CN104711651B - A kind of aluminum alloy resin complex - Google Patents
A kind of aluminum alloy resin complex Download PDFInfo
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- CN104711651B CN104711651B CN201510155667.3A CN201510155667A CN104711651B CN 104711651 B CN104711651 B CN 104711651B CN 201510155667 A CN201510155667 A CN 201510155667A CN 104711651 B CN104711651 B CN 104711651B
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Abstract
The invention provides a kind of aluminum alloy resin complex, including：Aluminum alloy base material and resin bed, the aluminum alloy base material includes the anode oxidation membrane on aluminium alloy body and its surface, the anode oxidation membrane is made up of appearance layer segment and inner portion, contain etch pit on the appearance layer segment, the aperture of the etch pit is 200nm 2000nm, the inner portion contains the nanometer micropore produced by anodic oxidation, and the etch pit is connected with the nanometer micropore；The resin combination for forming the resin bed is filled in the nanometer micropore and etch pit.In the present invention, aluminium alloy can have good adhesion with resin, and process is simple is easily mass produced, pollution-free.
Description
Related application
The application is the divisional application of the Chinese invention patent application of Application No. 201210043634.6.
Technical field
The present invention relates to a kind of aluminum alloy resin complex and preparation method thereof, more particularly, more particularly to one kind has
Aluminum alloy resin complex for having the aluminium alloy in double-deck duct integrated with thermoplastic resin and being formed and preparation method thereof.
Background technology
In the part manufacture field of automobile, household electrical appliance product, industrial machine etc., it is desirable to the one of metal and resin into
Type technology, current industry using adhesive under normal temperature or heating by combination that metal and synthetic resin are integrated.Using above-mentioned
Although method can prepare metal and integrally moulded complex, the complex metal obtained according to these methods and modeling
Adhesion is poor between glue, and adhesive acid-fast alkali-proof poor performance, and complex cannot be carried out at the surfaces such as follow-up anodic oxidation
Reason.Thus, all the time, people are examining whether to have always more reasonably by the engineering resin of high intensity and aluminium alloy etc
The method of alloy integration.
Those skilled in the art is by having researched and proposed nanoprocessing treatment technology, nanoprocessing treatment technology (NMT)
It is exactly metal combination technology integrated with plastic cement, it is by by metal-surface nanoization treatment, allowing plastic cement directly in metal surface
Upper ejection formation, makes metal and the plastic cement can be with integrated molding.For effective combination of metal and plastic cement, nanometer forming technique is
A kind of best methods, and embedded injection or zinc-aluminium, magnalium die casting conventional at present can be replaced, a kind of tool can be provided
There are price competition, high performance gold modeling integration product.Compared with bonding technique, NMT technologies have obvious advantage, for example：
Reduce the overall weight of product, excellent strength, processing efficiency high etc..NMT technology ranges of application cover vehicle, information technoloy equipment and 3C produces
Product, can allow product to develop towards more frivolous, more miniature direction.
It is existing just like the integrated molding technology for disclosing aluminium alloy and resin combination, using amine substance, for example：
The aqueous solution of carbamate, a hydrazine hydrate, ethylenediamine etc. to aluminium alloy be surface-treated and obtains nano level micropore, corrosion
Go out nano level hole, and amine groups are retained in aluminium alloy nano aperture, finally injection is by amine groups and injection
The reaction of material, resin is combined together with aluminum alloy junction, so as to the plastic-aluminum integration for obtaining certain tensile shear strength is produced
Product, and the technology of such amine substance corrosion is used, the hole that etching time is more long and aluminum alloy surface is formed is too small, and resin is difficult
Nano level hole is entered with directly injection, it is poor to reduce the bond strength of aluminium alloy and resin, i.e. tensile resistance, while
The combination of resin and aluminium alloy relies primarily on amine groups, and the species of the resin for using is extremely limited, and the current technology can be used
Resin there was only PPS (polyphenylene sulfide), PA (polyamide), PPA (polyphthalamide resin), PBT (poly terephthalic acid fourths
Diol ester) etc. four resinoids, practical ranges are also narrow, and the amine substance for using be it is poisonous, have volatile material,
It is unfavorable for that safety in production, environmental-protecting performance are poor.
