be only formed on stainless steel substrate 1 needs injection molding plastic material
2 region.Or, it is also possible to form cellular pore 11 in all surfaces of stainless steel substrate 1.Especially, it is described cellular
Oxide-film 12 is formed with the surface of pore 11, the oxide-film 12 is formed by high temperature oxidation process.Can be described
Stainless steel substrate 1 is placed in Equipment for Heating Processing, is heat-treated 120-10 minutes in 110-450 degrees Celsius of temperature, specifically,
Can be heat-treated 120-90 minutes in temperature range is for 110-200 degrees Celsius of condition, in temperature range for 200-300 takes the photograph
It is heat-treated 90-30 minutes in the condition of family name's degree, is heat-treated 30-10 minutes in temperature range is for 300-450 degrees Celsius of condition,
So as to form oxide-film 12 at least on the surface of cellular pore 11.Preferably, it is 200-300 degrees Celsius in temperature range
The scheme of 90-30 minutes is heat-treated in condition, the quality for generating oxide-film is preferable.Above-mentioned actual temp is only with the setting of time
Exemplary, the oxide-film of perfect condition is generally obtained, temperature and time is typically in inverse ratio trend, but this is not certainty
, need as the case may be, to the reduction of the quality requirement of oxide-film in the case of, temperature and time can be this
Set under trend, for example, in the case of 110 degrees Celsius, only heating 10-30 minutes.The oxide-film 12 mainly includes iron oxygen
In compound, chromated oxide or nickel oxide at least two, ferriferous oxide and chromated oxide can be for example included, or can wrap
Oxides-containing iron, chromated oxide and nickel oxide etc..Regulate and control by the temperature and time being heat-treated, oxidation can be adjusted
The thickness and composition of film, above-mentioned specific temperature and time are the present invention to reach technique effect preferred embodiment.
Especially, the volume content of oxygen, in 75%-100%, that is to say in the atmosphere of high temperature oxidation processes of the present invention
Carried out in the atmosphere of rich oxygen content.It is of the invention preferred embodiment in, formed oxide-film high temperature oxidation process it is excellent
Being selected under the atmosphere of volume content >=90% of oxygen is carried out, and can further be carried out under the atmosphere of pure oxygen.Contain above-mentioned
Processed in the atmosphere of oxygen amount, can effectively be controlled the material and thickness of oxide-film 12, the surface of the oxide-film 12 of formation
Feature be more favorable to and plastic material 2 combination.Plastic material 2 is injection molded with the surface of the stainless steel substrate 1, is moulded
Material material 2 is moulded on stainless steel substrate 1 region with cellular pore 11.In the plastic material 2 and stainless steel substrate 1
On contact surface, plastic material 2 is embedded in the cellular pore 11.
The stainless steel and the conjunction of plastics that the present invention is provided have the following technical effect that, first, at high-temperature oxydation
Manage the oxidation membrane volume for being formed to expand, surface forms trickle male and fomale(M＆F), increased the surface roughness of cellular pore,
The combination power of stainless steel substrate and plastic material is further increased on the basis of cellular pore.
Second, the oxide-film that high temperature oxidation process is formed is formed from the surface in situ oxidation growth of stainless steel substrate, oxygen
Change film is fine and close, thickness is thicker, has stronger adhesion between the oxide-film and stainless steel substrate.Therefore, conjunction entirety
In drawing or shear history, stainless steel substrate is not readily separated with plastic material, damages.Especially, in-situ oxidation growth and
Into oxide-film have relative to the oxide layer formed using the acid solution containing metal ion or salt solution impregnation, drying it is obvious
, stronger combination power.This oxide-film is stronger with the physical chemistry associativity of stainless steel substrate.And, it is of the invention
Compared with above-mentioned conventional oxidation film, structure is more closely knit, and corrosion resistance is stronger for oxide-film, and this design feature ensure that plastic material
The reliability on oxide-film is moulded in, situations such as prevent corrosion cracking, mechanics to be broken.
