CN103895151B - A kind of preparation method of stainless steel resin composite body and the stainless steel resin composite body of preparation thereof - Google Patents
A kind of preparation method of stainless steel resin composite body and the stainless steel resin composite body of preparation thereof Download PDFInfo
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- CN103895151B CN103895151B CN201210582987.3A CN201210582987A CN103895151B CN 103895151 B CN103895151 B CN 103895151B CN 201210582987 A CN201210582987 A CN 201210582987A CN 103895151 B CN103895151 B CN 103895151B
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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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- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides a kind of preparation method of stainless steel resin composite body and the stainless steel resin composite body of preparation thereof, the preparation method of this stainless steel resin composite body, comprise following steps: S1, need the surface attachment ink of binding resin at the stainless steel substrate through pre-treatment, obtain the stainless steel substrate that part surface is attached with ink layer; S2, the stainless steel substrate part surface of step S1 gained being attached with to ink layer carries out oxidative deactivation; The ink layer of S3, removal step S2 gained stainless steel substrate surface attachment; S4, puts into the A containing 2-30wt% by the stainless steel substrate of step S3 gained
-acid and/or salting liquid in carry out electrochemical corrosion, described A is halogen; S5, resin combination is injection-moulded in the stainless steel substrate surface of step S4 gained, stainless steel resin composite body is obtained after shaping, product stainless steel and the adhesion of resin of preparation are strong, and technique is simple and easy to large-scale production, can not cause the corrosion in the non-injection moulding region of stainless steel, simultaneously pollution-free, cost is low.
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, the stronger stainless steel of a kind of adhesion and the preparation method of stainless steel resin composite body that formed and the stainless steel resin composite body of preparation thereof integrated with thermoplastic resin is particularly related to.
Background technology
In the part manufacture field of automobile, household electrical appliance goods, industrial machine etc., require the integral molding techniques of metal and resin, current industry adopts adhesive under normal temperature or heating by combination integrated with synthetic resin for metal.Although adopt said method can prepare metal and integrally moulded complex, but adhesion is poor between the complex metal obtained according to these methods and plastic cement, 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, the seamless combination of stainless steel and resin cannot be realized.Also there is employing inmold injection technique, by the mode of punching press or welding, generate on stainless steel and draw plastic structure, thus with resin-bonded to together with, but adopt in-mould injection, need design to draw plastic structure, and stainless steel body and resin-bonded power very little,, also there is requirement in easy generation gap to the design of product, affects its scope of application, add cost, thus, all the time, people are examining whether more reasonably by the engineering resin of high strength and the method for metal-integral always.
Those skilled in the art is by having researched and proposed nanoprocessing treatment technology, nanoprocessing treatment technology (NMT) is exactly metal combination technology integrated with plastic cement, it passes through metal-surface nano process, allow plastic cement directly ejection formation on the metal surface, make metal and 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 embedding injection conventional at present or zinc-aluminium, magnalium die casting, one can be provided to have price competition, high performance gold moulds integration product.Compared with bonding technique, NMT technology has obvious advantage, such as: the overall weight of minimizing product, excellent strength, working (machining) efficiency are high.NMT technology range of application contains vehicle, information technoloy equipment and 3C Product, and product can be allowed towards more frivolous, more miniature future development.
Have the mode by chemical etching disclosed in existing, erode away nano level ultra tiny concaveconvex shape at stainless steel surfaces, and with specific resin carry out injection moulding by resin and corrupt split to together with.But because chemical corrosion liquid has severe corrosive to stainless steel substrate itself, the corrosion in the non-injection moulding region of stainless steel product can be caused, especially to the corrosion of appearance, increase polishing or CNC is needed to carry out subsequent treatment to non-corrosive region, complex process, thus limit its scope of application, simultaneously the stainless steel of stainless steel resin composite body prepared of this kind of forms of corrosion and the adhesion of resin also do not reach ideal effect.