Also have and directly corroded in aluminum alloy surface by the acidic etching liquid containing inorganic halogen compounds, be then molded
Plastic-aluminum integration product, and the technology of such etching corrosion aluminum alloy surface is used, it is long to there is the etchant concentration low time, erosion
Carve liquid concentration exothermic heat of reaction high big, the bad control of temperature is unfavorable for large-scale production, and adopts this method, metal and resin
Between adhesion it is poor.
It is existing also to have the aluminum oxide for preparing the cave with diameter 0.05-0.08 microns by anodic oxidation in aluminum alloy surface
Film layer, then plastic-aluminum integration product is obtained with resin-bonded, but the hole that is formed of the aluminum alloy surface that obtains of the method is too small and tree
Fat is difficult to directly injection and enters nano level hole, reduces the bond strength of aluminium alloy and resin, i.e. tensile resistance poor.
The content of the invention
Adhesion in order to solve aluminium alloy and resin during preparation aluminum alloy resin complex of the prior art of the invention
Weak technical problem.There is provided one kind can have good adhesion, and the aluminium alloy tree that process is simple is easily mass produced with resin
Fat complex and preparation method thereof.
First purpose of the invention is to provide a kind of aluminum alloy resin complex, and the aluminum alloy resin complex includes aluminium
Alloy base material and resin bed, the aluminum alloy base material include the anode oxidation membrane on aluminium alloy body and its surface, the anode
Oxidation film layer is made up of appearance layer segment and inner portion, and etch pit, the hole of the etch pit are contained on the appearance layer segment
Footpath is 200nm-2000nm, and the inner portion contains the nanometer micropore produced by anodic oxidation, the etch pit with it is described
Nanometer micropore is connected；The resin combination for forming the resin bed is filled in the nanometer micropore and etch pit..
Second object of the present invention is to provide the preparation method of above-mentioned aluminum alloy resin complex, comprises the steps of：
S1, the part surface of binding resin part the need for by the surface of the aluminium alloy of pre-treatment or aluminium alloy is passed through
Anodic oxidation obtains the aluminium alloy that the anode oxidation membrane with nanometer micropore is contained on surface；
S2, step S1 aluminium alloys of the gained containing the anode oxidation membrane with nanometer micropore is dipped into etching liquid
It is the etch pit of 200nm-2000nm that anode oxidation membrane extexine forms aperture, obtains surface treated aluminium alloy base
Material；
S3, the step S2 surface treated aluminum alloy base materials of gained are placed in mould, then note resin combination
Mould and be combined with the surface treated aluminum alloy base material in mould, aluminum alloy resin complex is obtained after shaping.This
The inventor of invention is surprised to find that the double-deck stereo hole knot of uniqueness can be formed in aluminum alloy surface by technology of the invention
Structure, aluminum alloy surface forms aluminum oxide film layer, itself has the nanometer micropore of the 10-100nm of excellent performance, and the structure in hole is only
Spy, has good associativity, while being to contain with the surface of resin-bonded in the outer surface of aluminum oxide film layer in itself with resin
The big etch pit of 200nm-2000nm aperture ratio nanometer micropores, by surface pore-creating again, the pore structure for not only being formed is unique, carries
The adhesion of high resin and aluminium alloy, and the resin of injection can preferably penetrate into internal layer by the macroporous structure of outer surface
Aperture in, shaping is easier, aluminium alloy of the invention be not required to it is higher with resin strong bonded, intensity by extra group,
And small is influenceed on metallic matrix size, heat release is small, on aluminium alloy outward appearance substantially without influence.Resin is directly molded and enters micron simultaneously
In the surface macropore of level, it is easier to, synthetic resin is not also specially required, the scope of application is wider, and environmentally safe, more
It is adapted to large-scale production.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention prepare anode oxidation membrane present in double-deck stereo pore structure schematic diagram.
Fig. 2 is scanning electron microscope diagram of the embodiment of the present invention 1 by the aluminum alloy sheet surface of surface treatment 1.
