CN103451704B - The preparation method of a kind of metal-resin composite and the metal-resin composite of preparation thereof - Google Patents
The preparation method of a kind of metal-resin composite and the metal-resin composite of preparation thereof Download PDFInfo
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Abstract
The invention provides the metal-resin composite of the preparation method of a kind of metal-resin composite and preparation thereof.The preparation method of metal-resin composite, comprises the steps of S1, anodic oxidation: by anodic oxidation, the metal base through pre-treatment is obtained the metal base that anode oxidation membrane is contained on surface, and described metal base is aluminum alloy base material or aluminium base；S2, phosphoric acid processes: the metal base that step S1 gained contains anode oxidation membrane immerses process in phosphoric acid solution, obtains surface treated metal base；S3, injection moulding: resin combination is injection-moulded in surface treated metallic substrate surface, obtain metal-resin composite after molding, metal is strong with the adhesion of resin, and technique simply easily large-scale production, pollution-free.
Description
Technical field
The present invention relates to the metal-resin composite of the preparation method of a kind of metal-resin composite and preparation thereof.
Background technology
In the part manufacture field of automobile, household electrical appliance goods, industrial machine etc., it is desirable to the integral molding techniques of metal and resin, current industry adopts binding agent by combination integrated with synthetic resin for metal under room temperature or heating.Although adopting said method can prepare metal and integrally moulded complex, but it is poor according to adhesion between complex metal and plastic cement that these methods obtain, and adhesive acid-fast alkali-proof poor performance, complex cannot be carried out the surface treatments such as follow-up anodic oxidation.Thus, all the time, people are examining whether to have more reasonably by method that the engineering resin of high intensity is integrated with the alloy of aluminium alloy etc always.
Those skilled in the art is by having researched and proposed nanometer processing treatment technology, nanometer processing treatment technology (NMT) is exactly metal combination technology integrated with plastic cement, it is by processing metal-surface nanoization, allow plastic cement directly ejection formation on the metal surface, make metal and the plastic cement can integrated molding.For effective combination of metal with 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, it is provided that one has price competition, high performance gold moulds integration product.Compared with bonding technique, NMT technology has obvious advantage, for instance: the minimizing overall weight of product, excellent strength, working (machining) efficiency are high.NMT technology range of application contains vehicle, information technoloy equipment and 3C Product, it is possible to allow product develop towards more frivolous, more miniature direction.
nullExisting have the integrated molding technology disclosing aluminium alloy with resin combination，Adopt amine substance，Such as: carbamate、One hydrazine hydrate、Aluminium alloy is carried out surface treatment and obtains nano level micropore by the aqueous solution of ethylenediamine etc.，Erode away nano level hole，And amine groups is retained in aluminium alloy nano aperture，Last injection moulding is by the reaction of amine groups with injected plastics material，Resin and aluminum alloy junction are combined together，Thus obtaining the plastic-aluminum integration product having certain tensile shear strength，And adopt the technology that this type of amine substance corrodes，The hole that aluminum alloy surface is formed is too little，Resin is difficult to direct injection moulding and enters nano level hole，Reduce the bond strength of aluminium alloy and resin，I.e. stretch-proof poor-performing，The combination of resin and aluminium alloy simultaneously relies primarily on amine groups，The kind of the resin used is extremely limited，The resin that this technology can adopt at present only has PPS(polyphenylene sulfide)、PA(polyamide)、PPA(polyphthalamide resin)、PBT(polybutylene terephthalate (PBT)) etc. four resinoids，Practical ranges is also narrow，And the amine substance adopted is poisonous、There is volatile material，It is unfavorable for safety in production、Environmental-protecting performance is poor.
Also have and directly corroded in aluminum alloy surface by the acidic etching liquid containing inorganic halogen compounds, then injection moulding obtains plastic-aluminum integration product, and adopt the technology of this type of etching solution corrosion aluminum alloy surface, there is the etchant concentration low time long, etchant concentration high exothermic heat of reaction is big, the bad control of temperature, and along with the rising corrosion of temperature can be more violent, form vicious cycle, easily cause the quick volatilization of corrosive liquid, the situation such as corrosive liquid splashing and aluminum alloy surface serious discoloration during vigorous reaction, it is unfavorable for large-scale production, and adopt this method, adhesion between metal and resin is poor.
The existing aluminium oxide rete also having the cave by anodic oxidation preparation with diameter 0.05-0.08 micron in aluminum alloy surface, plastic-aluminum integration product is obtained again with resin-bonded, but the hole that the aluminum alloy surface that the method obtains is formed is too little and resin is difficult to direct injection moulding and enters nano level hole, reducing the bond strength of aluminium alloy and resin, namely tensile property is poor.
Summary of the invention
The present invention is to solve the technical problem that in metal-resin composite prepared by prior art, metal is weak with the adhesion of resin.There is provided a kind of metal strong with the adhesion of resin, and technique simply easily large-scale production, the preparation method of free of contamination metal-resin composite and the metal-resin composite of preparation thereof.
The preparation method that first purpose of the present invention is to provide a kind of metal-resin composite, comprises the steps of
S1, anodic oxidation: by anodic oxidation, the metal base through pre-treatment is obtained the metal base that anode oxidation membrane is contained on surface, and described metal base is aluminum alloy base material or aluminium base；
S2, phosphoric acid processes: the metal base that step S1 gained contains anode oxidation membrane immerses process in phosphoric acid solution, obtains surface treated metal base；
S3, injection moulding: resin combination is injection-moulded in surface treated metallic substrate surface, obtains metal-resin composite after molding.
Second purpose of the present invention is to provide the metal-resin composite that above-mentioned preparation method is made, including: metal base and the resin bed with its surface combination.
