CN104711651A - Aluminum alloy resin complex - Google Patents
Aluminum alloy resin complex Download PDFInfo
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- CN104711651A CN104711651A CN201510155667.3A CN201510155667A CN104711651A CN 104711651 A CN104711651 A CN 104711651A CN 201510155667 A CN201510155667 A CN 201510155667A CN 104711651 A CN104711651 A CN 104711651A
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Abstract
The invention provides an aluminum alloy resin complex comprising an aluminum alloy substrate and a resin layer, wherein the aluminum alloy substrate comprises an aluminum alloy body and an anode oxide film layer on the surface of the aluminum alloy body, the anode oxide film layer is composed of an outer surface layer part and an inner layer part, a corrosion hole is formed in the outer surface layer part, the aperture of the corrosion hole is 200-2000 nm, the inner layer part contains a nanopore produced by anode oxidation, and the corrosion hole is communicated with the nanopore; the nanopore and the corrosion hole are filled with a resin composition forming the resin layer. In the aluminum alloy resin complex provided by the invention, the aluminum alloy has a good binding force with the resin, and moreover the process is simple, easily achieves large-scale production and is pollution-free.
Description
Related application
The divisional application of the application's to be application number be Chinese invention patent application of 201210043634.6.
Technical field
The present invention relates to a kind of aluminum alloy resin complex and preparation method thereof, more particularly, particularly relate to a kind of aluminium alloy with double-deck duct and aluminum alloy resin complex of being formed and preparation method thereof integrated with thermoplastic resin.
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 tackiness agent under normal temperature or heating by combination integrated with synthetic resins for metal.Although adopt aforesaid method can prepare metal and integrally moulded complex body, but bonding force is poor between the complex body metal obtained according to these methods and plastic cement, and tackiness agent acid-fast alkali-proof poor performance, complex body cannot carry out the surface treatments such as follow-up anodic oxidation.Thus, all the time, people are examining whether more reasonably by the engineering resin of high strength and the integrated method of the alloy of aluminium alloy and so on 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 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.
The existing integrated molding technology just like disclosing aluminium alloy and resin combination, adopt amine substance, such as: carbamate, one hydrazine hydrate, the aqueous solution of quadrol etc. carries out surface treatment to aluminium alloy and obtains nano level micropore, 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 and injectable plastic material, resin and aluminum alloy junction are combined together, thus obtain the plastic-aluminum integration product of certain tensile shear strength, and adopt the technology that this type of amine substance corrodes, etching time is longer and hole that is aluminum alloy surface formation is too little, resin is difficult to direct injection moulding and enters nano level hole, reduce the bonding strength of aluminium alloy and resin, i.e. stretch-proof poor-performing, the combination of resin and aluminium alloy simultaneously mainly relies on amine groups, the kind of the resin used is very limited, the resin that this technology can adopt at present only has PPS (polyphenylene sulfide), PA (polymeric amide), PPA (polyphthalamide resin), four resinoids such as PBT (polybutylene terephthalate), practical ranges is also narrow, and the amine substance adopted is poisonous, there is volatile material, be 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 this type of etching solution to corrode the technology of aluminum alloy surface, there is the etchant concentration low time long, etchant concentration high exothermic heat of reaction is large, and the bad control of temperature, is unfavorable for scale operation, and adopting this kind of method, the bonding force between metal and resin is poor.
Existing also have by anodic oxidation preparation, there is the aluminum oxide rete in the cave of 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 enters nano level hole, reduce the bonding strength of aluminium alloy and resin, i.e. stretch-proof poor-performing.
Summary of the invention
The technical problem that when the present invention is in order to solve preparation aluminum alloy resin complex of the prior art, the bonding force of aluminium alloy and resin is weak.There is provided one can have good bonding force with resin, and technique aluminum alloy resin complex being simple and easy to scale operation and preparation method thereof.