Fig. 3 a, 3b are scanning electron microscope diagram of the embodiment of the present invention 1 by the aluminum alloy sheet surface of surface treatment 2.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention, is not intended to limit the present invention.
The invention provides a kind of aluminium alloy of surface treatment, including aluminium alloy body and its surface anode oxide film
Layer, wherein, anode oxidation membrane is made up of appearance layer segment and inner portion, and etch pit, etch pit are contained on appearance layer segment
Aperture be 200nm-2000nm, inner portion contains nanometer micropore, and the aperture of nanometer micropore is 10-100nm, can be had with resin
Adhesion, and process is simple well is easily mass produced, pollution-free.
The aperture of further preferred nanometer micropore is 20-80nm, is further 20-60nm；It is preferred that the aperture of etch pit
It is 200-1000nm, is still more preferably 400-1000nm.Further optimize the structure of double-hole, be more beneficial for tree during injection
The combination being directly injected into resin and alloy of fat.
It is preferred that the depth of etch pit is 0.5-9.5um, more preferably 0.5-5um, further optimize the knot of etch pit
Structure, makes casting resin be more beneficial for infiltration.
It is preferred that etch pit is connected with nanometer micropore, further preferred double-deck stereo pore space structure is conducive to further providing for
The permeability of resin, improves the adhesion of resin and alloy, and is more beneficial for shaping.
The thickness of preferred anodes oxidation film layer is 1-10um, more preferably 1-5um.Anode oxidation membrane and aluminium alloy
Body can also have adhesion higher, while can also optimize the space of etching complex pore space structure, be easy to produce structure more excellent
Etch pit.
It is preferred that, the depth of nanometer micropore is 0.5-9.5um, more preferably 0.5-5um, optimizes the knot of nanometer micropore
Structure, improves the compactedness of the resin to nanometer micropore of melting, can guarantee that the resin melted in general Shooting Technique is permeable full
The nanometer micropore of this depth, does not reduce the bonded area of resin and anode oxidation membrane not only, and does not exist in nanometer micropore yet
Gap etc., further improves the adhesion of resin and aluminium alloy.
Invention also provides the method for above-mentioned aluminum alloy surface treatment, comprise the steps of：
S1, by by the aluminium alloy of pre-treatment by anodic oxidation obtain surface contain it is micro- with aperture 10-100nm nanometers
The aluminium alloy of the anode oxidation membrane in hole；The anodizing technology that anodic oxidation is known to the skilled person, the present invention can
Using including will be put into 10wt%-30wt% concentration H2SO4 as anode by the aluminium alloy of pre-treatment, 10-30 DEG C of temperature in
1-40min is electrolysed under 10V-100V voltages and obtains the aluminium alloy that the thick anode oxidation membranes of 1-10um are contained on surface, anodic oxidation
Equipment is using known anodic oxidation equipment, such as anodizing tank.
S2, the aluminium alloy immersion containing the anode oxidation membrane with aperture 10-100nm nanometer micropores by step S1 gained
Aperture is formed for the etch pit of 200nm-2000nm is obtained by surface treatment in anode oxidation membrane extexine in etching liquid
Aluminium alloy.This step is that anode oxide film layer surface is corroded using etching liquid so that outside anode oxidation membrane
Top layer forms micron-sized big etch pit, and by this corrosion pore-creating again, in follow-up forming process, resin combination exists
Can be easier to be directly entered in the surface holes of aluminium alloy in injection moulding process, so as to be formed well with aluminium alloy after resin bed is formed
Combination.Etching liquid can be the solution for corroding aluminum oxide film layer, and general use can dissolve the solution regulation concentration of aluminum oxide i.e.
