CN103895161A - Preparation method of stainless steel-resin composite and stainless steel-resin composite prepared by same - Google Patents
Preparation method of stainless steel-resin composite and stainless steel-resin composite prepared by same Download PDFInfo
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- CN103895161A CN103895161A CN201210582285.5A CN201210582285A CN103895161A CN 103895161 A CN103895161 A CN 103895161A CN 201210582285 A CN201210582285 A CN 201210582285A CN 103895161 A CN103895161 A CN 103895161A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B29C2045/1486—Details, accessories and auxiliary operations
- B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
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Abstract
The invention relates to a preparation method of a stainless steel-resin composite and a stainless steel-resin composite prepared by the same. The preparation method comprises the following steps: S1. putting a pretreated stainless steel substrate in a corrosive solution to perform electrochemical corrosion, wherein the corrosive solution is a 2-25 wt% hydrochloric acid and/or 5-35 wt% iron trichloride solution; and S2. carrying out injection molding on a resin composition to the surface of the stainless steel substrate obtained in the step S1, and forming to obtain the stainless steel-resin composite. The stainless steel-resin composite has the advantages of high binding force between stainless steel and resin, simple technique, low requirements for resin, wide application range and no pollution, and can easily implement large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of stainless steel resin composite body and the stainless steel resin composite body of preparation thereof, more particularly, relate in particular to stainless steel that a kind of adhesion is stronger and thermoplastic resin integrated and the preparation method of stainless steel resin composite body and the stainless steel resin composite body of preparation thereof that form.
Background technology
In the part manufacture field of automobile, household electrical appliance goods, industrial machine etc., require the one-body molded technology of metal and resin, at present industry adopt adhesive under normal temperature or heating by metal and the integrated combination of synthetic resin.Can prepare metal and integrally moulded complex although adopt said method, but between the complex metal obtaining according to these methods and plastic cement, adhesion is poor, and adhesive acid-fast alkali-proof poor performance, complex cannot carry out the surface treatments such as follow-up anodic oxidation, adhesive has certain thickness simultaneously, inapplicable for complicated shape region, cannot realize the seamless combination of stainless steel and resin.Also there is the in-mould injection of employing technology, by the mode of punching press or welding, on stainless steel, generate and draw plastic structure, thereby together with arriving with resin-bonded, but adopt in-mould injection, need design draw plastic structure, and stainless steel body and resin-bonded power are very little, easily produce gap, the design of product is also had to requirement, affect its scope of application, increase cost, thereby all the time, people are examining whether more reasonably the method for high-intensity engineering resin and metal-integral always.
Those skilled in the art is by having researched and proposed nanoprocessing treatment technology, nanoprocessing treatment technology (NMT) is exactly the integrated combination technology of metal and plastic cement, it passes through metal-surface nano processing, allow directly ejection formation on metal surface of plastic cement, make metal and the plastic cement can integrated molding.For effective combination of metal and plastic cement, nanometer forming technique is a kind of best methods, and can replace at present conventional embedding ejaculation or zinc-aluminium, magnalium die casting, can provide one to have price competition, high performance gold is moulded integration product.Compared with bonding technique, NMT technology has obvious advantage, for example: the overall weight, excellent strength, the working (machining) efficiency that reduce product are high.NMT technology range of application contains vehicle, information technoloy equipment and 3C Product, can allow product towards more frivolous, more miniature future development.
The existing disclosed mode having by chemical etching, erodes away nano level ultra tiny concaveconvex shape at stainless steel surfaces, and carries out injection moulding with specific resin resin and metal are combined.But because this kind of mode had relatively high expectations to resin, define the scope of application, the stainless steel of stainless steel resin composite body and the adhesion of resin prepared by while this kind of forms of corrosion do not reach ideal effect yet.
Summary of the invention
A little less than the adhesion of the present invention for stainless steel and resin in the stainless steel resin composite body that solves prior art and prepare, and the technical problem of having relatively high expectations to resin in Shooting Technique.Provide the adhesion of a kind of stainless steel and resin strong, and technique is simple and easy to large-scale production, to resin require lowly, the scope of application is wide, the stainless steel resin composite body of the preparation method of free of contamination stainless steel resin composite body and preparation thereof.
First object of the present invention is to provide a kind of preparation method of stainless steel resin composite body, comprises following steps:
S1, carries out electrochemical corrosion by putting into corrosive liquid through the stainless steel substrate of pre-treatment, and described corrosive liquid is that mass concentration is the hydrochloric acid of 2-25wt% and/or the liquor ferri trichloridi that mass concentration is 5-35wt%;
s2, resin combination is injection-moulded in to the stainless steel substrate surface of step S1 gained, after moulding, obtain stainless steel resin composite body.