First object of the present invention is to provide a kind of aluminum alloy resin complex, this aluminum alloy resin complex comprises aluminum alloy base material and resin layer, described aluminum alloy base material comprises the anode oxidation membrane on aluminium alloy body and surface thereof, described anode oxidation membrane is made up of extexine part and interior layer segment, containing corrosion hole in described extexine part, the aperture of described corrosion hole is 200nm-2000nm, described interior layer segment contains the nanometer micropore produced because of anodic oxidation, and described corrosion hole is communicated with described nanometer micropore; The resin combination forming described resin layer is filled in described nanometer micropore and corrosion hole.。
Second object of the present invention is to provide the preparation method of above-mentioned aluminum alloy resin complex, comprises following steps:
S1, obtains surface containing the aluminium alloy of anode oxidation membrane with nanometer micropore by the part surface of binding resin part that needs of the surface of the aluminium alloy through pre-treatment or aluminium alloy by anodic oxidation;
S2, the aluminium alloy that step S1 gained is contained the anode oxidation membrane with nanometer micropore is dipped into and forms aperture at anode oxidation membrane extexine in etching liquid is the corrosion hole of 200nm-2000nm, obtains surface treated aluminum alloy base material;
S3, is placed in mould by surface treated for step S2 gained aluminum alloy base material, then resin combination injection moulding is entered in mould and combines with described surface treated aluminum alloy base material, obtain aluminum alloy resin complex after shaping.[0012] the present inventor is surprised to find that the double-deck stereo pore space structure that can be formed uniqueness by technology of the present invention in aluminum alloy surface, aluminum alloy surface forms aluminum oxide rete, itself there is the nanometer micropore of the 10-100nm of excellent performance, the structure in hole is unique, with resin itself, there is good associativity, namely contain the large corrosion hole of 200nm-2000nm aperture ratio nanometer micropore with the surface of resin-bonded at the outside surface of aluminum oxide rete simultaneously, by surface pore-creating again, the pore structure not only formed is unique, improve the bonding force of resin and aluminium alloy, and the resin of injection moulding is by the macroporous structure of outside surface, better penetrate in the aperture of internal layer, shaping easier, aluminium alloy of the present invention do not need extra group can with resin mortise, intensity is higher, and it is little to metallic matrix size impact, heat release is little, on aluminium alloy outward appearance substantially without impact.The direct injection moulding of resin simultaneously enters in micron-sized surperficial macropore, is easier to, does not also specially require synthetic resins, and the scope of application is wider, and environmentally safe, be more suitable for scale operation.
Accompanying drawing explanation
Fig. 1 is the double-deck stereo pore structure schematic diagram existed in the anode oxidation membrane prepared of the embodiment of the present invention.
Fig. 2 is the scanning electron microscope diagram of the embodiment of the present invention 1 through the aluminum alloy sheet surface of surface treatment 1.
Fig. 3 a, 3b are the scanning electron microscope diagram of the embodiment of the present invention 1 through the aluminum alloy sheet surface of surface treatment 2.
Embodiment
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 surface-treated aluminium alloy, comprise the anode oxidation membrane on aluminium alloy body and surface thereof, wherein, anode oxidation membrane is made up of extexine part and interior layer segment, containing corrosion hole in extexine part, the aperture of corrosion hole is 200nm-2000nm, interior layer segment contains nanometer micropore, and the aperture of nanometer micropore is 10-100nm, can have good bonding force with resin, and technique is simple and easy to scale operation, pollution-free.
Preferably the aperture of nanometer micropore is 20-80nm further, is further 20-60nm; The aperture of preferred corrosion hole is 200-1000nm, is further preferably 400-1000nm.The structure of further optimization double-hole, is more conducive to the direct injection of resin and the combination of resin and alloy during injection moulding.
The degree of depth of preferred corrosion hole is 0.5-9.5um, more preferably 0.5-5um, optimizes the structure of corrosion hole further, makes casting resin more be conducive to infiltration.
Preferred corrosion hole is communicated with nanometer micropore, and preferred double-deck stereo pore space structure, is conducive to the perviousness providing resin further further, improves the bonding force of resin and alloy, and is more conducive to shaping.