Can, for example can be acid/base etching liquid, the solution of pH=10-13 can be selected from.Can be pH=10-13's under preferable case
Single alkaline solution or composite buffering solution, the single alkaline solution of pH=10-13 can for Na2CO3, NaHCO3, NaOH,
The aqueous solution of K2CO3, KHCO3, KOH etc., the more preferably Na2CO3 and/or NaHCO3 aqueous solution, can make etch pit exist
Aluminum alloy surface is uniformly distributed, and uniform pore diameter, can make the binding ability of resin bed and aluminum alloy base material more preferably, with more
Good tensile strength so that the integration of Al alloy complex combines more preferable.The above-mentioned Na2CO3 and/or NaHCO3 aqueous solution
Solid content can be 0.1wt%-15wt%.Composite buffering solution can be molten for the mixing of soluble phosphoric acid hydrogen salt and water soluble alkali
The solid content of the aqueous solution of the aqueous solution of liquid, such as sodium dihydrogen phosphate and NaOH, sodium dihydrogen phosphate and NaOH can be with
Be 0.1wt%-15wt%, or the aqueous solution of K3PO4 and K2HPO4, composite buffering solution can also for ammonia spirit,
The hydrazine aqueous solution, the hydrazine derivate aqueous solution, the water-soluble amine based compound aqueous solution, NH3-NH4Cl aqueous solution etc..Gained is contained into tool
The aluminium alloy for having the anode oxidation membrane of aperture 10-100nm nanometer micropores be dipped into etching liquid include aluminium alloy is repeatedly more
In secondary immersion etching liquid, the time of each dipping is 1-60min, is washed with deionized water only after dipping every time, and the number of times of immersion can
Think 2 to 10 times.It can be put into rinsing bowl cleaning 1 to 5min to clean, or is put into rinsing bowl and places 1 to 5min.
The pretreatment procedure carried out to aluminum alloy surface that pre-treatment is commonly used for those skilled in the art, generally comprising is carried out
Mechanical grinding or the grinding removal obvious foreign matter in surface, the processing oil for then being adhered to metal surface etc. carry out degreasing, cleaning.It is excellent
Choosing, pre-treatment includes polishing aluminum alloy surface, for example, can be：First using 100-400 mesh sand paper or put
Enter in polishing machine makes the micron-sized aperture of generation to aluminum alloy surface polishing.Then carry out successively oil removing, the first washing, alkaline etching,
The steps such as the second washing, neutralization, the 3rd washing, the various solvents commonly used with those skilled in the art clean the aluminium in ultrasonic wave
Alloy, scavenging period 0.5-2h removes the greasy dirt of aluminum alloy surface；Then aluminium alloy is placed in the acid/base aqueous solution, ultrasound
Aluminum alloy surface is washed under the conditions of ripple.The solvent can be ethanol or acetone.The acid/base aqueous solution is art technology
The various acid/base aqueous solution that personnel commonly use, for example：Can be hydrochloric acid, sulfuric acid, NaOH, potassium hydroxide etc..In the present invention
In, the hydrogen-oxygen for immersing 30-70g/L, 40-80 DEG C of temperature after wiped clean again will be preferably washed after aluminium alloy oil removing with absolute ethyl alcohol
Change and carry out alkaline etching in sodium water solution, taking-up is rinsed well with deionized water after 1~5min, after carried out with the HNO3 of 10-30%
With, the alkaline solution of remained on surface is removed, then rinsed well with deionized water, can be in aluminium alloy base by preferred pre-treatment
The surface of material forms micron-sized aperture, a diameter of 1-10 microns of the aperture.
Need the aluminium alloy present invention of pre-treatment to be not particularly limited, it is possible to use industrial standard 1000-7000 series matters or
The various aluminium alloys of molding grade；Heretofore described aluminium alloy for those skilled in the art commonly use it is variously-shaped, structure
Aluminium alloy, the present invention is not particularly limited.Variously-shaped, the structure of aluminium alloy, can be completed by being machined.
Invention also provides a kind of aluminum alloy resin complex, including：Aluminum alloy base material and resin bed, wherein, aluminium
Alloy base material is the aluminium alloy of above-mentioned surface treatment, formed the resin bed resin combination be filled in the nanometer micropore and
In etch pit.