Further, the present invention is regulated and controled by the temperature to high temperature oxidation process, time, atmosphere, can make oxidation
The material of film is mainly ferriferous oxide, chromated oxide or nickel oxide.The coefficient of heat conduction of above-mentioned three kinds of oxides is respectively less than not
Rust steel substrate, the oxide-film is equivalent to covering one layer of thermal insulation layer on the stainless steel substrate.Especially, due to high-temperature oxydation
Oxygen content is in 75%-100% in the atmosphere for the treatment of, i.e. oxygen pressure is higher.In the atmosphere of hyperoxia air pressure, the abundant oxygen of ferro element
Change, primarily form di-iron trioxide, the content of ferrous oxide is very low.The thermal conductivity of di-iron trioxide is much smaller than ferrous oxide, energy
Enough play more preferable effect of heat insulation.Wherein, in the case of 400 DEG C, the thermal conductivity factor of stainless steel is 16.3W/mK, three oxidations
The thermal conductivity factor of two iron is 5.1W/mK, and the thermal conductivity factor of ferrous oxide is 15.0W/mK.Further, since chromium is active
In ferro element, in the atmosphere that hyperoxia air pressure is increased temperature, metal reaction speed is accelerated, chromium oxide film is finer and close, 400
In the case of DEG C, the thermal conductivity factor of chromium oxide is 10W/mK or so.And, the atmosphere of hyperoxia air pressure can also shorten high temperature oxygen
Change the time for the treatment of.
When Shooting Technique is carried out, the heat that the oxide-film can reduce plastic material scatters and disappears, and reduces plastic material
Heat scatters and disappears from the side of stainless steel substrate.This effect has delayed plastic material solidification, the time of crystallization, enables plastic material
Enough to be more fully filled in cellular pore, the bottom of cellular pore is also obtained in that preferably filling.So, stainless steel
More preferable air-tightness can be presented between base material and plastic material, and connection reliability is higher.
The regular oxidation film of ferrous materials is mainly the natural oxide film of iron, or Mn oxide, zinc phosphorous oxides etc.,
The thermal conductivity of this oxide-film is larger, it is impossible to play heat-insulated effect.Wherein, for stainless steel material, after chemical etching
Stainless steel material, because chromium is vivaciously preferentially corroded in ferro element, thus stainless steel natural oxide film also include it is dilute
Pine, very thin chromated oxide.This oxide skin(coating) is vulnerable to the destruction of external environment and Mechanical Contact.If directly by plastics
On this oxide skin(coating), other metallic atoms such as metallic iron can be separated out constantly material injection, form loose oxide-film.It is this
Oxide-film can not only play heat-insulated effect, nor with etch-proof effect, to the combination reliability of plastic material
Impact.
In one embodiment of the invention, regulated and controled by the condition to high temperature oxidation process, Momentum profiles point
Analysis, the oxide-film of formation is fine and close and thicker, wherein being primarily present Fe, Cr, Ni, O element, wherein Ni constituent contents are relatively low.So,
Oxide-film is main based on smaller thermal conductivity factor ferriferous oxide and chromated oxide, shows more excellent effect of heat insulation.
On the other hand, because the conjunction that the present invention is provided has above-mentioned technique effect, so in the present invention, Ke Yishi
When the aperture for reducing cellular pore, the combination power between stainless steel substrate and plastic material is still ensured that.Reduce honeycomb
The aperture of shape pore, corresponding pore-forming technique is also simplified, and thus brings the simplification of technological process and the reduction of time cost.
After the aperture of cellular pore reduces, hole is more evenly distributed, and hole quality is higher.Fig. 2 is shown by high-temperature oxydation
After reason, the pattern of the cellular pore on stainless steel substrate surface, cellular broad pore distribution is uniform.
Alternatively, the plastic material can be by polyphenylene sulfide, poly terephthalic acid butanol resin, polyamide, poly-
At least one material in carbonic ester and polyolefin is made.These materials can combine the crystalline resin combination to form high rigidity
Thing, in Shooting Technique, composition cooling after can in cellular pore crystallization and freezing.
Alternatively, the average pore size scope of the cellular pore can be 10-150nm, and the cellular pore is never
The mean depth scope that the surface of rust steel substrate extends inward is 10-200nm.Can be by the regulation and control to pore-forming technique to upper
Architectural feature is stated to be adjusted.Alternatively, the mean pore size of the cellular pore is 50-100nm.
Alternatively, the thickness range of the oxide-film can be 1-20nm, can by the temperature to high temperature oxidation process,
The conditions such as time, atmosphere are regulated and controled, so that the thickness of oxide-film is adjusted, further, by checking, the cellular pore
Mean pore size be 50-100nm, and oxide-film thickness range in 10-20nm, the corrosion resistant of plastic material and stainless steel
Erosion, crack resistence effect are optimal.