Present inventors have unexpectedly found that the three-layer stereo pore space structure that can be formed uniqueness by the technology of the present invention in metal surface, resin directly injection moulding to hole, can obtain the product that adhesion is good, does not need to increase extra group and produces exothermic reaction, to resin also without particular/special requirement, the scope of application is wider；nullThe metal surface of the present invention can form the hole of up-small and down-big unique texture，Speculate probably due to the anodic oxidation membrane micropore that phosphoric acid solution can pass through the weaker zone of anode oxidation membrane enters internal，The barrier layer of corrosion bottom，Enter back into metal body surface，Corroding metal body surface，Owing to phosphoric acid has the character of homogeneous corrosion，Bigger hole or concave pit is easily gone out in metal body surface corrosion，And the barrier layer character of bottom is similar to natural oxide film，Acid simultaneously is high to the corrosion rate of aluminum，The corrosion rate of oxide-film is low，Namely the corrosion rate of metal body is fast，The corrosion of antianode oxidation film layer is slow，Thus forming big etch pit on metal body surface near anode oxidation membrane place，Anode oxide film also part blocks the acid etching liquid corrosion to metal body simultaneously，Namely corrosion rate is reduced，Reduce erosional surface，The vigorous reaction existed when avoiding acid etching liquid to metal body directly etching，Heat release is violent，Etching liquid quick heating，And the time is more long，Corrosive liquid temperature is more high，React also more violent，As many flake products corrode simultaneously，React more violent，The product corrosion put into after in the identical time is more serious，It is unfavorable for controlling the appearance of the problems such as product quality，Technical scheme，Metal appearance is without significant change，Exothermic heat of reaction is few，Etching liquid heats up slow，It is more suitable for large-scale production，The etching liquid consumed is also less，And the corrosion of equipment is little.Metal surface forms aluminium oxide rete simultaneously, itself there is the micropore of excellent performance, the structure in hole is unique, with resin itself, there is good associativity, aluminium oxide rete is carried out acid etching liquid corrosion simultaneously, acid etching liquid is little on weaker zone impact, the metal body surface impact contacted with oxidation film layer is big, thus forming the hole that aperture is bigger under aluminium oxide rete, pore structure is unique, improve the adhesion of resin and metal, the metal of the present invention can with resin strong bonded, intensity is higher, and the impact of metallic matrix size is little, heat release is little, temperature stabilization in processing procedure, on metal appearance substantially without impact, to synthetic resin also without special requirement, the scope of application is wider, and do not have harmful gas and evaporate, environmentally safe, it is more suitable for large-scale production.
Accompanying drawing explanation
System temperature-time variation diagram when Fig. 1 is the embodiment of the present invention 7 and the immersion of comparative example 3 etching liquid.
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 is only in order to explain the present invention, is not intended to limit the present invention.
The preparation method that the invention provides a kind of metal-resin composite, comprises the steps of
S1, anodic oxidation: by anodic oxidation, the metal base through pre-treatment is obtained the metal base that anode oxidation membrane is contained on surface, and described metal base is aluminum alloy base material or aluminium base；The anodizing technology that anodic oxidation is known to the skilled person, the present invention preferably can include putting in 10wt%-30wt% concentration sulphuric acid or phosphoric acid solution using the metal base through pre-treatment as anode, temperature 10-30 DEG C under 5V～35V voltage electrolysis 2-15min obtain surface and contain the metal base of anode oxidation membrane thick for 1-20um, anodised equipment adopts known anodic oxidation equipment, for instance anodizing tank.The thickness of the anode oxidation membrane of preferred anodes oxidation preparation is 1-10um.
S2, phosphoric acid processes: the metal base that step S1 gained contains anode oxidation membrane immerses process in phosphoric acid solution, obtains surface treated metal base；Namely the main improvements of the present invention are in that to adopt phosphoric acid that the metal base with anode oxidation membrane is corroded, metal body surface under anode oxidation membrane forms big etch pit, by this corrosion pore-creating again, in follow-up forming process, resin combination enters in metal body surface metal etch pit in injection moulding process, thus forming good combination with metal after forming resin bed.
In preferably phosphoric acid solution of the present invention, the mass percentage concentration of phosphoric acid is 3wt%～40wt%, more preferably 5wt%～30wt%, further it is preferably 5wt%～20wt%.Metal erosion hole can be made to be uniformly distributed on metal body surface, and uniform pore diameter, it is possible to make the binding ability of resin bed and metal base more preferably, there is tensile strength more preferably so that the integration of composite metal combines better.
Preferably, phosphoric acid solution is also added with Halogen inorganic matter, has increased the reaming speed of acid corrosion further, reduce the operating time further, optimize pore structure simultaneously.Preferably, Halogen inorganic matter is soluble-salt hydrochlorate, chloride ion is prone to be formed in metal surface spot corrosion in acid condition, easily going out more hole in corrosion, and widen original hole, soluble-salt is the hydrochlorate present invention do not limit, the various soluble-salt hydrochlorates that can be known to the skilled person, general and phosphoric acid does not react, and produces precipitation and gas, does not affect the performance of phosphoric acid preferably.One or more in sodium chloride, potassium chloride or aluminum chloride of preferred soluble-salt hydrochlorate.It is preferred that, in phosphoric acid solution, the mass percentage concentration of soluble-salt hydrochlorate is 0.01wt%～10wt%.
Wherein, immerse phosphoric acid solution to process adopt and well known to a person skilled in the art the mode that various immersion processes, such as all or part of immersion etc., multi-disc can immerse and can also a piece of immerse, the present invention does not limit, it is preferable that immersing the temperature processed in phosphoric acid solution is 20 DEG C-30 DEG C, the time of process in phosphoric acid solution of immersing is 1-60min, optimizes the thickness of corrosion layer and the structure in metal erosion hole further.