Wherein, resin combination is the various resin combinations that can be combined with aluminium alloy, and the present invention is not particularly limited,
Can according to actual needs be selected, for example, can be thermoplastic resin composition.Preferred resin composition is thermoplastic resin
Fat.Preferred thermoplastic resin is the blend containing matrix resin and vistanex.It is preferred that matrix resin is noncrystalline
Matrix resin, from noncrystalline matrix resin as injection molding material, its lustrous surface, toughness are better than height of the prior art
Crystalline resin, while with the use of the vistanex that fusing point is 65 DEG C -105 DEG C, need not be in specific mould temperature in shaping
Lower injection, moulding process simplifies, while can guarantee that the metal-resin composite for obtaining has at more preferable mechanical strength and surface
Reason characteristic, so as to solve the problems, such as the incrustation of working of plastics, meets the diversified demand of client.By noncrystalline what is used
In matrix resin, with the use of the vistanex that fusing point is 65 DEG C -105 DEG C, resin can be increased and flow into metal-surface nano level
The ability of micropore, so as to ensure that formed metal has good adhesive force, mechanical strength with plastics.Under preferable case, with
On the basis of the thermoplastic resin of 100 weight portions, wherein the content of matrix resin is 70-95 weight portions, the content of vistanex
It is 5-30 weight portions.
As a further improvement on the present invention, present inventor has further discovered that, in thermoplastic resin use mobility
Modifier, moreover it is possible to improve the fluid ability of resin, further improves the adhesive force and the injection performance of resin of metal and resin.It is excellent
In the case of choosing, on the basis of the thermoplastic resin of 100 weight portions, the flowing of 1-5 weight portions is also contained in the thermoplastic resin
Property modifier.Under preferable case, the fluidity improver is cyclic polyester.
As it was previously stated, in the present invention, the matrix resin is non-crystalline resin.And specifically, it is preferable to, matrix resin is poly-
The mixture of phenylate (PPO) and polyphenylene sulfide (PPS), under preferable case, the weight ratio of PPO and PPS is 3：1-1：3, more preferably
It is 2：1-1：1.Or preferably matrix resin is the mixture of polyphenylene oxide (PPO) and polyamide (PA), under preferable case, PPO with
The weight ratio of PA is 3：1-1：3, more preferably 2：1-1：1.Or preferably matrix resin is makrolon (PC), it can be selected from
Various Linear polycarbonates and/or branched polycarbonate, the present invention is without particular provisions.
In the present invention, the fusing point of the vistanex for being used is 65 DEG C -105 DEG C.Under preferable case, the polyolefin tree
Fat can use grafted polyethylene.In the case of more preferably, it is 100 DEG C or 105 DEG C that the vistanex can use fusing point
Grafted polyethylene.
Resin combination of the invention can also be containing other property-modifying additives etc., and the present invention is not particularly limited, can root
According to needing to set, such as can also contain filler in resin combination.Described filler for those skilled in the art commonly use it is various
Filler, for example, can be various fiberfill or powdery filler.The fiberfill can selected from glass fibre, carbon fiber and
One or more in aramid fibre；The powder-type filler can be selected from calcium carbonate, magnesium carbonate, silica, weight
One or more in matter barium sulfate, talcum powder, glass and clay.In the case of more preferably, to make the horizontal, vertical of plastics composite
To being respectively provided with the linear expansion coefficient close with aluminum alloy base material, in the present invention, on the basis of the matrix resin of 100 weight portions,
Fiberfill content is 50-150 weight portions, and the content of powder-type filler is 50-150 weight portions.
Invention also provides the preparation method of above-mentioned aluminum alloy resin complex, comprise the steps of：At surface
The aluminum alloy base material of reason is placed in mould, is then mutually tied the aluminum alloy base material that resin combination is injected in mould with surface treatment
Close, Al alloy complex is obtained after shaping, wherein, the aluminum alloy base material of surface treatment is the aluminium alloy of above-mentioned surface treatment.
The preparation method of the aluminum alloy resin complex provided according to the present invention, matrix resin, vistanex are mixed
Uniformly, resin combination is prepared.The preparation method of the resin combination is using those skilled in the art often with physical blending
Method is obtained, will matrix resin, vistanex be well mixed, it is stand-by by double screw extruder extruding pelletization.
The preparation method of the Al alloy complex provided according to the present invention, can also fill out toward adding in the matrix resin
Material, fluidity improver, be well mixed, be obtained resin combination so that resin combination it is horizontal, longitudinal direction be respectively provided with
The close linear expansion coefficient of aluminum alloy base material.