Second object of the present invention is to provide a kind of stainless steel resin composite body, employing said method is made, comprise: stainless steel substrate and with the resin bed of its surface conjunction, the surface of described stainless steel substrate is formed with the hole of 1 ~ 100 micron pore size, and the resin combination that forms described resin bed is filled in described hole.
The present invention surprisingly finds to adopt method of the present invention, can form better erosional surface on stainless steel substrate surface, the pore space structure uniqueness forming on stainless steel substrate surface, hole is that opening is little, inner large structure, hole diameter can reach tens of microns simultaneously, and in substrate surface dense distribution, nearly all thermoplastic resin can enter hole in the process of injection mo(u)lding, resin injection molding is easy, synthetic resin is not had to special requirement yet, the scope of application is wider, and because hole opening is little, inner large structure, make cooling rear resin also be difficult for deviating from hole, hole quantity in unit are of this kind of structure is many simultaneously, strengthen the adhesion of stainless steel and resin, improve resin and stainless adhesion, and method of the present invention is little to metallic matrix size impact, provide cost savings, technique is simple, be more suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is the surperficial metallograph of 50 times of surface treated stainless steel substrate in embodiments of the invention 1.
Fig. 2 is the cross section metallograph of 200 times of surface treated stainless steel substrate in embodiments of the invention 1.
The specific embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The preparation method who the invention provides a kind of stainless steel resin composite body, comprises following steps:
S1, carries out electrochemical corrosion by putting into corrosive liquid through the stainless steel substrate of pre-treatment, and described corrosive liquid is that mass concentration is the hydrochloric acid of 2-25wt% and/or the liquor ferri trichloridi that mass concentration is 5-35wt%.Surface treatment is carried out in stainless steel substrate surface, form unique surface texture, can form unique pore space structure on stainless steel substrate surface, and in substrate surface dense distribution, resin injection moulding is easy, difficulty deviates from easier to obtain in the better situation of stainless steel resin composite body of adhesion excellence, corrosive liquid is that mass concentration is the hydrochloric acid of 5-20wt% and/or the liquor ferri trichloridi that mass concentration is 10-35%, and more preferably corrosive liquid is that mass concentration is the hydrochloric acid of 10-20wt% and/or the liquor ferri trichloridi that mass concentration is 15-35wt%.Further guarantee the effect of efficiency, life-span and the electrochemical corrosion of corrosive liquid economy.
Wherein, equipment and the operating technology of electrochemical corrosion are known to the skilled person, for example, can in electrolytic cell, carry out, using stainless steel substrate as anode, graphite electrode, as negative electrode, makes to need injection moulding region towards minus plate, preferably, the voltage of electrochemical corrosion is 2-8V, and the time is 2-20min, further preferred, the voltage of electrochemical corrosion is 3-6V, time is 3-15min, and corrosive effect is more excellent, and heat release is little.Preferably, the temperature of corrosive liquid is 15-50 ℃, more preferably 25-40 ℃, i.e. and electrochemical corrosion is carried out at the temperature of 25-40 ℃.Electrochemical corrosion can be for once, also can be repeated multiple times.In better situation, form the hole of 1～100 micron pore size on stainless steel substrate surface, pore structure uniqueness, can make the binding ability of resin bed and stainless steel substrate better, has better tensile strength, makes the integrated combination of stainless steel double zoarium better.
Wherein, pre-treatment is the pretreatment procedure that stainless steel surfaces is carried out that those skilled in the art commonly use, generally make its surfacing, clean, generally comprise and carry out mechanical grinding or grind and remove significantly foreign matter of surface, the processing wet goods then metal surface being adhered to carries out degreasing, cleaning.Preferably, pre-treatment comprises polishes to surface, stainless steel substrate surface, for example, can be: first adopt 100-400 object sand paper or put it in polishing machine stainless steel substrate surface finish.Then carry out successively oil removing, the first washing, sandblast, the second washing, drying and other steps, the various solvents of commonly using with those skilled in the art clean this stainless steel in ultrasonic wave, scavenging period 0.5-2h, the greasy dirt of removal stainless steel surfaces, described solvent can be ethanol or acetone.In the present invention, preferably with absolute ethyl alcohol by carrying out again sandblast after stainless steel oil removing after washing wiped clean, can increase stainless steel base surface roughness, then rinse well by deionized water, finally at 50-90 ℃, dry.
Need stainless steel the present invention of pre-treatment to be not particularly limited, can use various commercially available stainless steels; Stainless steel described in the present invention is the various shapes commonly used of those skilled in the art, the stainless steel of structure, and the present invention is not particularly limited.Stainless various shape, structure, can complete by machining.