Especially, the surface of the oxide-film can also be adsorbed with profit hole agent, and profit hole agent is terephthalic acid (TPA), second two
In amine tetraacethyl, p-nitrophenyl sulfonic acid, water-soluble amino acids, ethylenediamine, triethanolamine, ammoniacal liquor, chloroethanes, epoxychloropropane
It is at least one.Profit hole agent can improve the surface characteristics of oxide-film so that when carrying out injection molding process, plastic material energy
It is enough smoothly to flow in cellular pore.
In addition, oxide-film of the present invention is formed by high temperature oxidation process, this processing mode can improve profit hole
Absorption of the agent on oxide-film.And, it is also possible to absorption, filling effect of the plastic material in injection are improved, makes plastic material
More fully, in the reliable absorption insertion cellular pore.Main reason is that, it is raw during high temperature oxidation process
Into the interface of oxide and oxygen atom there is oxygen molecule reduction reaction, form substantial amounts of O2 -Active ion.Such active ion
Generation and aggregation on oxide-film surface are more beneficial for the absorption of follow-up wetting agent and plastic cement.This technique effect is in existing skill
Natural oxide film in art is aoxidized on the oxide-film to be formed and not existed through soda acid, is the incomparable skill of regular oxidation film
Art effect.
Especially, can also be doped with packing material in the plastic material, the packing material is nylon fiber, carbon fibre
At least one in dimension, glass fibre, aromatic polyamide fibre, calcium carbonate, magnesium carbonate, silica and clay, it is described to fill out
The scope for filling material shared mass percent in the plastic material is 5-40wt%.The packing material can noted
Filling is adulterated before modeling processing technology in a plastic material.
The linear expansion coefficient of stainless steel is 1.5 × 10-5/ DEG C, and the linear expansion coefficient of plastic material is in 6-8 × 10-5/ DEG C,
The linear expansion coefficient for differing larger between stainless steel and plastic material is unfavorable for the solidification process of plastic material.Therefore, it is necessary to right
It is modified to reduce the linear expansion coefficient of plastic material in plastic material.For example, the linear expansion coefficient of glass fiber material is only
It is 3.8 × 10-5/ DEG C, can mix the materials such as glass fibre in a plastic material, makes the line of plastic material composition expand system
Number with stainless steel as close as.
Present invention also offers a kind of stainless steel and the processing method of the combination of plastics, first, there is provided stainless steel substrate,
Treatment is etched to stainless steel substrate, cellular pore is formed with the surface in stainless steel substrate；Then, to the stainless steel
Base material carries out high temperature oxidation process, and oxide-film is formed on the surface of the stainless steel substrate, and the oxide-film at least includes iron oxygen
Two kinds in compound, chromated oxide or nickel oxide, for example, ferriferous oxide and chromated oxide can be included, or iron can be included
Oxide, chromated oxide and nickel oxide etc..The temperature range of the high temperature oxidation process is 110-450 degrees Celsius, during treatment
Between be 120-10 minute, in the atmosphere of high temperature oxidation process the volume content scope of oxygen be 75%-100%；Finally, described
The surface injection molding plastic material of stainless steel substrate, makes the part-structure of plastic material be embedded in the cellular pore, is formed not
Become rusty steel and the integrated combination of plastics.The processing method provided by the present invention, can prepare the stainless steel of present invention offer
With the combination of plastics.
It is of the invention preferred embodiment in, high temperature oxidation process be temperature range be 200-300 degrees Celsius
It is heat-treated 90-30 minutes in condition, the quality for generating oxide-film is preferable.And high temperature oxidation process preferably contains in the volume of oxygen
Carried out under the atmosphere of amount >=90%, can further be carried out under the atmosphere of pure oxygen.
Before treatment is etched to stainless steel substrate, the step of pre-processing can also be included.It is alternatively possible in advance
Carry out the oil removing ungrease treatment of stainless steel substrate.Stainless steel substrate is soaked in 35-80 DEG C of stainless steel cleaner at ultrasound
Reason 60-600s, is subsequently placed at during electrical conductivity is less than the pure water of 20us/cm and cleans 60s.The stainless steel cleaner is 100-
The acid of 300g/L, alkali or organic solvent etc..