Summary of the invention
The present invention is in order to the weak technical problem of the adhesion of stainless steel in the stainless steel resin composite body that solves prior art and prepare and resin.There is provided the adhesion of a kind of stainless steel and resin strong, and technique is simple and easy to large-scale production, can not cause the corrosion in the non-injection moulding region of stainless steel, the preparation method of free of contamination stainless steel resin composite body and the stainless steel resin composite body of 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, needs the surface attachment ink of binding resin at the stainless steel substrate through pre-treatment, obtain the stainless steel substrate that part surface is attached with ink layer;
S2, the stainless steel substrate part surface of step S1 gained being attached with to ink layer carries out oxidative deactivation;
The ink layer of S3, removal step S2 gained stainless steel substrate surface attachment;
S4, puts into the A containing 2-30wt% by the stainless steel substrate of step S3 gained
-acid and/or salting liquid in carry out electrochemical corrosion, described A is halogen;
S5, is injection-moulded in the stainless steel substrate surface of step S4 gained, obtains stainless steel resin composite body after shaping by resin combination.
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 the resin bed with its surface conjunction, the surface of described stainless steel substrate comprises injection moulding region and non-injection moulding region, described non-injection moulding region is formed with oxidation film layer, described injection moulding region is formed with erosional surface, and described resin bed combines with described erosional surface.
The present invention surprisingly finds to adopt method of the present invention, the surface attachment ink layer of binding resin is first needed at stainless steel substrate, injection moulding region is needed to cover to stainless steel substrate surface, through oxidative deactivation, passivation is carried out to the uncovered non-injection moulding region of stainless steel surfaces again, this region surface is made to generate layer oxide film layer, after removing ink layer, electrochemical corrosion is carried out to stainless steel substrate, find that the corrosion resistance through Passivation Treatment region is better, injection moulding region is needed more easily to corrode when electrochemical corrosion, and resistance through Passivation Treatment region is higher, non-passivation need injection moulding zone current density larger, also make to need injection moulding region more easily to corrode, thus can obtain and need injection moulding zonal corrosion stronger, but not injection moulding region almost free from corrosion product, the outward appearance in the non-injection moulding region of stainless steel product can not be affected, do not need or only need carry out little subsequent treatment to product, little to metallic matrix size impact, and raw material is simple and easy to get, without particular/special requirement, preparation process heat release is little, provide cost savings, technique is simple, be more suitable for large-scale production.Better erosional surface can be formed on stainless steel substrate surface by method of the present invention simultaneously, with resin itself, there is good associativity, improve resin and stainless adhesion and resin injection molding easy, also do not specially require synthetic resin, the scope of application is wider.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, 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, be not intended to limit the present invention.
The invention provides a kind of preparation method of stainless steel resin composite body, comprise following steps:
S1, needs the surface attachment ink of binding resin at the stainless steel substrate through pre-treatment, obtain the stainless steel substrate that part surface is attached with ink layer.Method the present invention of attachment ink is not particularly limited, such as coating can be adopted, the modes such as spraying, such as the stainless steel substrate through pre-treatment is put into and cover tool, ink is sprayed needing the injection moulding region that needs of binding resin, equipment and the operating technology of spraying are known to the skilled person, generally also baking and curing is needed after spraying, ink layer is formed at the part surface of stainless steel substrate, by needing the stainless steel surfaces of binding resin formation ink layer to cover needing injection moulding region, make follow-up oxidative deactivation not to needing injection moulding region to impact, only form oxidation film layer in the non-injection moulding region of non-attaching oil layer of ink.Generally according to the condition of oxidative deactivation, can select ink, preferred ink is acid-proof ink, such as, can select epoxy resin, organic siliconresin etc., and can be common ink, cost be low.The thickness of the ink layer be preferably formed is 5-20 micron.
S2, the stainless steel substrate part surface of step S1 gained being attached with to ink layer carries out oxidative deactivation.