The present invention is preferred, before step S1, also comprise and will not need the surface shaded of binding resin through the stainless steel substrate of pre-treatment, the uncovered injection moulding region current density in the time of electrochemical corrosion that needs is larger, need injection moulding region more easily to corrode, but not injection moulding region is almost corrosion-free, can not affect the outward appearance in the non-injection moulding of stainless steel product region, do not need or only need carry out little subsequent treatment to product.
Cover the present invention and be preferably and adhere to ink layer, at the surface attachment ink that does not need binding resin through the stainless steel substrate of pre-treatment, by ink simply to not needing injection moulding region to cover.Preferably the thickness of ink layer is 5-20 micron, and now ink is generally the ink of electrochemical corrosion resistant, saves the energy and has reduced the consumption of corrosive liquid.
The present invention also can preferably be covered for preparing oxidation film layer, do not need the surface of binding resin to contain oxidation film layer at the stainless steel substrate through pre-treatment, by oxidation film layer to not needing injection moulding region to cover, the thickness of preferential oxidation rete is 100nm-3000nm, more preferably 1000nm-2500nm.Wherein, oxidation film layer can, for utilizing exterior material preparation, can be also to utilize stainless steel substrate itself to be prepared, and makes its top layer have the oxidation film layer of passivation.The present invention preferably prepares oxidation film layer and comprises and will need the surface attachment ink of binding resin through the stainless steel substrate of pre-treatment; Again stainless steel substrate is oxidized to passivation; Rear removal ink.Wherein, oxidation passivation can preferably include stainless steel substrate is contacted with passivating solution, mode the present invention of contact does not limit, for example can be by whole being immersed in passivating solution of stainless steel substrate after spraying ink, can be under the condition of heating, also can be under the condition not heating, in better situation, the temperature that preferably stainless steel substrate contacts with passivating solution is 10-90 ℃, more preferably 50-80 ℃, the time that stainless steel substrate contacts with passivating solution is 3-300min, more preferably 30-180min, the temperature that passivating solution for example can be set is 50-80 ℃, stainless steel substrate is immersed and in passivating solution, processes cleaning, drying after 30-180min.Wherein, one or more in passivating solution preferably sulfuric acid solution, salpeter solution, potassium bichromate solution, chromium trioxide solution and sodium nitrite solution.Also can be preferred, oxidation passivation comprises carries out stainless steel substrate electrochemical passivation in oxidizing acid solution, wherein, oxidizing acid solution is selected from one or more in sulfuric acid solution, salpeter solution, chromium trioxide solution, potassium bichromate solution, hydrogenperoxide steam generator and citric acid solution.The condition of described electrochemical passivation is temperature 40-90 ℃, voltage is 50mV-1000mV, time is 2-15min, is specially using stainless steel substrate as anode, puts into temperature and be the oxidizing acid solution of the 40-90 ℃ oxidation 2-15min that switches under the voltage of 50mV-1000mV.Form oxidation film layer top layer in the non-injection moulding of stainless steel substrate region by oxidation passivation, by first needing injection moulding region to adhere to ink on stainless steel substrate surface, passivation is carried out in the non-injection moulding region of through peroxidating passivation, stainless steel surfaces not being adhered to ink again, make non-injection moulding area surfaces generate layer oxide film layer, after removing ink, again stainless steel substrate is carried out to electrochemical corrosion, the corrosion resistance with oxidation film layer through Passivation Treatment is better, need the more easily corrosion in the time of electrochemical corrosion of injection moulding region, and higher through the resistance with oxidation film layer of Passivation Treatment, also make to need injection moulding region more easily to corrode, need injection moulding zonal corrosion stronger thereby can make, but not almost free from corrosion product of injection moulding region, can not affect the outward appearance in the non-injection moulding of stainless steel product region, do not need or only need carry out little subsequent treatment to product.In this step to graphite require low; can be any graphite; for example ink can be acid-proof ink; can select common epoxy resin, organic siliconresin etc.; can be common ink, cost be low, and the oxidation film layer stable performance of preparing in this step; do not come off, to not needing casting resin region to have good protection.The method the present invention who removes ink in this step does not limit, and can adopt paint stripper, for example, in the time that ink is acid resistance ink, stainless steel substrate can be immersed to the ink that fades away in alkali paint remover.
Wherein, above-mentioned method the present invention who adheres to ink is not particularly limited, for example can adopt the modes such as coating, spraying, for example will put into and cover tool through the stainless steel substrate of pre-treatment, at the region of design graphite linings spraying ink, equipment and the operating technology of spraying are known to the skilled person, and generally also need baking and curing after spraying.