The number of times present invention that immersion processes is also without restriction, preferably, contain gained the metal base immersion phosphoric acid solution of anode oxidation membrane processes and include to repeated multiple times for metal base immersion phosphoric acid solution to process, the time of process in phosphoric acid solution of every time immersing is 1-10min, immersing every time and clean with deionized water after processing in phosphoric acid solution, the number of times of immersion can be 2 to 10 times.Cleaning can be put into clean 1 in rinsing bowl to 5min, or puts into and place 1 to 5min in rinsing bowl.
Anode oxidation membrane in the surface treated metal base of step S2 gained includes the barrier layer contacted with metal base and the weaker zone being positioned at barrier layer outer surface, preferably, the thickness of weaker zone is 1-50um, more preferably 1-30um, the thickness on barrier layer is 10nm-1um, more preferably 50-300nm.Wherein, containing anodic oxidation membrane micropore in weaker zone, it is preferable that, the aperture of anodic oxidation membrane micropore is 10nm-500um, more preferably 10nm-200um, containing barrier layer etch pit in barrier layer, preferably, the aperture of barrier layer etch pit is 10nm-500um, more preferably 15nm-200um.Metal body in the surface treated metal base of step S2 gained includes the corrosion layer contacted with anode oxidation membrane, preferably, the thickness of corrosion layer is 10nm-200um, more preferably 10nm-100um, wherein, corrosion layer and other metal bodies do not have obvious boundary, and the thickness present invention of corrosion layer can refer to corrode the degree of depth of pore-creating on metal body.Containing metal erosion hole in corrosion layer, it is preferable that the aperture in metal erosion hole is 10nm-1mm, more preferably 20nm-800um.Optimize the surface hole defect structure of surface treated metal base further, optimize the adhesion of metal and resin.
S3, injection moulding: resin combination is injection-moulded in surface treated metallic substrate surface, obtains metal-resin composite after molding.Such as can surface treated metal base be placed in mould, then resin combination be injected in mould and combine with surface treated metal base, after molding, obtain metal-resin composite.
Pre-treatment is the pretreatment procedure that metal surface is carried out that those skilled in the art commonly use, and generally comprises and carries out mechanical grinding or grind the obvious foreign body in removal surface, and the processing wet goods then metal surface adhered to carries out defat, cleaning.Preferably, pre-treatment includes being polished in metal surface, for instance Ke Yiwei: first adopts the sand paper of 100-400 order or puts it in buffing machine metal surface polishing is made the micron-sized aperture of generation.Then being sequentially carried out the steps such as oil removing, the first washing, alkaline etching, the second washing, neutralization, the 3rd washing, the various solvents commonly used with those skilled in the art clean this metal, scavenging period 0.5-2h in ultrasound wave, remove the greasy dirt of metal surface；Then metal is placed in acid/base aqueous solution, under Ultrasonic Conditions, washs metal surface.Described solvent can be ethanol or acetone.Described acid/base aqueous solution is the various acid/base aqueous solutions that those skilled in the art commonly use, for instance: can be hydrochloric acid, sulphuric acid, sodium hydroxide, potassium hydroxide etc..In the present invention, preferably with dehydrated alcohol by wash after wiped clean after metal degreasing immerse 40g/L again, temperature is carry out alkaline etching in the sodium hydrate aqueous solution of 40 ~ 80 DEG C, after 1 ~ 5min, taking-up deionized water is rinsed well, it is neutralized with the HNO3 of 10 ~ 30% afterwards, remove the alkaline solution of remained on surface, rinsing well with deionized water, can form micron-sized aperture on the surface of metal base through preferred pre-treatment, the diameter of described aperture is 1-10mm.
The aluminum alloy base material or the aluminium base present invention that need pre-treatment are not particularly limited, for instance aluminum alloy base material can use industrial standard 1000-7000 series matter or the various aluminium alloys of molding level；Heretofore described aluminium alloy is the aluminium alloy of variously-shaped, the structure that those skilled in the art commonly use, and the present invention is not particularly limited.Variously-shaped, the structure of aluminium alloy, can be completed by machining.
Resin combination is the present invention be not particularly limited, it is possible to adopt well known to a person skilled in the art various can with the resin combination of melts combine, it is preferable that resin combination is thermoplastic resin.Can be such as nylon, it is preferable that 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, simultaneously with the use of the vistanex that fusing point is 65 DEG C-105 DEG C, need not injection moulding under specific mould temperature when molding, moulding process simplifies, can guarantee that the metal-resin composite obtained has better mechanical strength and surface treatment characteristics simultaneously, thus solving the incrustation problem of working of plastics, meet the diversified demand of client.By in the noncrystalline matrix resin adopted, with the use of the vistanex that fusing point is 65 DEG C-105 DEG C, resin can be increased and flow into the ability of metal-surface nano level micropore, thus ensureing that the metal 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, present inventor have further discovered that, thermoplastic resin adopts fluidity improver, moreover it is possible to improve the fluid ability of resin, improve the injection moulding performance of the metal adhesive force with resin and resin further.Under preferable case, with the thermoplastic resin of 100 weight portions for benchmark, possibly together with the fluidity improver of 1-5 weight portion in described thermoplastic resin.Under preferable case, described fluidity improver is cyclic polyester.