The thickness of preferred anodes oxidation film layer is 1-10um, more preferably 1-5um.Anode oxidation membrane and aluminium alloy body also can have higher bonding force, also can optimize the space of etching complex pore space structure simultaneously, be convenient to produce the more excellent corrosion hole of structure.
Preferably, the degree of depth of nanometer micropore is 0.5-9.5um, more preferably 0.5-5um, optimize the structure of nanometer micropore, the resin improving melting, to the compactedness of nanometer micropore, can ensure that the resin of melting in general Shooting Technique can permeate the nanometer micropore of this degree of depth full, not only not reduce the bonded area of resin and anode oxidation membrane, and also there is not gap etc. in nanometer micropore, improve the bonding force of resin and aluminium alloy further.
Invention also provides the method for above-mentioned aluminum alloy surface process, comprise following steps:
S1, obtains surface containing the aluminium alloy of anode oxidation membrane with aperture 10-100nm nanometer micropore by the aluminium alloy through pre-treatment by anodic oxidation; The anodizing technology that anodic oxidation is known to the skilled person, the present invention can comprise the aluminium alloy through pre-treatment is put into 10wt%-30wt% concentration H2SO4 as anode, temperature 10-30 DEG C under 10V-100V voltage electrolysis 1-40min obtain the surperficial aluminium alloy containing the thick anode oxidation membrane of 1-10um, anodised equipment adopts known anodic oxidation equipment, such as anodizing tank.
S2, the aluminium alloy that step S1 gained is contained the anode oxidation membrane with aperture 10-100nm nanometer micropore is dipped into the corrosion hole being 200nm-2000nm in anode oxidation membrane extexine formation aperture in etching liquid and obtains surface treated aluminium alloy.This step is to adopt etching liquid antianode oxidation film layer surface to corrode, the extexine of anode oxidation membrane is made to form micron-sized large corrosion hole, by this corrosion pore-creating again, in follow-up moulding process, resin combination can more easily directly enter in the surface holes of aluminium alloy in injection moulding process, thus forms good combination with aluminium alloy after formation resin layer.Etching liquid can be the solution corroded by aluminum oxide rete, and the general solution with energy dissolved oxygen aluminium regulates concentration, such as, can be acid/alkaline etching liquid, can be selected from the solution of pH=10-13.Can be single basic solution or the composite buffering solution of pH=10-13 under preferable case, the single basic solution of pH=10-13 can be the aqueous solution of Na2CO3, NaHCO3, NaOH, K2CO3, KHCO3, KOH etc., more preferably Na2CO3 and/or the NaHCO3 aqueous solution, corrosion hole can be made to be uniformly distributed in aluminum alloy surface, and uniform pore diameter, the bonding properties of resin layer and aluminum alloy base material can be made better, there is better tensile strength, the integration of Al alloy complex is combined better.The solid content of above-mentioned Na2CO3 and/or the NaHCO3 aqueous solution can be 0.1wt%-15wt%.Composite buffering solution can be the mixing solutions of soluble phosphoric acid hydrogen salt and water soluble alkali, the aqueous solution of such as SODIUM PHOSPHATE, MONOBASIC and sodium hydroxide, the solid content of the aqueous solution of SODIUM PHOSPHATE, MONOBASIC and sodium hydroxide can be 0.1wt%-15wt%, also can be the aqueous solution of K3PO4 and K2HPO4, composite buffering solution can also be ammonia soln, the hydrazine aqueous solution, the hydrazine derivative aqueous solution, the water-soluble amine based compound aqueous solution, the NH3-NH4Cl aqueous solution etc.Aluminium alloy gained being contained the anode oxidation membrane with aperture 10-100nm nanometer micropore is dipped into etching liquid and comprises in repeated multiple times for aluminium alloy immersion etching liquid, the time of each dipping is 1-60min, clean with deionized water after each dipping, the number of times of immersion can be 2 to 10 times.Cleaning can be put into washing bath cleaning 1 to 5min, or puts into washing bath placement 1 to 5min.