After preferred steps S1 of the present invention, before step S2, also comprise the stainless steel substrate of step S1 gained is contacted to 1 ~ 30min with alkaline solution, neutralize, preferably, alkaline solution is selected from the sodium carbonate liquor that mass percentage concentration is 1 ~ 30wt%, sodium bicarbonate solution or the mass percentage concentration that mass percentage concentration is 1 ~ 30wt% is 1 ~ 30wt% sodium hydroxide solution, general cleaning, drying after neutralization.
s2, resin combination is injection-moulded in to the stainless steel substrate surface of step S1 gained, after moulding, obtain stainless steel resin composite body.Be specifically as follows dried stainless steel substrate is proceeded in mould, carry out integrated treatment with the resin combination making, after moulding, can obtain stainless steel double zoarium provided by the invention, in the present invention, can make the integrated molding mode of metallo-plastic all can be used for the present invention, the condition of injection moulding can be nozzle temperature 200-350 ℃, mold temperature 50-200 ℃, the amount of the general resin combination injecting is 0.1-1000g, and the complex surfaces of preparation has the resin bed that 0.1-10mm is thick.
Resin combination the present invention be not particularly limited, and can adopt and well known to a person skilled in the art the various resin combinations that can be combined with stainless steel, and preferred resin composition is thermoplastic resin.Preferred thermoplastic resin is the blend that contains matrix resin and vistanex.Preferably matrix resin is noncrystalline matrix resin, select noncrystalline matrix resin as injection molding material, its lustrous surface, toughness are all due to high crystalline resin of the prior art, be used in conjunction with fusing point simultaneously and be the vistanex of 65 ℃-105 ℃, need to injection moulding under specific mould temperature in the time of moulding, moulding process is simplified, can guarantee that the metal-resin composite obtaining has better mechanical strength and surface treatment characteristics simultaneously, thereby solve the incrustation problem of working of plastics, meet client's diversified demand.By in adopted noncrystalline matrix resin, be used in conjunction with fusing point and be the vistanex of 65 ℃-105 ℃, can increase the ability that resin flows into metal-surface nano level micropore, thereby guarantee that the metal and the plastics that form have good adhesive force, mechanical strength.Under preferable case, take the thermoplastic resin of 100 weight portions as benchmark, wherein the content of matrix resin is 70-95 weight portion, and the content of vistanex is 5-30 weight portion.
As a further improvement on the present invention, the present inventor also finds, adopts fluidity improver in thermoplastic resin, can also improve the fluid ability of resin, further improves the injection moulding performance of adhesive force and the resin of metal and resin.Under preferable case, take the thermoplastic resin of 100 weight portions as benchmark, in described thermoplastic resin, also contain the fluidity improver of 1-5 weight portion.Under preferable case, described fluidity improver is cyclic polyester.
As previously mentioned, in the present invention, described matrix resin is non-crystalline resin.Particularly, preferably, matrix resin is the mixture of polyphenylene oxide (PPO) and polyphenylene sulfide (PPS), and under preferable case, the weight ratio of PPO and PPS is 3:1-1:3, more preferably 2:1-1:1.Or preferably matrix resin is the mixture of polyphenylene oxide (PPO) and polyamide (PA), and under preferable case, the weight ratio of PPO and PA is 3:1-1:3, more preferably 2:1-1:1.Or preferably matrix resin is Merlon (PC), and it can be selected from various straight chain Merlon and/or straight chain Merlon, and the present invention does not have particular provisions.
In the present invention, the fusing point of the vistanex adopting is 65 ℃-105 ℃.Under preferable case, described vistanex can adopt grafted polyethylene.More preferably in situation, it is the grafted polyethylene of 100 ℃ or 105 ℃ that described vistanex can adopt fusing point.
Resin combination of the present invention can also contain other property-modifying additives etc., and the present invention is not particularly limited, and can arrange as required, for example, in resin combination, can also contain filler.Described filler is the various fillers that those skilled in the art commonly use, for example, can be various fiberfill or powdery filler.Described fiberfill can be selected from one or more in glass fibre, carbon fiber and aromatic polyamide fibre; Described powder-type filler can be selected from one or more in calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talcum powder, glass and clay.More preferably in situation, for make plastics composite laterally, longitudinally all there is the linear expansion coefficient close with stainless steel substrate, in the present invention, take the matrix resin of 100 weight portions as benchmark, fiberfill content is 50-150 weight portion, and the content of powder-type filler is 50-150 weight portion.
According to the preparation method of stainless steel resin composite body provided by the invention, matrix resin, vistanex are mixed, prepare resin combination.The preparation method of described resin combination adopts the method for the conventional physical blending of those skilled in the art to obtain, and mixes by matrix resin, vistanex, by double screw extruder extruding pelletization, stand-by.