As it was previously stated, in the present invention, described matrix resin is non-crystalline resin.And specifically, it is preferable to, matrix resin is the mixture of polyphenylene oxide (PPO) and polyphenylene sulfide (PPS), it is preferable that in situation, and 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), it is preferable that in situation, 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 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, the grafted polyethylene that described vistanex can adopt fusing point to be 100 DEG C or 105 DEG C.
The resin combination of the present invention can also contain other property-modifying additives etc., and the present invention is not particularly limited, and can be arranged as required to, for instance can also contain filler in resin combination.Described filler is the various fillers that those skilled in the art commonly use, for instance 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, silicon dioxide, heavy barium sulfate, Pulvis Talci, glass and clay.More preferably in situation, for making the horizontal, longitudinal of plastics composite be respectively provided with the linear expansion coefficient close with metal base, in the present invention, with the matrix resin of 100 weight portions for benchmark, fiberfill content is 50-150 weight portion, and the content of powder-type filler is 50-150 weight portion.
Preparation method according to metal-resin composite provided by the invention, by matrix resin, vistanex mix homogeneously, prepares 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, by matrix resin, vistanex mix homogeneously, by double screw extruder extruding pelletization, stand-by.
Preparation method according to composite metal provided by the invention, filler, fluidity improver can also be added in described matrix resin, mix homogeneously, prepares resin combination, so that the horizontal, longitudinal of resin combination is respectively provided with the linear expansion coefficient close with metal base.
Metal base can also be carried out some modifications before being placed in mould by the metal base of surface treatment, for instance surface modification treatment, present invention preferably comprises in water-soluble polymer, soaks the metal base of surface treatment and modifiy.Water-soluble polymer is made to adsorb on metal base, stay on metal base after drying, metal base is modified, it it is organism simultaneously, resin is had the good compatibility, by water-soluble polymer, metal base is carried out lipophile to modifiy, resin is made to be more easy to the pore space structure entering metal base, accelerate the entrance of casting resin, improve the adhesion of metal and resin further, and improve process efficiency and product yield further, and Polymer adsorption enters the air that can effectively discharge in micropore in micropore, and during injection moulding, resin is more easy to full whole hole.
Preferably soaking modified temperature is 15 DEG C-60 DEG C, and more preferably 20-40 DEG C, the time is 1-30min, more preferably 5-20min, optimizes modified face, the water-soluble polymer that filling capacity is excellent in the micropore district hole of metal base.
Water-soluble polymer is the present invention do not limit, the various water-soluble polymers that can be known to the skilled person, immerse in its solution by metal base, can adsorb on metal base, stay on metal base after drying, metal base is modified, one or more in polyvinyl alcohol, Polyethylene Glycol, polyacrylic acid, polyacrylate, polymethylacrylic acid, poly-methyl acrylate, polyvinyl sulfonic acid, polyvinyl sulfonate, polystyrolsulfon acid or poly styrene sulfonate of the preferred water-soluble polymer of the present invention.Preferably, the concentration of water-soluble polymer is 1wt%-20wt%.
Dried metal base is proceeded in mould, carry out close-coupled processing with prepared resin combination, composite metal provided by the invention can be obtained after molding, in the present invention, the method of described molding is injection mo(u)lding, it is understood that the molding mode of metallo-plastic integration can be made to be used equally to the present invention, it is not limited to the mode of injection mo(u)lding.Wherein, the condition of injection moulding can be mould temperature 50 ~ 300 DEG C, nozzle temperature: 200 ~ 450 DEG C, dwell time: 1 ~ 50s, injection pressure: 50 ~ 300MPa, time delay: 1 ~ 30s, cool time: 1 ~ 60s, the amount of the general resin combination injected is 1 ~ 100g, and the complex surfaces of preparation has the resin bed that 0.5 ~ 10mm is thick.
The 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 to adopt the method for acid liquid corrosion also to significantly reduce etching time, breach the restriction of resin types, direct injection moulding is only needed to realize after adopting the inventive method to process, simultaneously good by adhesion between resin bed and the metal base of the metal-resin composite obtained by preparation method of the present invention, there is preferably tensile shear strength.
Invention also provides metal-resin composite prepared by above-mentioned preparation method, including: metal base and the resin bed with its surface combination.Wherein, resin combination be known to the skilled person various can with the resin combination of metal composite.
The metal-resin composite that the present invention prepares can directly use, it is also possible to carries out some follow-up post processings as required, for instance CNC(Digit Control Machine Tool is processed), 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 aluminum alloy resin complex；
1, pre-treatment: by thick for commercially available 1mm 6063 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it in buffing machine and grind, after it is carried out oil removing cleaning, then its alkaline etching in the solution that 60 DEG C of sodium hydrate contents are 40g/L being processed 10s, clear water puts into HNO after cleaning3Content is about in the neutralization chamber of 6wt% neutralization 30s, after clean with clear water, obtain the aluminum alloy sheet through pre-treatment；
2, surface treatment 1: above-mentioned aluminum alloy sheet is put into the H containing about 15wt% concentration as anode2SO4In anodizing tank, in 15V voltage, electrolysis 5min at 18 DEG C, 80 DEG C are dried 20min；
3, surface treatment 2: preparation is containing 10wt%H in beaker3PO4Aqueous solution 500ml, under room temperature, aforementioned gained aluminum alloy sheet 10PCS is immersed, is drawn off after 2min, put into equipped with in the beaker of water soak 2min, with a H3PO4It is a circulation that water-soluble vacuole adds a blister, so circulation 2 times, after last water soaking, is put into by aluminum alloy sheet in 80 DEG C of baking ovens and dries.
Adopt metallurgical microscope and SEM field emission scanning electron microscope to observe the cross section of the aluminum alloy sheet through surface treatment 2, record aluminum alloy sheet surface and prepare the thick corrosion layer of the thick weaker zone of 6-6.5um, the barrier layer of 80-110nm thickness and 20nm-40um.