Oxidative deactivation preferably can comprise the stainless steel substrate part surface of step S1 gained being attached with ink layer and contact with passivating solution, mode the present invention of contact does not limit, such as can the stainless steel substrate after spraying ink is whole be immersed in passivating solution, can under the condition of heating, also can under the condition do not heated, in better situation, the temperature that preferred stainless steel substrate contacts with passivating solution is 10-90 DEG C, more preferably 50-80 DEG C, the time that stainless steel substrate contacts with passivating solution is 3-300min, more preferably 30-180min, the temperature that such as can arrange passivating solution is 50-80 DEG C, stainless steel substrate is immersed in passivating solution and process 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.
Oxidative deactivation of the present invention preferably can also comprise the stainless steel substrate part surface of step S1 gained being attached with ink layer and carry out 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 electrochemical passivation is temperature 40-90 DEG C, voltage is 50mV-1000mV, and the time is 2-15min.Be specially and step S1 gained part is attached with the stainless steel substrate of ink layer as anode, putting into temperature is that the oxidizing acid solution of 40-90 DEG C is energized oxidation 2-15min under the voltage of 50mV-1000mV.
Oxidation film layer is formed on the surface of stainless steel substrate non-attaching oil layer of ink and non-injection moulding region by oxidative deactivation, preferably, oxidative deactivation forms the oxidation film layer of 100-3000nm in the surface of the non-attaching oil layer of ink of stainless steel substrate, in better situation, the thick of oxidation film layer of formation is 1000-2500nm.
The ink layer of the stainless steel substrate surface attachment after S3, removal step S2 oxidative deactivation, namely removal step S1 covers ink layer what need the stainless steel substrate of binding resin to need injection moulding region to be formed.The method the present invention removing ink layer does not limit, and such as, when ink is acid resistance ink, stainless steel substrate can be immersed in alkali paint remover to fade away and cover ink.
S4, puts into the A containing 2-30wt% by the stainless steel substrate of step S3 gained
-acid and/or salting liquid in carry out electrochemical corrosion, surface treatment is carried out to stainless steel substrate surface, forms unique surface texture.Wherein, A is halogen, more preferably chlorine, i.e. preferred A
-for chlorion, the hole of unique texture can be formed on stainless steel substrate surface, pore space structure is that opening is little, inner large structure, hole diameter can reach some tens of pm simultaneously, and in substrate surface dense distribution, therefore nearly all thermoplastic resin can, hole is entered in the process of injection mo(u)lding, and due to hole opening little, inner large structure, makes to cool rear resin and not easily deviates from hole, and this kind of hole quantity in unit are is many, the stainless steel resin composite body that adhesion is more excellent therefore can be obtained.Wherein, A
-acid and/or salting liquid can be hydrochloric acid and/or liquor ferri trichloridi, the preferred A of the present invention
-acid and/or the hydrochloric acid of salting liquid to be mass percentage concentration be 5-20wt%, the more preferably hydrochloric acid of 10-20wt%, preferably, electrochemical corrosion to comprise the stainless steel substrate of step S3 gained as anode, is immersed in the A containing 2-30wt%
-acid and/or salting liquid in, make to need injection moulding region towards minus plate, under 2-8V voltage, corrosion 3-20min, more preferably 5-20min, strong to needing injection moulding zonal corrosion, non-injection moulding region almost without affecting, further by A
-acid and/or salting liquid in the electrochemical corrosion hole that needing injection moulding region to form 1 ~ 100 unique micron pore size, pore structure is excellent, the binding ability of resin bed and stainless steel substrate can be made better, there is better tensile strength, the integration of stainless steel double zoarium be combined better.The temperature of general electrochemical corrosion is 15-50 DEG C.Electrochemical corrosion can be once, also can be repeated multiple times.
Also comprise before step S5 after the further preferred steps S4 of the present invention and the stainless steel substrate of step S4 gained is contacted 1 ~ 30min with alkaline solution, neutralize, alkaline solution can be selected from one or more in sodium carbonate liquor, sodium bicarbonate solution or sodium hydroxide solution.Preferably, the sodium bicarbonate solution that alkaline solution is selected from sodium carbonate liquor that mass percentage concentration is 1 ~ 30wt%, mass percentage concentration is 1 ~ 30wt% or mass percentage concentration are 1 ~ 30wt% sodium hydroxide solution, general cleaning, drying after neutralization.