According to the preparation method of stainless steel double zoarium provided by the invention, can also in described matrix resin, add filler, fluidity improver, mix, make resin combination, thus make resin combination laterally, longitudinally all there is the linear expansion coefficient close with stainless steel substrate.
Preparation method of the present invention is simple, the work simplification of more existing employing adhesive production procedure, shorten the production time, and need add heat erosion and define the plastics kind that can use compared with existing nano surface injection moulding, energy resource consumption is few, the scope of application is wider, and between the resin bed by the prepared stainless steel resin composite body of preparation method of the present invention and stainless steel substrate, adhesion is good simultaneously, has preferably tensile shear strength.
The stainless steel resin composite body that the present invention provides above-mentioned preparation method to prepare simultaneously, comprise stainless steel substrate and the resin bed with its surface conjunction, the surface of described stainless steel substrate is formed with the hole of 1 ~ 100 micron pore size, and the resin combination that forms described resin bed is filled in described hole.The shear fracture power of stainless steel substrate and resin bed can reach 5-30MPa.Wherein, the various resin combinations that can be compound with stainless steel that resin combination is known to the skilled person.
The stainless steel resin composite body that the present invention makes can directly use, and also can carry out as required some follow-up post processings, such as CNC(Digit Control Machine Tool processing), spraying etc., the present invention does not limit.
Below by specific embodiment, the present invention is described in further detail.
embodiment 1
The present embodiment is prepared stainless steel resin composite body.
1, pre-treatment: by thick 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it in polishing machine and grind, clean with absolute ethyl alcohol afterwards, then sandblast, rinse well, dry at 80 ℃ by deionized water, obtain the stainless steel substrates through pre-treatment;
2, surface treatment: the hydrochloric acid 500ml for preparing 10wt% in beaker, put into thermostat and be warming up to 30 ℃, take graphite electrode as negative electrode, above-mentioned stainless steel substrates is anode, and voltage is 3V, after constant voltage energising 3min, takes out sample, washing, put into 5wt% sodium carbonate liquor and soak 10min, take out afterwards washing, dry at 80 ℃;
Adopt metallographic microscope to observe the surface of the stainless steel substrate after above-mentioned surface treatment, obtain surperficial metallograph as shown in Figure 1, cross section metallograph as shown in Figure 2, record the hole that approximately 40 microns of maximums diameter of hole are contained on stainless steel substrate surface, on erosional surface, hole is very intensive, hole is circular substantially, pore size is more even, there is no king-sized hole, hole cross section ovalisation, hole opening diameter is less, and inner space diameter is large, this structure enters the resin in hole can block injection moulding time, the widest part reaches more than 40 microns;
3, moulding: the stainless steel substrates after drying is inserted in injecting molding die, polyphenylene sulfide (PPS) resin combination that injection moulding contains 20wt% glass fibre, the demoulding and cooling after obtain strong bonded stainless steel together and the stainless steel resin composite body sample S1 of resin combination.
embodiment 2
Adopt the method identical with embodiment 1 to prepare stainless steel resin composite body sample S2.Different is step 2, and the voltage of electrochemical corrosion is 6V, and the time is 3min, and the temperature of hydrochloric acid is 30 ℃.Adopt the method identical with embodiment 1 to record the hole that approximately 70 microns of maximums diameter of hole are contained on stainless steel substrate surface.
embodiment 3
Adopt the method identical with embodiment 1 to prepare stainless steel resin composite body sample S3.Different is step 2, and the voltage of electrochemical corrosion is 3V, and the time is 6min, and the temperature of hydrochloric acid is 30 ℃.Adopt the method identical with embodiment 1 to record the hole that approximately 50 microns of maximums diameter of hole are contained on stainless steel substrate surface.
embodiment 4
Adopt the method identical with embodiment 1 to prepare stainless steel resin composite body sample S4.Different is step 2, and the voltage of electrochemical corrosion is 3V, and the time is 3min, and the temperature of hydrochloric acid is 50 ℃.Adopt the method identical with embodiment 1 to record the hole that approximately 60 microns of maximums diameter of hole are contained on stainless steel substrate surface.
embodiment 5
Adopt the method identical with embodiment 1 to prepare stainless steel resin composite body sample S5.Different is step 2, and the mass percentage concentration of hydrochloric acid is 20wt%.Adopt the method identical with embodiment 1 to record the hole that approximately 50 microns of maximums diameter of hole are contained on stainless steel substrate surface.
embodiment 6
Adopt the method identical with embodiment 1 to prepare stainless steel resin composite body sample S6.Different is step 2, and the mass percentage concentration of hydrochloric acid is 3wt%.Adopt the method identical with embodiment 1 to record the hole that approximately 20 microns of maximums diameter of hole are contained on stainless steel substrate surface.