Pre-treatment is the pretreatment procedure carried out aluminum alloy surface that those skilled in the art commonly use, and generally comprises and carries out mechanical grinding or grinding removal surface significantly foreign matter, then carry out degreasing, cleaning to the processing wet goods that metallic surface adheres to.Preferably, pre-treatment comprises polishes to aluminum alloy surface, such as, can be: first adopt 100-400 object sand paper or put it in polishing machine and make the micron-sized aperture of generation to aluminum alloy surface polishing.Then carry out the steps such as oil removing, the first washing, alkaline etching, the second washing, neutralization, the 3rd washing successively, all kinds of SOLVENTS commonly used with those skilled in the art cleans this aluminium alloy in ultrasonic wave, scavenging period 0.5-2h, removes the greasy dirt of aluminum alloy surface; Then aluminium alloy is placed in acid/alkaline aqueous solution, under Ultrasonic Conditions, washs aluminum alloy surface.Described solvent can be ethanol or acetone.Described acid/alkaline aqueous solution is various acid/alkaline aqueous solutions that those skilled in the art commonly use, such as: can be hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide etc.In the present invention, preferably carry out alkaline etching with dehydrated alcohol by immersing again in the aqueous sodium hydroxide solution of 30-70g/L, temperature 40-80 DEG C after aluminium alloy oil removing after washing wiped clean, after 1 ~ 5min, taking-up deionized water rinsing is clean, neutralize with the HNO3 of 10-30% afterwards, the basic solution of removing remained on surface, clean with deionized water rinsing again, can form micron-sized aperture on the surface of aluminum alloy base material through preferred pre-treatment, the diameter of described aperture is 1-10 micron.
Need aluminium alloy the present invention of pre-treatment to be not particularly limited, the various aluminium alloys of industrial standards 1000-7000 series matter or die casting level can be used; Aluminium alloy described in the present invention be those skilled in the art commonly use different shape, structure aluminium alloy, the present invention is not particularly limited.The different shape of aluminium alloy, structure, complete by mechanical workout.
Invention also provides a kind of aluminum alloy resin complex, comprising: aluminum alloy base material and resin layer, wherein, aluminum alloy base material is above-mentioned surface-treated aluminium alloy, and the resin combination forming described resin layer is filled in described nanometer micropore and corrosion hole.
Wherein, resin combination is the various resin combinations that can be combined with aluminium alloy, and the present invention is not particularly limited, and can select according to actual needs, such as, can be thermoplastic resin composition.Preferred resin composition is thermoplastic resin.Preferred thermoplastic resin is the blend containing matrix resin and polyolefin resin.Preferred matrix resin is noncrystalline matrix resin, select noncrystalline matrix resin as injection molding material, its surface luster, toughness are all better than high crystalline resin of the prior art, it is the polyolefin resin 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 physical strength and surface treatment characteristics simultaneously, thus solve the surface decoration problem of plastic component, meet the diversified demand of client.By in adopted noncrystalline matrix resin, with the use of the polyolefin resin 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 sticking power, physical strength.Under preferable case, with the thermoplastic resin of 100 weight parts for benchmark, wherein the content of matrix resin is 70-95 weight part, and the content of polyolefin resin is 5-30 weight part.
As a further improvement on the present invention, the present inventor also finds, in thermoplastic resin, adopt fluidity improver, can also improve the flow capacity of resin, improves further metal and the sticking power of resin and the injection moulding performance of resin.Under preferable case, with the thermoplastic resin of 100 weight parts for benchmark, the fluidity improver also containing 1-5 weight part 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 polymeric amide (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 polycarbonate (PC), and it can be selected from various Linear polycarbonate and/or branched polycarbonate, and the present invention does not have special stipulation.