S5, is injection-moulded in the stainless steel substrate surface of step S4 gained, obtains stainless steel resin composite body after shaping by resin combination.Be specifically as follows and dried stainless steel substrate is proceeded in mould, integrated treatment is carried out with obtained resin combination, stainless steel double provided by the invention can be obtained fit after shaping, in the present invention, the molding mode of metallo-plastic integration can be made all to can be used for the present invention, and the condition of injection moulding can be nozzle temperature 200-350 DEG C, mold temperature 50-200 DEG C, the amount of the resin combination of general injection is 0.1-1000g, and the complex surfaces of preparation has the thick resin bed of 0.1-10mm.
Pre-treatment is the pretreatment procedure carried out stainless steel surfaces that those skilled in the art commonly use, generally make its surfacing, clean, generally comprise and carry out mechanical grinding or grinding removal surface significantly foreign matter, then degreasing, cleaning are carried out to the processing wet goods that metal surface adheres to.Preferably, pre-treatment comprises polishes to stainless steel substrate surface, such as, can be: first adopt 100-400 object sand paper or put it in polishing machine stainless steel substrate surface finish.Then oil removing, the first washing, sandblasting, the second washing, drying and other steps is carried out successively, in ultrasonic wave, this stainless steel is cleaned with the various solvents that those skilled in the art commonly use, scavenging period 0.5-2h, remove the greasy dirt of stainless steel surfaces, described solvent can be ethanol or acetone.In the present invention, preferably carry out sandblasting with absolute ethyl alcohol again by after stainless steel oil removing after washing wiped clean, the roughness of stainless steel surfaces can be increased, cleaner with deionized water rinsing, finally dry at 50-90 DEG C.
Need stainless steel the present invention of pre-treatment to be not particularly limited, various commercially available stainless steel can be used; Stainless steel described in the present invention be those skilled in the art commonly use various shapes, structure stainless steel, the present invention is not particularly limited.Stainless various shape, structure, complete by machining.
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 combination that can be combined with stainless steel, preferred resin composition is thermoplastic resin.Preferred thermoplastic resin is the blend containing matrix resin and vistanex.Preferred 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, it is the vistanex of 65 DEG C-105 DEG C with the use of fusing point simultaneously, injection moulding under specific mould temperature is not needed when shaping, moulding process simplifies, can ensure that the metal-resin composite obtained has better mechanical strength and surface treatment characteristics simultaneously, thus solve the incrustation problem of working of plastics, meet the diversified demand of client.By in adopted noncrystalline matrix resin, with the use of the vistanex that fusing point is 65 DEG C-105 DEG C, the ability that resin flows into metal-surface nano level micropore can be increased, thus ensure that the metal that formed and plastics have good adhesive force, mechanical strength.Under preferable case, with the thermoplastic resin of 100 weight portions for 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, in thermoplastic resin, adopt fluidity improver, can also improve the fluid ability of resin, improves further metal and the adhesive force of resin and the injection moulding performance of resin.Under preferable case, with the thermoplastic resin of 100 weight portions for benchmark, the fluidity improver also containing 1-5 weight portion in described thermoplastic resin.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, is 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, is more preferably 2:1-1:1.Or preferably matrix resin is Merlon (PC), and it can be selected from various Linear polycarbonate and/or Linear polycarbonate, and the present invention does not have particular provisions.
In the present invention, the fusing point of the vistanex adopted is 65 DEG C-105 DEG C.Under preferable case, described vistanex can adopt grafted polyethylene.More preferably, in situation, described vistanex can adopt fusing point to be the grafted polyethylene of 100 DEG C or 105 DEG C.