embodiment 7
Adopt the method identical with embodiment 1 to prepare stainless steel resin composite body sample S7.Different is step 2, surface treatment: the liquor ferri trichloridi 500ml for preparing 25wt% in beaker, put into thermostat and be warming up to 30 ℃, take graphite electrode as negative electrode, above-mentioned stainless steel substrates is anode, voltage is 3V, after constant voltage energising 3min, take out sample, washing, puts into 5wt% sodium carbonate liquor and soaks 10min, take out afterwards washing, dry at 80 ℃.Adopt the method identical with embodiment 1 to record the hole that approximately 60 microns of maximums diameter of hole are contained on stainless steel substrate surface.
embodiment 8
Adopt the method identical with embodiment 1 to prepare stainless steel resin composite body sample S8.Different is step 2, surface treatment: the mixed solution 500ml for preparing the hydrochloric acid of 10wt% and the ferric trichloride of 5wt% in beaker, put into thermostat and be warming up to 30 ℃, take graphite electrode as negative electrode, above-mentioned stainless steel substrates is anode, voltage is 3V, after constant voltage energising 3min, take out sample, washing, puts into 5wt% sodium carbonate liquor and soaks 10min, take out afterwards washing, dry at 80 ℃.Adopt the method identical with embodiment 1 to record the hole that approximately 50 microns of maximums diameter of hole are contained on stainless steel substrate surface.
embodiment 9
1, pre-treatment: by thick 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it in polishing machine and grind, clean with absolute ethyl alcohol afterwards, then sandblast, rinse well, dry at 80 ℃ by deionized water, obtain the stainless steel substrates through pre-treatment;
2, adhere to ink layer: above-mentioned stainless steel substrates is put into mould, utilize mould to hide and need injection moulding region, hide 15mm*5mm region, stainless steel substrates one end, mould is put into flush coater, spraying ink 5680 photosensitive-ink (Wan Jiayuan Chemical Co., Ltd. of Shenzhen), at 80 ℃, dry, UV solidifies, and is not needing injection moulding region to form the ink layer of 15 micron thickness;
3, surface treatment: the hydrochloric acid 500ml for preparing 10wt% in beaker, put into thermostat and be warming up to 30 ℃, take graphite electrode as negative electrode, above-mentioned stainless steel substrates is anode, and voltage is 3V, after constant voltage energising 3min, takes out sample, washing, put into 5wt% sodium carbonate liquor and soak 10min, take out afterwards washing, dry at 80 ℃;
Adopt the method identical with embodiment 1 to record the hole that approximately 40 microns of maximums diameter of hole are contained on stainless steel substrate surface;
3, moulding: the stainless steel substrates after drying is inserted in injecting molding die, polyphenylene sulfide (PPS) resin combination that injection moulding contains 20wt% glass fibre, the demoulding and cooling after obtain strong bonded stainless steel together and the stainless steel resin composite body sample S9 of resin combination.
embodiment 10
1, pre-treatment: by thick 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it in polishing machine and grind, clean with absolute ethyl alcohol afterwards, then sandblast, rinse well, dry at 80 ℃ by deionized water, obtain the stainless steel substrates through pre-treatment;
2, adhere to ink layer: above-mentioned stainless steel substrates is put into mould, utilize mould to cover non-injection moulding region, does not cover in 15mm*5mm region, stainless steel substrates one end, mould is put into flush coater, spraying acid-proof ink TER-15 SC1508(Taiwan Taiyo Ink Mfg Co., Ltd.), at 80 ℃, dry, UV solidifies, and forms the ink layer of 15 micron thickness in shaded areas not;
3, oxidation passivation: prepare passivating solution 500ml in beaker, preparation of passivation solution is: 30wt% salpeter solution.Aforementioned stainless steel substrates is put into passivating solution, and passivating solution temperature is 50 ℃, soaks 1 hour, afterwards product is taken out to clean and dries;
The thickness that adopts metallographic microscope to record the oxidation film layer of formation is approximately 1500nm;
4, remove ink layer: above-mentioned stainless steel substrates is put into alkali paint remover sodium hydroxide solution, soak 30min at 80 ℃, fade away and cover ink layer, afterwards product is taken out to washing and dry;
5, electrochemical corrosion: the hydrochloric acid 500ml of preparation 10wt%, above-mentioned gained stainless steel substrates is put into as anode, make to need injection moulding region towards minus plate, under 3V voltage, corrosion 3min, takes out stainless steel substrates, cleans and dries up;
6, neutralization: the sodium carbonate liquor that above-mentioned gained stainless steel substrates is put into 5wt% soaks 10min.Take out stainless steel substrates, clean and dry up, in baking oven, dry 30min for 80 ℃;
Adopt the method identical with embodiment 1 to record the hole that approximately 40 microns of maximums diameter of hole are contained on stainless steel substrate surface;
7, moulding: the stainless steel substrates after drying is inserted in injecting molding die, polyphenylene sulfide (PPS) resin combination that injection moulding contains 20wt% glass fibre, the demoulding and cooling after obtain strong bonded stainless steel together and the stainless steel resin composite body sample S10 of resin combination.