In the present invention, the fusing point of the polyolefin resin adopted is 65 DEG C-105 DEG C.Under preferable case, described polyolefin resin can adopt grafted polyethylene.More preferably, in situation, described polyolefin resin 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 fibrous packing or powdery filler.Described fibrous packing can be selected from one or more in glass fibre, carbon fiber and Kevlar; Described powder-type filler can be selected from one or more in calcium carbonate, magnesiumcarbonate, silicon-dioxide, heavy barium sulfate, talcum powder, glass and clay.More preferably in situation, all there is the coefficient of linear expansion close with aluminum alloy base material, in the present invention, with the matrix resin of 100 weight parts for benchmark for making the horizontal, longitudinal of plastics composite, fibrous packing content is 50-150 weight part, and the content of powder-type filler is 50-150 weight part.
Invention also provides the preparation method of above-mentioned aluminum alloy resin complex, comprise following steps: surface-treated aluminum alloy base material is placed in mould, then resin combination is injected mould to combine with surface-treated aluminum alloy base material, Al alloy complex is obtained after shaping, wherein, surface-treated aluminum alloy base material is above-mentioned surface-treated aluminium alloy.
According to the preparation method of aluminum alloy resin complex provided by the invention, matrix resin, polyolefin resin 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, polyolefin resin, by twin screw extruder extruding pelletization, stand-by.
According to the preparation method of Al alloy complex 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 coefficient of linear expansion close with aluminum alloy base material.
Dried aluminum alloy base material is proceeded in mould, carry out close-coupled processing with obtained resin combination, Al alloy complex provided by the invention can be obtained after shaping, in the present invention, described shaping method is injection moulding, is understandable that, the molding mode of metal plastic integration can be made all to can be used for the present invention, being not limited to the mode of injection moulding, such as, can also be injection molding mode.The condition of preferred injection moulding is mould temperature 50 ~ 300 DEG C, nozzle temperature: 200 ~ 450 DEG C, dwell time: 1 ~ 50s, injection pressure: 50 ~ 300MPa, the injection time: 1 ~ 30s, time of lag: 1 ~ 30s, cooling time: 1 ~ 60s, more preferably mould temperature: 80 ~ 200 DEG C, nozzle temperature is: 200 ~ 350 DEG C, injection pressure is: 90 ~ 140MPa, dwell time: 1 ~ 10s, injection time: 3 ~ 10s, time of lag: 15 ~ 30s, cooling time: 15 ~ 25s, the thickness of the resin layer of formation is 0.5 ~ 10mm.
Preparation method of the present invention is simple, the work simplification of more existing employing sizing agent Production Flow Chart, shorten the production time, and more existing nano surface hole injection moulding need adopt the method that amine substance corrodes 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 process, simultaneously good by bonding force between the resin layer of the aluminum alloy resin complex obtained by preparation method of the present invention and aluminum alloy base material, there is preferably tensile shear strength.
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 5052 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, clean with dehydrated alcohol afterwards, then aluminum alloy base material is immersed in the aqueous sodium hydroxide solution of 40g/L, after 2min, taking-up is clean with deionized water rinsing, obtains the aluminum alloy sheet through pre-treatment;
2, surface treatment 1: above-mentioned aluminum alloy sheet is put into H2SO4 anodizing tank containing about 20wt% concentration as anode, in 20V voltage, electrolysis 10min at 18 DEG C, dries up;
3, surface treatment 2: the sodium carbonate 500ml (pH=12) preparing 10wt% in beaker, soaks gained aluminum alloy sheet wherein by 20 DEG C, taken out after 5min, put into the beaker that water is housed and soak 1min, so circulation 5 times, after last water soaking, aluminum alloy sheet is dried up;
Adopt metallography microscope sem observation through the cross section of the aluminum alloy sheet of surface treatment 1, record the aluminum oxide rete that the obtained 5um in the surface of the aluminum alloy sheet after electrolysis is thick, adopt electron microscope observation through the aluminum alloy sheet surface (as Fig. 2) of surface treatment 1, can obtain aluminum oxide rete and include the nanometer micropore that aperture is about 40-60nm, the hole depth of nanometer micropore is about 1um;