Resin combination of the present invention can also containing other property-modifying additives etc., and the present invention is not particularly limited, and can arrange as required, such as, can also contain filler in resin combination.Described filler is the various fillers that those skilled in the art commonly use, such as, can be various fiberfill or powdery filler.Described fiberfill can be selected from one or more in glass fibre, carbon fiber and aramid 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, all there is the linear expansion coefficient close with stainless steel substrate, in the present invention, with the matrix resin of 100 weight portions for benchmark for making the horizontal, longitudinal of plastics composite, 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, prepares resin combination.The method that the preparation method of described resin combination adopts those skilled in the art to commonly use physical blending obtains, 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, filler, fluidity improver can also be added in described matrix resin, mix, obtained resin combination, thus make the horizontal, longitudinal of resin combination all have the linear expansion coefficient close with stainless steel substrate.
Preparation method of the present invention is simple, the technique of more existing employing adhesive simplifies production procedure, shorten the production time, and more existing nano surface hole injection moulding need adopt the two-step method of injection moulding hot pressing injection moulding more also to significantly reduce process complexity, direct injection moulding is only needed to realize, simultaneously good by adhesion between the resin bed of the stainless steel resin composite body obtained by preparation method of the present invention and stainless steel substrate, there is preferably tensile shear strength.
Invention also provides stainless steel resin composite body prepared by above-mentioned preparation method, stainless steel substrate and the resin bed with its surface conjunction, the surface of described stainless steel substrate comprises injection moulding region and non-injection moulding region, described non-injection moulding region is formed with oxidation film layer, described injection moulding region is formed with erosional surface, described resin bed combines with described erosional surface, and the shear fracture power of stainless steel substrate and resin bed can up to 5-30MPa.Wherein, resin combination be known to the skilled person various can with the resin combination of stainless steel compound.
The stainless steel resin composite body that the present invention obtains can directly use, and also can carry out some follow-up post processings as required, 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 prepares stainless steel resin composite body;
1, pre-treatment: by thick for 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, rear absolute ethyl alcohol is cleaned, then sandblasting, clean with deionized water rinsing, dry at 80 DEG C, obtain the stainless steel substrates through pre-treatment;
2, attaching oil layer of ink: above-mentioned stainless steel substrates is put into mould, mould is utilized to cover non-injection moulding region, 5mm*80mm region, stainless steel substrates one end is not covered, mould is put into flush coater, spraying acid-proof ink 5680 photosensitive-ink (Jia Yuan Chemical Co., Ltd. of Shenzhen ten thousand), dry at 80 DEG C, UV solidifies, and forms the ink layer of 15 micron thickness in non-shaded areas;
3, oxidative deactivation: 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 DEG C, soaks 1 hour, is taken out to clean by product afterwards and dries;
The thickness adopting 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, soaks 30min at 80 DEG C, fade away and cover ink layer, afterwards product is taken out washing and dry;
5, electrochemical corrosion: the hydrochloric acid 500ml of preparation 10wt%, puts into as anode using above-mentioned gained stainless steel substrates, makes to need injection moulding region towards minus plate, and under 3V voltage, corrosion 3min, takes out stainless steel substrates, cleans and dries up;
6, neutralize: the sodium carbonate liquor that above-mentioned gained stainless steel substrates puts into 5wt% is soaked 10min.Take out stainless steel substrates, clean and dry up, dry 30min for 80 DEG C in an oven;
7, shaping: the stainless steel substrates after drying is inserted in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) resin combination of 20wt% glass fibre, and the demoulding also obtains strong bonded stainless steel together and the stainless steel resin composite body sample S1 of resin combination after cooling.
embodiment 2
The method identical with embodiment 1 is adopted to prepare stainless steel resin composite body sample S2.Unlike step 3, oxidative deactivation: preparation oxidizing acid solution 500ml, oxidizing acid solution formula is: 450g/L sulfuric acid and 230g/L chromium trioxide mixed solution, above-mentioned gained stainless steel substrates is put into oxidizing acid solution as anode, under 600mV voltage, oxidation 10min, the temperature of oxidizing acid solution is 60 DEG C, is taken out to clean by product afterwards to dry up.The thickness adopting the method identical with embodiment 1 to record the oxidation film layer of formation is approximately 2000nm.