comparative example 1
1, pre-treatment: by thick 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it in polishing machine and grind, clean with absolute ethyl alcohol afterwards, then sandblast, rinse well, dry at 80 ℃ by deionized water, obtain the stainless steel substrates through pre-treatment;
2, surface treatment: aforementioned stainless steel substrates is put into 5wt% sodium carbonate liquor and soak 10min, take out afterwards washing, dry at 80 ℃;
3, moulding: the stainless steel substrates after drying is inserted in injecting molding die, polyphenylene sulfide (PPS) resin combination that injection moulding contains 20wt% glass fibre, the demoulding and cooling after obtain stainless steel resin composite body sample DS1.
comparative example 2
1, pre-treatment: by thick 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it in polishing machine and grind, clean with absolute ethyl alcohol afterwards, then sandblast, rinse well, dry at 80 ℃ by deionized water, obtain the stainless steel substrates through pre-treatment;
2, surface treatment: preparation 500mL chemical corrosion liquid, corrosion liquid formula is: the sulfuric acid solution of 10wt%.Aforementioned stainless steel substrates is put into corrosive liquid, and corrosive liquid temperature is 70 ℃, soaks 15min, takes out product and cleans oven dry;
3, moulding: the stainless steel substrates after drying is inserted in injecting molding die, polyphenylene sulfide (PPS) resin combination that injection moulding contains 20wt% glass fibre, the demoulding and cooling after obtain strong bonded stainless steel together and the stainless steel resin composite body sample DS2 of resin combination.
performance test:
The adhesion of stainless steel and resin: stainless steel resin composite body S1-S10 prepared by embodiment 1-10 and comparative example 1-2 and DS1, DS2 are fixed on universal testing machine and carry out product extension test, in test result, shear fracture power can be considered the size of the adhesion between stainless steel and resin, and test result is as table 1.
Table 1
| ? | Shear fracture power/MPa |
| Embodiment 1 | 19.14 |
| Embodiment 2 | 17.66 |
| Embodiment 3 | 18.43 |
| Embodiment 4 | 16.47 |
| Embodiment 5 | 18.83 |
| Embodiment 6 | 8.31 |
| Embodiment 7 | 14.94 |
| Embodiment 8 | 17.29 |
| Embodiment 9 | 19.06 |
| Embodiment 10 | 18.93 |
| Comparative example 1 | Come off |
| Comparative example 2 | 7.57 |
Stainless steel substrate surface prepared by the present invention has better erosional surface, the pore space structure uniqueness forming on stainless steel substrate surface, hole is that opening is little, inner large structure, hole diameter can reach tens of microns simultaneously, and in substrate surface dense distribution, aperture homogeneous, nearly all thermoplastic resin can enter hole in the process of injection mo(u)lding, resin injection molding is easy, synthetic resin is not had to special requirement yet, the scope of application is wider, and because hole opening is little, inner large structure, make cooling rear resin also be difficult for deviating from hole, hole quantity in unit are of this kind of structure is many simultaneously, strengthen the adhesion of stainless steel and resin, improve resin and stainless adhesion, and method of the present invention is little to metallic matrix size impact, provide cost savings, technique is simple, be more suitable for large-scale production.
Those skilled in the art easily know; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (27)
1. a preparation method for stainless steel resin composite body, is characterized in that, comprises following steps:
S1, carries out electrochemical corrosion by putting into corrosive liquid through the stainless steel substrate of pre-treatment, and described corrosive liquid is that mass concentration is the hydrochloric acid of 2-25wt% and/or the liquor ferri trichloridi that mass concentration is 5-35wt%;
s2, resin combination is injection-moulded in to the stainless steel substrate surface of step S1 gained, after moulding, obtain stainless steel resin composite body.
2. preparation method according to claim 1, is characterized in that, described corrosive liquid is that mass concentration is the hydrochloric acid of 10-20wt% and/or the liquor ferri trichloridi that mass concentration is 15-35wt%.
3. preparation method according to claim 1, is characterized in that, the voltage of described electrochemical corrosion is 2-8V, and the time is 2-20min.
4. preparation method according to claim 3, is characterized in that, the voltage of described electrochemical corrosion is 3-6V, and the time is 3-15min.
5. preparation method according to claim 1, is characterized in that, the temperature of described corrosive liquid is 15-50 ℃.