Adopting the aperture that SEM field emission scanning electron microscope records weaker zone Anodic Oxidation membrane micropore is 20nm-20um；Obtaining the aperture of barrier layer etch pit in barrier layer by observation cross section is 25nm-25um；In corrosion layer, the aperture in corrosion of aluminium alloy hole is 50nm-120um.Can also be observed that the aluminum alloy surface after process exists three-layer stereo pore structure, anodic oxidation membrane micropore, barrier layer etch pit and corrosion of aluminium alloy hole are interconnected.
4, molding: the aluminum alloy sheet after drying is divided into two batches, every crowd of each 5PCS, insert respectively in injecting molding die, a collection of injection molding nylon resin, polyphenylene sulfide (PPS) resin combination containing 30wt% glass fibre moulded in another annotation, and rear all demouldings also obtain strong bonded aluminium alloy together and the aluminum alloy resin complex A1 group of resin combination, B1 group after cooling down.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex A2 group, B2 group, the difference is that surface treatment 2 is that preparation contains 10wt%H in beaker3PO4Aqueous solution 500ml, room temperature, aforementioned gained aluminum alloy sheet 10PCS is immersed, is drawn off after 10min, place into and soak after 2min equipped with in the beaker of water, aluminium alloy is put in 80 DEG C of baking ovens and dry.Adopt the method identical with embodiment 1 to record the aluminum alloy sheet surface after electrolysis and prepare the thick corrosion layer of the thick weaker zone of 5-6um, the barrier layer of 75-100nm thickness and 25nm-50um.The aperture of weaker zone Anodic Oxidation membrane micropore is 30nm-45um；In barrier layer, the aperture of barrier layer etch pit is 30nm-50um；In corrosion layer, the aperture in corrosion of aluminium alloy hole is 60nm-200um.Can also be observed that the aluminum alloy surface after process exists three-layer stereo pore structure, anodic oxidation membrane micropore, barrier layer etch pit and corrosion of aluminium alloy hole are interconnected.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex A3 group, B3 group, the difference is that H in surface treatment 23PO4Mass percentage concentration be 5wt%, under room temperature, aforementioned gained aluminum alloy sheet 10PCS is immersed, is drawn off after 2min, put into equipped with in the beaker of water soak 2min, with a H3PO4It is a circulation that water-soluble vacuole adds a blister, so circulation 2 times, after last water soaking, is put into by aluminum alloy sheet in 80 DEG C of baking ovens and dries.Adopt the method identical with embodiment 1 to record the aluminum alloy sheet surface after electrolysis and prepare the thick corrosion layer of the thick weaker zone of 7-7.5um, the barrier layer of 80-100nm thickness and 15nm-25um.The aperture of weaker zone Anodic Oxidation membrane micropore is about 15nm-10um；In barrier layer, the aperture of barrier layer etch pit is about 20nm-15um；In corrosion layer, the aperture in corrosion of aluminium alloy hole is about 40nm-60um.Can also be observed that the aluminum alloy surface after process exists three-layer stereo pore structure, anodic oxidation membrane micropore, barrier layer etch pit and corrosion of aluminium alloy hole are interconnected.
Embodiment 4
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex A4 group, B4 group, the difference is that H in surface treatment 23PO4Mass percentage concentration be 20wt%, under room temperature, aforementioned gained aluminum alloy sheet 10PCS is immersed, is drawn off after 2min, put into equipped with in the beaker of water soak 2min, with a H3PO4It is a circulation that water-soluble vacuole adds a blister, so circulation 2 times, after last water soaking, is put into by aluminum alloy sheet in 80 DEG C of baking ovens and dries.Adopt the method identical with embodiment 1 to record the aluminum alloy sheet surface after electrolysis and prepare the thick corrosion layer of the thick weaker zone of 3-4um, the barrier layer of 80-100nm thickness and 30nm-80um.The aperture of weaker zone Anodic Oxidation membrane micropore is 30nm-60um；In barrier layer, the aperture of barrier layer etch pit is 40nm-80um；In corrosion layer, the aperture in corrosion of aluminium alloy hole is 80nm-300um.Can also be observed that the aluminum alloy surface after process exists three-layer stereo pore structure, anodic oxidation membrane micropore, barrier layer etch pit and corrosion of aluminium alloy hole are interconnected.
Embodiment 5
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex A5 group, B5 group, the difference is that surface treatment 2 is that preparation contains 10wt%H in beaker3PO4, 1wt%NaCl aqueous solution 500ml.Adopt the method identical with embodiment 1 to record the aluminum alloy sheet surface after electrolysis and prepare the thick corrosion layer of the thick weaker zone of 4.5-5um, the barrier layer of 80-100nm thickness and 25nm-60um.The aperture of weaker zone Anodic Oxidation membrane micropore is 25nm-50um；In barrier layer, the aperture of barrier layer etch pit is 30nm-50um；In corrosion layer, the aperture in corrosion of aluminium alloy hole is 50nm-250um.Can also be observed that the aluminum alloy surface after process exists three-layer stereo pore structure, anodic oxidation membrane micropore, barrier layer etch pit and corrosion of aluminium alloy hole are interconnected.
Embodiment 6
Adopt and prepare aluminum alloy resin complex A6 group, B6 group with the identical method of embodiment 1, soak 5min the difference is that being put into by the aluminum alloy sheet after drying before the forming in the poly-vinyl alcohol solution of 2wt%, dry after taking-up place in mould.