embodiment 3
The method identical with embodiment 1 is adopted to prepare stainless steel resin composite body sample S3.Unlike step 5, the mass percentage concentration of hydrochloric acid is 5wt%.
embodiment 4
The method identical with embodiment 1 is adopted to prepare stainless steel resin composite body sample S4.Unlike step 5, the mass percentage concentration of hydrochloric acid is 20wt%.
embodiment 5
The method identical with embodiment 1 is adopted to prepare stainless steel resin composite body sample S5.Unlike step 5, electrochemical corrosion: the ferric trichloride 500ml of preparation 10wt%, puts into as anode using above-mentioned gained stainless steel substrates, makes to need injection moulding region towards minus plate, and under 3V voltage, corrosion 3min, takes out stainless steel substrates, cleans and dries up.
embodiment 6
The method identical with embodiment 1 is adopted to prepare stainless steel resin composite body sample S6.Unlike step 5, electrochemical corrosion: the mixed solution 500ml of the preparation ferric trichloride of 5wt% and the hydrochloric acid of 10wt%, puts into as anode using above-mentioned gained stainless steel substrates, make to need injection moulding region towards minus plate, under 3V voltage, corrosion 3min, take out stainless steel substrates, clean and dry up.
comparative example 1
1, pre-treatment: by thick for 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, rear absolute ethyl alcohol is cleaned, then sandblasting, clean with deionized water rinsing, dry at 80 DEG C, 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 DEG C, soaks 15min, takes out product and cleans oven dry;
3, shaping: the stainless steel substrates after drying is inserted in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) resin combination of 20wt% glass fibre, and the demoulding also obtains strong bonded stainless steel together and the stainless steel resin composite body sample DS1 of resin combination after cooling.
comparative example 2
1, pre-treatment: by thick for 1mm 304 corrosion resistant plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, rear absolute ethyl alcohol is cleaned, then sandblasting, clean with deionized water rinsing, dry at 80 DEG C, obtain the stainless steel substrates through pre-treatment;
2, shaping: inserted in injecting molding die by the stainless steel substrates after drying, injection moulding contains polyphenylene sulfide (PPS) resin combination of 20wt% glass fibre, the demoulding also obtains stainless steel resin composite body sample DS2 after cooling.
performance test:
The adhesion of stainless steel and resin: stainless steel resin composite body S1-S6 and DS1, the DS2 that are prepared by embodiment 1-6 and comparative example 1-2 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.
Non-injection moulding region is apparent: stainless steel resin composite body S1-S6 and DS1, the DS2 that are prepared by embodiment 1-6 and comparative example 1-2 observe under standard light is according to D65 condition, and get the untreated stainless steel substrate S0 of a slice and contrast, eyes are 30 centimetres to sample distance, observe sample surfaces contrast S0 with or without obvious corrosion, the defect that record occurs, test result is as table 1.
Table 1
| Shear fracture power/MPa | Non-injection moulding region is apparent | |
| Embodiment 1 | 15.31 | Without obviously corrosion |
| Embodiment 2 | 15.73 | Without obviously corrosion |
| Embodiment 3 | 8.45 | Without obviously corrosion |
| Embodiment 4 | 17.20 | Slight erosion, can remove in polishing |
| Embodiment 5 | 7.96 | Without obviously corrosion |
| Embodiment 6 | 8.92 | Without obviously corrosion |
| Comparative example 1 | 8.41 | Have obvious corrosion, and the simple and mechanical method such as polishing thoroughly cannot be removed |
| Comparative example 2 | Come off | - |
Product stainless steel prepared by the present invention and the adhesion of resin are strong, and technique is simple and easy to large-scale production, can not cause the obvious corrosion in stainless steel non-injection moulding region, without the need to carrying out subsequent treatment, also little to stainless steel base size impact, on stainless outward appearance substantially without impact, cost is low.