6. preparation method according to claim 1, is characterized in that, described step S1 forms the hole of 1 ~ 100 micron pore size on stainless steel substrate surface.
7. preparation method according to claim 1, is characterized in that, after described step S1, before step S2, also comprises the stainless steel substrate of step S1 gained is contacted to 1 ~ 30min with alkaline solution.
8. preparation method according to claim 7, it is characterized in that, described alkaline solution is selected from the sodium carbonate liquor that mass percentage concentration is 1 ~ 30wt%, sodium bicarbonate solution or the mass percentage concentration that mass percentage concentration is 1 ~ 30wt% is 1 ~ 30wt% sodium hydroxide solution.
9. preparation method according to claim 1, is characterized in that, also comprises and will not need the surface shaded of binding resin through the stainless steel substrate of pre-treatment before described step S1.
10. preparation method according to claim 9, is characterized in that, described in cover for adhering to ink layer, the thickness of described ink layer is 5-20 micron.
11. preparation methods according to claim 9, is characterized in that, described in cover for preparing oxidation film layer, the thickness of described oxidation film layer is 100nm-3000nm.
12. preparation methods according to claim 11, is characterized in that, the described oxidation film layer of preparing comprises and will need the surface attachment ink of binding resin through the stainless steel substrate of pre-treatment; Again stainless steel substrate is oxidized to passivation; Rear removal ink.
13. preparation methods according to claim 12, it is characterized in that, described oxidation passivation comprises stainless steel substrate contacted with passivating solution, and described passivating solution is selected from one or more in sulfuric acid solution, salpeter solution, potassium bichromate, chromium trioxide and sodium nitrite solution; The temperature that described stainless steel substrate contacts with passivating solution is 10-90 ℃, and the time that described stainless steel substrate contacts with passivating solution is 3-300min.
14. preparation methods according to claim 12, it is characterized in that, described oxidation passivation comprises carries out stainless steel substrate electrochemical passivation in oxidizing acid solution, described oxidizing acid solution is selected from one or more in sulfuric acid solution, salpeter solution, chromium trioxide solution, potassium bichromate solution, hydrogenperoxide steam generator and citric acid solution, the condition of described electrochemical passivation is temperature 40-90 ℃, voltage is 50mV-1000mV, and the time is 2-15min.
15. preparation methods according to claim 1, is characterized in that, pre-treatment comprises polishes to stainless steel substrate surface, then carry out successively oil removing, the first washing, sandblast, the second washing, 50-90 ℃ dry.
16. preparation methods according to claim 1, is characterized in that, described resin combination is thermoplastic resin composition.
17. preparation methods according to claim 16, is characterized in that, described thermoplastic resin is the blend that contains matrix resin and vistanex.
18. preparation methods according to claim 17, is characterized in that, described matrix resin is the mixture of polyphenylene oxide and polyphenylene sulfide, and the fusing point of described vistanex is 65 ℃-105 ℃.
19. preparation methods according to claim 18, is characterized in that, in described matrix resin, the weight ratio of polyphenylene oxide and polyphenylene sulfide is 3:1-1:3.
20. preparation methods according to claim 17, is characterized in that, described matrix resin is the mixture of polyphenylene oxide and polyamide, and the fusing point of described vistanex is 65 ℃-105 ℃.
21. preparation methods according to claim 20, is characterized in that, in described matrix resin, the weight ratio of polyphenylene oxide and polyamide is 3:1-1:3.
22. preparation methods according to claim 17, is characterized in that, described matrix resin is Merlon, and the fusing point of described vistanex is 65 ℃-105 ℃.
23. preparation methods according to claim 17, is characterized in that, take the thermoplastic resin of 100 weight portions as benchmark, wherein the content of matrix resin is 70-95 weight portion, and the content of vistanex is 5-30 weight portion.
24. preparation methods according to claim 17, is characterized in that, described vistanex is grafted polyethylene.
25. preparation methods according to claim 16, is characterized in that, take the thermoplastic resin of 100 weight portions as benchmark, also contain the fluidity improver of 1-5 weight portion in described thermoplastic resin; Described fluidity improver is cyclic polyester.
26. preparation methods according to claim 16, it is characterized in that, in described resin combination, contain filler, described filler comprises fiberfill or inorganic powder filler, described fiberfill is more than one in glass fibre, carbon fiber and Fypro, and inorganic powder filler is more than one in silica, talcum powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, glass and kaolin.
27. 1 kinds of stainless steel resin composite bodies, it is characterized in that, adopt the method as described in claim 1-26 any one to be made, comprise: stainless steel substrate and with the resin bed of its surface conjunction, the surface of described stainless steel substrate is formed with the hole of 1 ~ 100 micron pore size, and the resin combination that forms described resin bed is filled in described hole.
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