Adopt electron microscope observation through the aluminum alloy sheet surface (as Fig. 3 a, 3b) of surface treatment 2, there is the corrosion hole in 300-1000nm aperture on aluminum alloy sheet surface after can soaking, the degree of depth of corrosion hole is 4um, also can observe the double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete, in nanometer micropore and corrosion hole, there is connectivity structure;
4, shaping: the aluminum alloy sheet after drying is inserted in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) resin combination of 30wt% glass fibre, and the demoulding also obtains mortise aluminium alloy together and the aluminum alloy resin complex of resin combination after cooling.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex, be that above-mentioned aluminum alloy sheet is put into H2SO4 anodizing tank containing about 20wt% concentration as anode unlike surface treatment 1, in 15V voltage, electrolysis 10min at 18 DEG C, dry up.Aluminum alloy sheet surface after adopting the method identical with claim 1 to record electrolysis obtains the thick aluminum oxide rete of 5um, and aluminum oxide rete includes the nanometer micropore that aperture is 20-40nm, and the hole depth of nanometer micropore is 1um.Record the corrosion hole that there is 300-1000nm aperture on the surface of the aluminum alloy sheet after immersion, the hole depth of corrosion hole is 4um.The double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete can be observed, in nanometer micropore and corrosion hole, there is connectivity structure.Obtained aluminum alloy resin complex.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex, be that above-mentioned aluminum alloy sheet is put into H2SO4 anodizing tank containing about 20wt% concentration as anode unlike surface treatment 1, in 40V voltage, electrolysis 10min at 18 DEG C, dry up.Aluminum alloy sheet surface after adopting the method identical with claim 1 to record electrolysis obtains the thick aluminum oxide rete of 5um, and aluminum oxide rete includes the nanometer micropore that aperture is 60-80nm.Record the corrosion hole that there is 300-1000nm aperture on the surface of the aluminum alloy sheet after immersion, the hole depth of corrosion hole is 4um, and the hole depth of nanometer micropore is 1um.The double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete can be observed, in nanometer micropore and corrosion hole, there is connectivity structure.Obtained aluminum alloy resin complex.
Embodiment 4
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex, be that above-mentioned aluminum alloy sheet is put into H2SO4 anodizing tank containing about 20wt% concentration as anode unlike surface treatment 1, in 20V voltage, electrolysis 15min at 18 DEG C, dry up.Aluminum alloy sheet surface after adopting the method identical with claim 1 to record electrolysis obtains the thick aluminum oxide rete of 7um, and aluminum oxide rete includes the nanometer micropore that aperture is 40-60nm.Record the corrosion hole that there is 300-1000nm aperture on the surface of the aluminum alloy sheet after immersion, the hole depth of corrosion hole is 4um, and the hole depth of nanometer micropore is 3um.The double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete can be observed, in nanometer micropore and corrosion hole, there is connectivity structure.Obtained aluminum alloy resin complex.
Embodiment 5
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex, be that above-mentioned aluminum alloy sheet is put into H2SO4 anodizing tank containing about 20wt% concentration as anode unlike surface treatment 1, in 15V voltage, electrolysis 15min at 18 DEG C, dry up.Aluminum alloy sheet surface after adopting the method identical with claim 1 to record electrolysis obtains the thick aluminum oxide rete of 7um, and aluminum oxide rete includes the nanometer micropore that aperture is 20-40nm.Record the corrosion hole that there is 300-1000nm aperture on the surface of the aluminum alloy sheet after immersion, the hole depth of corrosion hole is 4um, and the hole depth of nanometer micropore is 3um.Can observe the double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete, nanometer micropore is communicated with corrosion hole.Obtained aluminum alloy resin complex.
Embodiment 6
The method identical with embodiment 1 is adopted to prepare aluminum alloy resin complex, be that above-mentioned aluminum alloy sheet is put into H2SO4 anodizing tank containing about 20wt% concentration as anode unlike surface treatment 1, in 40V voltage, electrolysis 15min at 18 DEG C, dry up.Aluminum alloy sheet surface after adopting the method identical with claim 1 to record electrolysis obtains the thick aluminum oxide rete of 7um, and aluminum oxide rete includes the nanometer micropore that aperture is 60-80nm.Record the corrosion hole that there is 300-1000nm aperture on the surface of the aluminum alloy sheet after immersion, the hole depth of corrosion hole is 4um, and the hole depth of nanometer micropore is 3um.Can observe the double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete, nanometer micropore is communicated with corrosion hole.Obtained aluminum alloy resin complex.