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 amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (25)
1. a preparation method for stainless steel resin composite body, is characterized in that, comprises following steps:
S1, needs the surface attachment ink of binding resin at the stainless steel substrate through pre-treatment, obtain the stainless steel substrate that part surface is attached with ink layer;
S2, the stainless steel substrate part surface of step S1 gained being attached with to ink layer carries out oxidative deactivation;
The ink layer of S3, removal step S2 gained stainless steel substrate surface attachment;
S4, puts into the A containing 2-30wt% by the stainless steel substrate of step S3 gained
-acid and/or salting liquid in carry out electrochemical corrosion, described A is halogen;
S5, is injection-moulded in the stainless steel substrate surface of step S4 gained, obtains stainless steel resin composite body after shaping by resin combination.
2. preparation method according to claim 1, it is characterized in that, described oxidative deactivation comprises the stainless steel substrate part surface of step S1 gained being attached with ink layer and contacts with passivating solution, and described passivating solution is selected from one or more in sulfuric acid solution, salpeter solution, potassium bichromate solution, chromium trioxide solution and sodium nitrite solution.
3. preparation method according to claim 2, is characterized in that, the temperature that stainless steel substrate contacts with passivating solution is 10-90 DEG C, and the time that stainless steel substrate contacts with passivating solution is 3-300min.
4. preparation method according to claim 1, it is characterized in that, described oxidative deactivation comprises the stainless steel substrate part surface of step S1 gained being attached with ink layer and carry out 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 DEG C, voltage is 50mV-1000mV, and the time is 2-15min.
5. preparation method according to claim 1, is characterized in that, described oxidative deactivation forms the oxidation film layer of 100nm-3000nm in the surface of the non-attaching oil layer of ink of stainless steel substrate.
6. preparation method according to claim 1, is characterized in that, described A
-for Cl
-.
7. preparation method according to claim 6, is characterized in that, described A
-acid and/or the hydrochloric acid of salting liquid to be mass percentage concentration be 5-20wt%.
8. preparation method according to claim 7, is characterized in that, described A
-acid and/or salting liquid be the hydrochloric acid of 10-20wt%.
9. preparation method according to claim 1, is characterized in that, described electrochemical corrosion comprises using the stainless steel substrate of step S3 gained as anode, under 2-8V voltage, and corrosion 3-20min.
10. preparation method according to claim 1, is characterized in that, described ink is acid-proof ink, and the thickness of described ink layer is 5-20 micron.
11. preparation methods according to claim 1, it is characterized in that, also comprise before step S5 after described step S4 and the stainless steel substrate of step S4 gained is contacted 1 ~ 30min with alkaline solution, described alkaline solution is selected from one or more in sodium carbonate liquor, sodium bicarbonate solution and sodium hydroxide solution.
12. preparation methods according to claim 11, it is characterized in that, also comprise before step S5 after described step S4 and the stainless steel substrate of step S4 gained is contacted 1 ~ 30min with alkaline solution, the sodium carbonate liquor of described alkaline solution to be mass percentage concentration be 1 ~ 30wt%, mass percentage concentration are the sodium bicarbonate solution of 1 ~ 30wt% or mass percentage concentration is 1 ~ 30wt% sodium hydroxide solution.
13. preparation methods according to claim 1, is characterized in that, described pre-treatment comprises polishes to stainless steel substrate surface, then carry out oil removing, the first washing, sandblasting, the second washing, 50-90 DEG C drying successively.
14. preparation methods according to claim 1, is characterized in that, described resin combination is thermoplastic resin composition.
15. preparation methods according to claim 14, is characterized in that, described thermoplastic resin is the blend containing matrix resin and vistanex.
16. preparation methods according to claim 15, 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 DEG C-105 DEG C.
17. preparation methods according to claim 16, is characterized in that, in described matrix resin, the weight ratio of polyphenylene oxide and polyphenylene sulfide is 3:1-1:3.