Embodiment 7
1, pre-treatment: by thick for commercially available 1mm 6063 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it in buffing machine and grind, after it is carried out oil removing cleaning, then its alkaline etching in the solution that 60 DEG C of sodium hydrate contents are 40g/L being processed 10s, clear water puts into HNO after cleaning3Content is about in the neutralization chamber of 6wt% neutralization 30s, after clean with clear water, obtain the aluminum alloy sheet through pre-treatment；
2, surface treatment 1: above-mentioned aluminum alloy sheet is put into the H containing about 15wt% concentration as anode2SO4In anodizing tank, in 15V voltage, electrolysis 5min at 18 DEG C, 80 DEG C are dried 20min；
3, surface treatment 2: preparation is containing 10wt%H in beaker3PO4Aqueous solution 500ml, put in 25 DEG C of temperature chambers and be warming up to 25 DEG C, and put into thermometer, make measurement point be positioned at Solutions Center position.Take aforementioned gained aluminum alloy sheet 20PCS, it is divided into two batches, every crowd of each 10PCS, a collection of it is immersed, it is drawn off after 2min, etching liquid temperature in record beaker before taking out, it is immediately placed into second batch aluminum alloy sheet, first aluminum alloy sheet is put into equipped with soaking 2min in the beaker of water simultaneously, second batch aluminum alloy sheet is taken out from etching liquid, record temperature before taking out, and first aluminum alloy sheet is put in etching liquid, second batch aluminum alloy sheet is put in water simultaneously and soak, so circulation, until two batches of aluminum alloy sheets all soaked 5 times in etching liquid, each aluminum alloy sheet records temperature before taking out from acid solution, obtain the curve chart (such as Fig. 1) of temperature and time.
Comparative example 1
1, pre-treatment: by thick for commercially available 1mm 6063 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it in buffing machine and grind, after it is carried out oil removing cleaning, then its alkaline etching in the solution that 60 DEG C of sodium hydrate contents are 40g/L being processed 10s, clear water puts into HNO after cleaning3Content is about in the neutralization chamber of 6wt% neutralization 30s, after clean with clear water, obtain the aluminum alloy sheet through pre-treatment；
2, surface treatment: aluminum alloy base material is immersed in the phosphate aqueous solution 500ml that concentration is 10wt%, put in 25 DEG C of temperature chambers and be warming up to 25 DEG C, aforementioned gained aluminum alloy sheet 10PCS is immersed, it is drawn off after 2min, put into equipped with the beaker of water soaks 2min, add a blister for a circulation once etching vacuole, so circulate 5 times, after last water soaking, aluminum alloy sheet is put in 80 DEG C of baking ovens and dry.
The method identical with embodiment 1 is adopted to record the corrosion layer of prepared 300nm-120um.The aperture in the hole in corrosion layer is 300nm-400um.
3, molding: the aluminum alloy sheet after drying is divided into two batches, every crowd of each 5PCS, insert respectively in injecting molding die, a collection of injection moulding contains polyphenylene sulfide (PPS) resin combination of 30wt% glass fibre, nylon resin moulded in another annotation, and rear all demouldings also obtain strong bonded aluminium alloy together and the aluminum alloy resin complex C1 group of resin combination, D1 group after cooling down.
Comparative example 2
1, pre-treatment: by thick for commercially available 1mm 6063 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it in buffing machine and grind, after it is carried out oil removing cleaning, then its alkaline etching in the solution that 60 DEG C of sodium hydrate contents are 40g/L being processed 10s, clear water puts into HNO after cleaning3Content is about in the neutralization chamber of 6wt% neutralization 30s, after clean with clear water, obtain the aluminum alloy sheet through pre-treatment；
2, surface treatment: being put in the H2SO4 anodizing tank containing about 20wt% concentration as anode by above-mentioned aluminum alloy sheet, electrolysis 10min, dries up under 15V voltage；
Adopting the aperture that the method identical with embodiment 1 records prepared anode oxide film mesopore is about 10-100nm, and hole depth is about 9-10um.
3, molding: the aluminum alloy sheet after drying is divided into two batches, every crowd of each 5PCS, insert respectively in injecting molding die, a collection of injection moulding contains polyphenylene sulfide (PPS) resin combination of 30wt% glass fibre, nylon resin moulded in another annotation, and rear all demouldings also obtain strong bonded aluminium alloy together and the aluminum alloy resin complex C2 group of resin combination, D2 group after cooling down.
Comparative example 3
1, pre-treatment: by thick for commercially available 1mm 6063 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it in buffing machine and grind, after it is carried out oil removing cleaning, then its alkaline etching in the solution that 60 DEG C of sodium hydrate contents are 40g/L being processed 10s, clear water puts into HNO after cleaning3Content is about in the neutralization chamber of 6wt% neutralization 30s, after clean with clear water, obtain the aluminum alloy sheet through pre-treatment；
2, surface treatment: prepare the phosphate aqueous solution 500ml of 10wt% in beaker, puts in 25 DEG C of temperature chambers and is warming up to 25 DEG C, and put into thermometer, makes measurement point be positioned at Solutions Center position.Take aforementioned gained aluminum alloy sheet 20PCS, it is divided into two batches, every crowd of each 10PCS, a collection of it is immersed, it is drawn off after 2min, etching liquid temperature in record beaker before taking out, it is immediately placed into second batch aluminum alloy sheet, first aluminum alloy sheet is put into equipped with soaking 2min in the beaker of water simultaneously, second batch aluminum alloy sheet is taken out from etching liquid, record temperature before taking out, and first aluminum alloy sheet is put in etching liquid, second batch aluminum alloy sheet is put in water simultaneously and soak, so circulation, until two batches of aluminum alloy sheets all soaked 5 times in etching liquid, each aluminum alloy sheet records temperature before taking out from acid solution, obtain the curve chart (such as Fig. 1) of temperature and time.