Embodiment 7
The method identical with embodiment 2 is adopted to prepare aluminum alloy resin complex, be the sodium carbonate 500ml (pH=11.9) preparing 5wt% in beaker unlike surface treatment 2,20 DEG C, gained aluminum alloy sheet is soaked wherein, taken out after 5min, put into the beaker that water is housed and soak 1min, circulation like this 5 times, after last water soaking, aluminum alloy sheet is dried up, aluminum alloy sheet surface after adopting the method identical with claim 1 to record electrolysis obtains the thick aluminum oxide rete of 5um, and aluminum oxide rete includes the nanometer micropore that aperture is 20-40nm.Record the corrosion hole that there is 300-600nm aperture on the surface of the aluminum alloy sheet after immersion, the hole depth of corrosion hole is 2um, and the hole depth of nanometer micropore is 3um.Can observe the double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete, nanometer micropore is communicated with corrosion hole.Obtained aluminum alloy resin complex.
Embodiment 8
The method identical with embodiment 2 is adopted to prepare aluminum alloy resin complex, be the sodium bicarbonate 500ml (pH=10) preparing 15wt% in beaker unlike surface treatment 2,20 DEG C, gained aluminum alloy sheet is soaked wherein, taken out after 5min, put into the beaker that water is housed and soak 1min, circulation like this 5 times, after last water soaking, aluminum alloy sheet is dried up, aluminum alloy sheet surface after adopting the method identical with claim 1 to record electrolysis obtains the thick aluminum oxide rete of 5um, and aluminum oxide rete includes the nanometer micropore that aperture is 20-40nm.Record the corrosion hole that there is 300-600nm aperture on the surface of the aluminum alloy sheet after immersion, the hole depth of corrosion hole is 2um, and the hole depth of nanometer micropore is 3um.Can observe the double-deck stereo hollow structure that there is similar as shown in Figure 1 in aluminum oxide rete, nanometer micropore is communicated with corrosion hole.Obtained aluminum alloy resin complex.
Comparative example 1
1, pre-treatment: by thick for commercially available 1mm 5052 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, clean with dehydrated alcohol afterwards, then aluminum alloy base material is immersed in the aqueous sodium hydroxide solution of 2wt%, after 2min, taking-up is clean with deionized water rinsing, obtains the aluminum alloy sheet through pre-treatment;
2, surface treatment: aluminum alloy base material being immersed in concentration is in a hydrazine hydrate aqueous solution (PH=11.2) of 5wt%, flood 2min at 50 DEG C after, taking-up washed with de-ionized water is clean, repeat this steeping process 30 times, then take out and put into loft drier, dry for standby at 60 DEG C;
3, shaping: the aluminum alloy sheet after drying is inserted in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) resin combination of 30wt% glass fibre, and the demoulding also obtains mortise aluminium alloy together and the aluminum alloy resin complex of resin combination after cooling.
Comparative example 2
1, pre-treatment: by thick for commercially available 1mm 5052 aluminium alloy plates, be cut into the rectangular pieces of 15mm*80mm, put it into grinding in polishing machine, clean with dehydrated alcohol afterwards, then aluminum alloy base material is immersed in the aqueous sodium hydroxide solution of 2wt%, after 2min, taking-up is clean with deionized water rinsing, obtains the aluminum alloy sheet through pre-treatment;
2, surface treatment: above-mentioned aluminum alloy sheet is put into H2SO4 anodizing tank containing about 20wt% concentration as anode, and electrolysis 10min, dries up under 15V voltage;
3, shaping: the aluminum alloy sheet after drying is inserted in injecting molding die, injection moulding contains polyphenylene sulfide (PPS) resin combination of 30wt% glass fibre, and the demoulding also obtains mortise aluminium alloy together and the aluminum alloy resin complex of resin combination after cooling.