Alternatively, natural oxide can also be carried out to the top layer of stainless steel substrate to process.By except stainless after grease
Steel substrate is placed in 40-80 DEG C except 60s or so is impregnated in film liquid, is subsequently placed in neutralizer and processes 60s or so, is then placed in pure water
Middle cleaning.It is described except film liquid is the alkaline solution such as 5-10vol.% NaOH, potassium hydroxide, the neutralizer is 100-
The alkaline solution remained in the dust technology and sulfuric acid liquid of 300g/L and on stainless steel substrate.Its main purpose is to remove stainless steel
The natural oxide film that substrate surface is formed, excludes adverse effect of the uneven oxide-film to etching process.
The etching process carried out to stainless steel substrate can also can be lost using chemical etching into hole machined using electrochemistry
Carve, the present invention is limited not to this, can be selected at specific etching according to the properity requirement to cellular pore
Reason.
For chemical etching, stainless steel substrate can be placed in 30-90 degrees Celsius of chemical etching liquor and impregnate 10-120
Minute, chemical etching liquor is sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, boric acid, formic acid, propionic acid, butyric acid, alginic acid, oxalic acid, citric acid
With at least one in caprolactam.Alternatively, the process of whole etching process pore-forming can include repeatedly different chemistry erosions
Step is carved, to regulate and control the pore-forming effect such as aperture, distribution situation of cellular pore.
For chemical etching, send out with the stainless steel substrate as anode, the region of cellular pore to be formed
Raw electrochemical corrosion, the voltage range of chemical etching is 5-60V, and the duration is 10-100 minutes.
Especially, it is also possible to chemical etching and chemical etching are respectively adopted in the different step of whole etching process.
This etching mode can obtain more rich pore-forming regulating effect, for example, it is larger first aperture can be formed using chemical etching
Hole, form the less cellular pore in aperture with chemical etching directional etching again afterwards.
Especially, after high temperature oxidation process, the treatment of profit hole can also be carried out to the stainless steel substrate, the treatment can be with
Improve the surface characteristic of oxide-film, plastic material is preferably filled into the cellular pore in enabling follow-up injection molding
In, form the form being embedded in cellular pore after plastic material solidification.The profit hole treatment can immerse stainless steel substrate
In profit hole agent, profit hole agent is terephthalic acid (TPA), ethylenediamine tetra-acetic acid, p-nitrophenyl sulfonic acid, water-soluble amino acids, second two
At least one of amine, triethanolamine, ammoniacal liquor, chloroethanes, epoxychloropropane.After stainless steel substrate is taken out from profit hole agent, can
So that dry naturally can also cleaning, drying.The uniform profit hole agent being attached in oxide layer can be with the plastic material in injection moulding process
Generation physical and chemical reaction so that plastic material accelerates to be full of in cellular pore, significantly improves plastic cement with stainless steel part
Adhesion.
Although being described in detail to some specific embodiments of the invention by example, the skill of this area
Art personnel it should be understood that example above is merely to illustrate, rather than in order to limit the scope of the present invention.The skill of this area
Art personnel to above example it should be understood that can modify without departing from the scope and spirit of the present invention.This hair
Bright scope is defined by the following claims.
Claims (17)
1. the conjunction of a kind of stainless steel and plastics, it is characterised in that the conjunction includes stainless steel substrate, the stainless steel
Cellular pore is formed with the surface of base material, it is described by 110-450 degrees Celsius, the high temperature oxidation process of 120-10 minutes
Oxide-film is formed with the surface of cellular pore, the volume content of oxygen is 75%- in the atmosphere of high temperature oxidation process
100%, the oxide-film at least includes two kinds in ferriferous oxide, chromated oxide or nickel oxide, on the stainless steel substrate
Plastic material is injection molded with, the plastic material is embedded in the cellular pore.
2. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that the oxide-film at least includes iron
Oxide and chromated oxide.
3. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that the gas of the high temperature oxidation process
Volume content >=90% of oxygen in atmosphere.
4. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that the temperature of the high temperature oxidation process
Degree scope is 200-300 degrees Celsius, and process time is 90-30 minutes.
5. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that the plastic material is by polyphenylene sulfide
At least one material in ether resin, poly terephthalic acid butanol resin, polyamide, makrolon and polyolefin is made.
6. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that the cellular pore it is average
Pore diameter range is 10-150nm, and the mean depth scope that the cellular pore is extended inward from the surface of stainless steel substrate is
10-200nm。
7. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that the thickness range of the oxide-film
It is 1-20nm.
8. the conjunction of stainless steel according to claim 7 and plastics, it is characterised in that the thickness range of the oxide-film
It is 10-20nm.
9. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that the adsorption of the oxide-film
There is profit hole agent, profit hole agent is terephthalic acid (TPA), ethylenediamine tetra-acetic acid, p-nitrophenyl sulfonic acid, water-soluble amino acids, second two
At least one in amine, triethanolamine, ammoniacal liquor, chloroethanes, epoxychloropropane.
10. the conjunction of stainless steel according to claim 1 and plastics, it is characterised in that adulterated in the plastic material
There is packing material, the packing material is nylon fiber, carbon fiber, glass fibre, aromatic polyamide fibre, calcium carbonate, carbon
At least one in sour magnesium, silica and clay, the packing material shared mass percent in the plastic material
Scope is 5-40wt%.
The processing method of the combination of a kind of 11. stainless steels and plastics, it is characterised in that stainless steel substrate is provided；To stainless steel
Base material is etched treatment, and cellular pore is formed on the surface of stainless steel substrate；High temperature oxygen is carried out to the stainless steel substrate
Change is processed, and oxide-film is formed on the surface of the stainless steel substrate, and the oxide-film includes ferriferous oxide, and including chromium oxidation
At least one in thing or nickel oxide, the temperature range of the high temperature oxidation process is 110-450 degrees Celsius, and process time is
120-10 minutes, the volume content scope of oxygen was 75%-100% in the atmosphere of high temperature oxidation process；In the stainless base steel
The surface injection molding plastic material of material, makes the part-structure of plastic material be embedded in the cellular pore, forms stainless steel with modeling
The integrated combination of material.
12. processing methods according to claim 11, it is characterised in that the oxide-film at least includes ferriferous oxide and chromium
Oxide.
13. processing methods according to claim 11, it is characterised in that oxygen in the atmosphere of the high temperature oxidation process
Volume content >=90%.
14. processing methods according to claim 11, it is characterised in that the temperature range of the high temperature oxidation process is
200-300 DEG C, process time is 90-30 minutes.
15. according to any described processing method of claim 11 to 14, it is characterised in that after high temperature oxidation process, to not
Rust steel substrate carries out the treatment of profit hole, and by stainless steel substrate immersion profit hole agent, profit hole agent is terephthalic acid (TPA), ethylenediamine tetraacetic
At least one in acetic acid, p-nitrophenyl sulfonic acid, water-soluble amino acids, ethylenediamine, triethanolamine, ammoniacal liquor, chloroethanes, epoxychloropropane
Kind.
16. according to any described processing method of claim 11 to 14, it is characterised in that the etching process is lost for chemistry
Carve, stainless steel substrate is placed in 30-90 degrees Celsius of chemical etching liquor impregnate 10-120 minute, chemical etching liquor be sulfuric acid,
In nitric acid, phosphoric acid, hydrofluoric acid, boric acid, formic acid, propionic acid, butyric acid, alginic acid, oxalic acid, citric acid and caprolactam at least one
Kind.
17. according to any described processing method of claim 11 to 14, it is characterised in that the etching process is lost for electrochemistry
Carve, with the stainless steel substrate as anode, make the region of cellular pore to be formed that electrochemical corrosion to occur, chemical etching
Voltage range is 5-60V, and the duration is 10-100 minutes.
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| CN201710029374.XA CN106903838A (en) | 2017-01-16 | 2017-01-16 | The conjunction and its processing method of stainless steel and plastics |
| PCT/CN2017/090623 WO2018129871A1 (en) | 2017-01-16 | 2017-06-28 | Stainless steel and plastic combined member, and processing method therefor |
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| WO2018129872A1 (en) * | 2017-01-16 | 2018-07-19 | 歌尔股份有限公司 | Stainless steel and plastic combined member, and processing method therefor |
| CN109183108A (en) * | 2018-08-23 | 2019-01-11 | 歌尔股份有限公司 | A kind of aluminum alloy materials and preparation method thereof and composite material |
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| CN114321693B (en) * | 2021-12-29 | 2024-03-12 | 富联裕展科技(深圳)有限公司 | Metal product and preparation method thereof, metal complex and preparation method thereof |
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