Performance test:
The adhesion of aluminium alloy and resin: aluminum alloy resin complex prepared by embodiment 1-6 and comparative example 1-2 is fixed on universal testing machine and carries out product extension test, in test result, maximum load can be considered the size of the adhesion between aluminium alloy and resin, and test result is table 2 such as.
Table 1
| Weaker zone thickness | The aperture of anodic oxidation membrane micropore | Barrier layer thickness | The aperture of barrier layer etch pit | Corrosion layer thickness | The aperture in corrosion of aluminium alloy hole | |
| Embodiment 1 | 6-6.5um | 20nm-20um | 80-110nm | 25nm-25um | 20nm-40um | 50nm-120um |
| Embodiment 2 | 5-6um | 30nm-45um | 75-100nm | 30nm-50um | 25nm-50um | 60nm-200um |
| Embodiment 3 | 7-7.5um | 15nm-10um | 80-100nm | 20nm-15um | 15nm-25um | 40nm-60um |
| Embodiment 4 | 3-4um | 30nm-60um | 80-100nm | 40nm-80um | 30nm-80um | 80nm-300um |
| Embodiment 5 | 4.5-5um | 25nm-50um | 80-100nm | 30nm-50um | 25nm-60um | 50nm-250um |
Table 2
| Sample | Adhesion | Sample | Adhesion |
| A1 | 845.48 | B1 | 854.65 |
| A2 | 808.47 | B2 | 815.96 |
| A3 | 612.04 | B3 | 636.58 |
| A4 | 934.22 | B4 | 916.78 |
| A5 | 907.10 | B5 | 939.50 |
| A6 | 891.27 | B6 | 874.08 |
| C1 | 354.65 | D1 | 421.12 |
| C2 | 121.00 | D2 | 86.50 |
The surface pore structure of aluminum alloy base material prepared by the present invention is unique as can be seen from the table, high with the adhesion of resin, N more than 900 can be reached, it is significantly larger than prior art, simultaneously applied widely, can be applied not only to PPS, and can be combined with nylon, adhesion is strong, technique simply easily large-scale production.Technical scheme exothermic heat of reaction is few as can be seen from Figure 1 simultaneously, and etching liquid heats up slow, is more suitable for large-scale production, and the etching liquid of consumption is also less and the corrosion of equipment is little.
Those skilled in the art are readily apparent that; the foregoing is only presently preferred embodiments of the present invention; not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (36)
1. the preparation method of a metal-resin composite, it is characterised in that comprise the steps of
S1, anodic oxidation: by anodic oxidation, the metal base through pre-treatment is obtained the metal base that anode oxidation membrane is contained on surface, and described metal base is aluminum alloy base material or aluminium base；
S2, phosphoric acid processes: the metal base that step S1 gained contains anode oxidation membrane immerses process in phosphoric acid solution, obtains surface treated metal base；
S3, injection moulding: resin combination is injection-moulded in surface treated metallic substrate surface, obtains metal-resin composite after molding.
2. preparation method according to claim 1, it is characterised in that the mass percentage concentration of described phosphoric acid is 3wt%～40wt%.
3. preparation method according to claim 2, it is characterised in that the mass percentage concentration of described phosphoric acid is 5wt%～30wt%.
4. preparation method according to claim 3, it is characterised in that the mass percentage concentration of described phosphoric acid is 5wt%～20wt%.
5. preparation method according to claim 1, it is characterised in that be also added with Halogen inorganic matter in described phosphoric acid solution.
6. preparation method according to claim 5, it is characterised in that described Halogen inorganic matter is soluble-salt hydrochlorate.
7. preparation method according to claim 6, it is characterised in that one or more in sodium chloride, potassium chloride or aluminum chloride of described soluble-salt hydrochlorate.
8. preparation method according to claim 6, it is characterised in that in described phosphoric acid solution, the mass percentage concentration of soluble-salt hydrochlorate is 0.01wt%～10wt%.
9. preparation method according to claim 1, it is characterised in that the temperature processed in described immersion phosphoric acid solution is 20 DEG C-30 DEG C.
10. preparation method according to claim 1, it is characterised in that the time processed in described immersion phosphoric acid solution is 1-60min.
11. preparation method according to claim 1, it is characterized in that, the metal base that described step S2 includes step S1 gained is contained anode oxidation membrane repeatedly immerses process in phosphoric acid solution, the time of process in phosphoric acid solution of every time immersing is 1-10min, immerses every time and washes after processing in phosphoric acid solution.
12. preparation method according to claim 11, it is characterised in that the number of times of described immersion is 2 to 10 times.
13. preparation method according to claim 1, it is characterised in that also include soaking surface treated metal base in water-soluble polymer solution modified after described step S2 before step S3.
14. preparation method according to claim 13, it is characterized in that, one or more in polyvinyl alcohol, Polyethylene Glycol, polyacrylic acid, polyacrylate, polymethylacrylic acid, poly-methyl acrylate, polyvinyl sulfonic acid, polyvinyl sulfonate, polystyrolsulfon acid or poly styrene sulfonate of described water-soluble polymer.
15. preparation method according to claim 13, it is characterised in that soaking modified temperature is 15 DEG C-60 DEG C, and the time is 1-30min.
16. preparation method according to claim 13, it is characterised in that the concentration of described water-soluble polymer is 1wt%-20wt%.
17. preparation method according to claim 13, it is characterised in that described immersion in water-soluble polymer solution dries removal solvent modified also including.