Performance test:
The bonding force of aluminium alloy and resin: aluminum alloy resin complex prepared by embodiment 1-8 and comparative example 1-2 is fixed on universal testing machine and carries out product Elongation test, in test result, ultimate load can be considered the size of the bonding force between aluminium alloy and resin, and test result is as table 1.
Table 1
The bonding force that can obtain resin and aluminium alloy in aluminum alloy resin complex of the present invention from table can reach more than 1211N, bonding force is excellent, and the bonding force of resin and aluminium alloy only only has tens or hundreds of in existing complex body, more existing aluminum alloy resin complex, performance is largely increased, and resin forming is easier, aluminium alloy do not need extra group can with resin mortise, intensity is higher, and little to metallic matrix size impact, heat release is little, on aluminium alloy outward appearance substantially without impact.The direct injection moulding of resin simultaneously enters in micron-sized surperficial macropore, is easier to, does not also specially require synthetic resins, and the scope of application is wider, and environmentally safe, be more suitable for scale operation.
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 (13)
1. an aluminum alloy resin complex, it is characterized in that, comprise: aluminum alloy base material and resin layer, described aluminum alloy base material comprises the anode oxidation membrane on aluminium alloy body and surface thereof, described anode oxidation membrane is made up of extexine part and interior layer segment, and containing corrosion hole in described extexine part, the aperture of described corrosion hole is 200nm-2000nm, described interior layer segment contains the nanometer micropore produced because of anodic oxidation, and described corrosion hole is communicated with described nanometer micropore; The resin combination forming described resin layer is filled in described nanometer micropore and corrosion hole.
2. aluminum alloy resin complex according to claim 1, is characterized in that, the aperture of described corrosion hole is 200-1000nm.
3. aluminium alloy aluminum alloy resin complex according to claim 2, is characterized in that, the aperture of described corrosion hole is 400-1000nm.
4. aluminum alloy resin complex according to claim 1, is characterized in that, the degree of depth of described corrosion hole is 0.5-9.5um.
5. aluminum alloy resin complex according to claim 1, is characterized in that, the thickness of described anode oxidation membrane is 1-10um.
6. aluminum alloy resin complex according to claim 1, is characterized in that, the degree of depth of described nanometer micropore is 0.5-9.5um.
7. aluminum alloy resin complex according to claim 1, is characterized in that, described resin combination is thermoplastic resin composition.
8. aluminum alloy resin complex according to claim 7, is characterized in that, described thermoplastic resin is the blend containing matrix resin and polyolefin resin.
9. aluminum alloy resin complex according to claim 8, is characterized in that, described matrix resin is the mixture of polyphenylene oxide and polyphenylene sulfide, and the fusing point of described polyolefin resin is 65 DEG C-105 DEG C.
10. aluminum alloy resin complex according to claim 9, is characterized in that, in described matrix resin, the weight ratio of polyphenylene oxide and polyphenylene sulfide is 3:1-1:3.
11. aluminum alloy resin complex according to claim 8, is characterized in that, described matrix resin is the mixture of polyphenylene oxide and polymeric amide, and the fusing point of described polyolefin resin is 65 DEG C-105 DEG C.
12. aluminum alloy resin complex according to claim 11, is characterized in that, in described matrix resin, the weight ratio of polyphenylene oxide and polymeric amide is 3:1-1:3.
13. aluminum alloy resin complex according to claim 8, is characterized in that, described matrix resin is polycarbonate, and the fusing point of described polyolefin resin is 65 DEG C-105 DEG C.
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Commission number: 4W107574 Conclusion of examination: Based on the claims submitted by the patentee on September 14, 2018, the patent right for invention No. 201510155667.3 is maintained to be valid. Decision date of declaring invalidation: 20200903 Decision number of declaring invalidation: 45971 Denomination of invention: An aluminum alloy resin composite Granted publication date: 20170531 Patentee: BYD Co.,Ltd. |