18. preparation methods according to claim 15, is characterized in that, described matrix resin is the mixture of polyphenylene oxide and polyamide, and the fusing point of described vistanex is 65 DEG C-105 DEG C.
19. preparation methods according to claim 18, is characterized in that, in described matrix resin, the weight ratio of polyphenylene oxide and polyamide is 3:1-1:3.
20. preparation methods according to claim 15, is characterized in that, described matrix resin is Merlon, and the fusing point of described vistanex is 65 DEG C-105 DEG C.
21. preparation methods according to claim 15, is characterized in that, with the thermoplastic resin of 100 weight portions for benchmark, wherein the content of matrix resin is 70-95 weight portion, and the content of vistanex is 5-30 weight portion.
22. preparation methods according to claim 15, is characterized in that, described vistanex is grafted polyethylene.
23. preparation methods according to claim 14, is characterized in that, with the thermoplastic resin of 100 weight portions for benchmark, and the fluidity improver also containing 1-5 weight portion in described thermoplastic resin; Described fluidity improver is cyclic polyester.
24. preparation methods according to claim 14, it is characterized in that, containing filler in described resin combination, described filler comprises fiberfill or inorganic powder filler, described fiberfill is more than one in glass fibre, carbon fiber and Fypro, and inorganic powdered filler is more than one in silica, talcum powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, glass and kaolin.
25. 1 kinds of stainless steel resin composite bodies, it is characterized in that, the method as described in claim 1-24 any one is adopted to be made, comprise: stainless steel substrate and the resin bed with its surface conjunction, the surface of described stainless steel substrate comprises injection moulding region and non-injection moulding region, described non-injection moulding region is formed with oxidation film layer, and described injection moulding region is formed with erosional surface, and described resin bed combines with described erosional surface.
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| CN105729717B (en) * | 2014-12-09 | 2018-05-29 | 深圳富泰宏精密工业有限公司 | The preparation method of the complex of metal and resin and complex obtained by this method |
| CN104943059B (en) * | 2015-05-18 | 2017-03-15 | 广东兴锐电子科技股份有限公司 | A kind of complex manufacture method of aluminium alloy and plastics |
| CN106476209B (en) * | 2016-10-25 | 2019-03-26 | 深圳市宝元金实业有限公司 | A method of nano aperture is formed in magnetism-free stainless steel substrate surface |
| CN106835222B (en) * | 2016-12-20 | 2019-05-17 | 维沃移动通信有限公司 | A kind of processing method of USB device, USB device and mobile terminal |
| CN106917061B (en) * | 2017-01-16 | 2019-06-04 | 歌尔股份有限公司 | The engaging member and its processing method of stainless steel and plastics |
| CN106917129B (en) * | 2017-01-16 | 2019-01-04 | 歌尔股份有限公司 | The engaging member and its processing method of stainless steel and plastics |
| CN107901329A (en) * | 2017-10-10 | 2018-04-13 | 横店集团东磁股份有限公司 | A kind of metal insert integrated injection forming magnet ring and preparation method thereof |
| CN109318432B (en) * | 2018-09-11 | 2020-11-20 | 吉林大学 | Composite processing method for metal-plastic composite interface microstructure |
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| CN101519782A (en) * | 2009-04-02 | 2009-09-02 | 北京化工大学 | Corrosion resistant hydrotalcite/polyelectrolyte composite film and preparation method thereof |
| CN102602079A (en) * | 2012-03-12 | 2012-07-25 | 海门市森达装饰材料有限公司 | Anti-stain and anti-fingerprint stainless steel plate and preparation method thereof |
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| CN101519782A (en) * | 2009-04-02 | 2009-09-02 | 北京化工大学 | Corrosion resistant hydrotalcite/polyelectrolyte composite film and preparation method thereof |
| CN102602079A (en) * | 2012-03-12 | 2012-07-25 | 海门市森达装饰材料有限公司 | Anti-stain and anti-fingerprint stainless steel plate and preparation method thereof |
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