18. preparation method according to claim 1, it is characterized in that, anode oxidation membrane in the surface treated metal base of step S2 gained includes the barrier layer contacted with metal base and the weaker zone being positioned at barrier layer outer surface, the thickness of described weaker zone is 1-50 μm, and the thickness on described barrier layer is 10nm-1 μm.
19. preparation method according to claim 18, it is characterized in that, containing anodic oxidation membrane micropore in described weaker zone, the aperture of described anodic oxidation membrane micropore is 10nm-500 μm, containing barrier layer etch pit in described barrier layer, the aperture of described barrier layer etch pit is 10nm-500 μm.
20. preparation method according to claim 1, it is characterised in that the metal body in the surface treated metal base of step S2 gained includes the corrosion layer contacted with anode oxidation membrane, and the thickness of described corrosion layer is 10nm-200 μm.
21. preparation method according to claim 20, it is characterised in that containing metal erosion hole in described corrosion layer, the aperture in described metal erosion hole is 10nm-1mm.
22. preparation method according to claim 1, it is characterized in that, described anodic oxidation includes putting in 10wt%-30wt% concentration sulphuric acid or phosphoric acid using the metal base through pre-treatment as anode, temperature 10-30 DEG C under 5V～35V voltage electrolysis 2-15min obtain the metal base that the anode oxidation membrane of 1-20 μ m-thick is contained on surface.
23. preparation method according to claim 1, it is characterised in that described pre-treatment includes metallic substrate surface is polished, then it is sequentially carried out oil removing, the first washing, alkaline etching, the second washing, neutralization, the 3rd water-washing step.
24. preparation method according to claim 1, it is characterised in that described resin combination is thermoplastic resin composition.
25. preparation method according to claim 24, it is characterised in that described thermoplastic resin composition is nylon.
26. preparation method according to claim 24, it is characterised in that described thermoplastic resin is the blend containing matrix resin and vistanex.
27. preparation method according to claim 26, it is characterised in that described matrix resin is the mixture of polyphenylene oxide and polyphenylene sulfide, the fusing point of described vistanex is 65 DEG C-105 DEG C.
28. preparation method according to claim 27, it is characterised in that in described matrix resin, polyphenylene oxide is 3:1-1:3 with the weight ratio of polyphenylene sulfide.
29. preparation method according to claim 26, it is characterised in that described matrix resin is the mixture of polyphenylene oxide and polyamide, the fusing point of described vistanex is 65 DEG C-105 DEG C.
30. preparation method according to claim 29, it is characterised in that in described matrix resin, polyphenylene oxide is 3:1-1:3 with the weight ratio of polyamide.
31. preparation method according to claim 26, it is characterised in that described matrix resin is Merlon, the fusing point of described vistanex is 65 DEG C-105 DEG C.
32. preparation method according to claim 26, it is characterised 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.
33. preparation method according to claim 26, it is characterised in that described vistanex is grafted polyethylene.
34. preparation method according to claim 25, it is characterised in that with the thermoplastic resin of 100 weight portions for benchmark, possibly together with the fluidity improver of 1-5 weight portion in described thermoplastic resin；Described fluidity improver is cyclic polyester.
35. preparation method according to claim 25, it is characterized in that, containing filler in described resin combination, described filler includes 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 silicon dioxide, Pulvis Talci, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, glass and Kaolin.
36. a metal-resin composite, it is characterised in that adopt the method as described in claim 1-35 any one to be made, including: metal base and the resin bed with its surface combination.
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| CN201210167814.5A CN103451704B (en) | 2012-05-28 | 2012-05-28 | The preparation method of a kind of metal-resin composite and the metal-resin composite of preparation thereof |
| TW102118702A TWI475132B (en) | 2012-05-28 | 2013-05-27 | Surface-treated metal, metal-resin composite and method for preparing the same |
| PCT/CN2013/076351 WO2013178057A1 (en) | 2012-05-28 | 2013-05-28 | Metal composite and method of preparing the same, metal-resin composite and method of preparing the same |
| EP13796944.0A EP2855740A4 (en) | 2012-05-28 | 2013-05-28 | Metal composite and method of preparing the same, metal-resin composite and method of preparing the same |
| US14/554,370 US9783894B2 (en) | 2012-05-28 | 2014-11-26 | Metal composite and method of preparing the same, metal-resin composite and method of preparing the same |
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| CN104790009B (en) * | 2014-01-16 | 2017-09-29 | 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 |
| CN103862748B (en) * | 2014-02-13 | 2016-01-20 | 东莞宜安科技股份有限公司 | A kind of aluminium alloy and polyphenylene sulfide thermal resin composite and preparation method thereof |
| CN105504788B (en) * | 2014-09-30 | 2016-09-07 | 比亚迪股份有限公司 | Injection-molded article of a kind of variety classes resin and preparation method thereof and the injection-molded article prepared by the method and application thereof |
| WO2018155383A1 (en) * | 2017-02-22 | 2018-08-30 | 株式会社Uacj | Surface-treated aluminum material and method for manufacturing same; and bonded body of surface-treated aluminum material and bonding member comprising said surface-treated aluminum material and bonding member such as resin, and method for manufacturing said bonded body |
| EP3453510B1 (en) | 2017-09-08 | 2022-03-02 | Apple Inc. | Bonding polymer material to anodized metal using cavities |
| JP6778724B2 (en) * | 2017-09-08 | 2020-11-04 | アップル インコーポレイテッドＡｐｐｌｅ Ｉｎｃ． | Etching to bond polymer material to anodized metal |
| EP3604605B1 (en) * | 2017-11-16 | 2023-06-07 | Mutsuki Electric Co., Ltd. | Method for producing metal member, and method for producing metal-resin joined body |
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