Dried aluminum alloy base material is transferred in mould, integrated treatment is carried out with obtained resin combination, be molded
The Al alloy complex of present invention offer is can obtain afterwards, and in the present invention, the method for the shaping is injection moulding, it is possible to understand 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 moulding, example
It such as can also be injection molding mode.It is preferred that the condition being molded is 50~300 DEG C of mould temperature, nozzle temperature：200~450 DEG C, protect
The pressure time：1~50s, projects pressure：50~300MPa, projects the time：1~30s, time delay：1~30s, cool 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, projects the time：3~10s, time delay：15~30s, cool time：15~25s, the resin of formation
The thickness of layer is 0.5~10mm.
Preparation method of the invention is simple, and the technique of more existing use adhesive simplifies production procedure, shortens life
The product time, and more existing nano surface hole injection need to using amine substance corrosion method also significantly reduce corrosion when
Between, the limitation of resin types is breached, only need to be directly molded after being processed using the inventive method and be capable of achieving, while by this hair
Adhesion is good between the resin bed and aluminum alloy base material of the aluminum alloy resin complex obtained by bright preparation method, with preferable
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；
1st, pre-treatment：By commercially available 1mm 5052 aluminium alloy plates of thickness, the rectangular pieces of 15mm*80mm are cut into, put it into throwing
Grinding in ray machine, after cleaned with absolute ethyl alcohol, then aluminum alloy base material is immersed in the sodium hydrate aqueous solution of 40g/L,
Taking-up is rinsed well with deionized water after 2min, is obtained by the aluminum alloy sheet of pre-treatment；
2nd, it is surface-treated 1：Above-mentioned aluminum alloy sheet is put into the H2SO4 anodic oxygens containing 20wt% or so concentration as anode
Change in groove, in 10min is electrolysed at 20V voltages, 18 DEG C, dry up；
3rd, 2 are surface-treated：The sodium carbonate 500ml (pH=12) of preparation 10wt% in beaker, 20 DEG C, by gained aluminium alloy
Piece soaks wherein, is drawn off after 5min, is put into the beaker equipped with water and soaks 1min, so circulation 5 times, last time water logging
After bubble, aluminum alloy sheet is dried up；
Using metallography microscope sem observation by the section of the aluminum alloy sheet of surface treatment 1, measure and closed by the aluminium after electrolysis
Gold plaque surface is obtained the thick aluminum oxide film layers of 5um, and the aluminum alloy sheet surface of surface treatment 1 is passed through using electron microscope observation
(such as Fig. 2), it is the nanometer micropore of 40-60nm or so that can obtain aluminum oxide film layer and be contained within aperture, and the hole depth of nanometer micropore is a 1um left sides
It is right；
Pass through the aluminum alloy sheet surface (such as Fig. 3 a, 3b) of surface treatment 2 using electron microscope observation, after can soaking
There is the etch pit in 300-1000nm apertures on aluminum alloy sheet surface, and the depth of etch pit is 4um, it is also possible to it was observed that aluminum oxide film layer
It is middle to there is the similar double-deck stereo hollow structure of structure as shown in Figure 1, there is connectivity structure in nanometer micropore and etch pit；
4th, it is molded：By in the aluminum alloy sheet insertion injecting molding die after drying, injection contains 30wt% glass fibres
Strong bonded aluminium alloy together is obtained after polyphenylene sulfide (PPS) resin combination, the demoulding and cooling with resin combination
Aluminum alloy resin complex.
Embodiment 2
Aluminum alloy resin complex is prepared using method same as Example 1, the difference is that surface treatment 1 is will be above-mentioned
Aluminum alloy sheet is put into the H2SO4 anodizing tanks containing 20wt% or so concentration as anode, in electricity at 15V voltages, 18 DEG C
Solution 10min, drying.The thick oxidations of 5um are obtained using the aluminum alloy sheet surface after electrolysis is measured with claim 1 identical method
Aluminum membranous layer, aluminum oxide film layer is contained within the nanometer micropore that aperture is 20-40nm, and the hole depth of nanometer micropore is 1um.After measuring immersion
Aluminum alloy sheet surface have the etch pit in 300-1000nm apertures, the hole depth of etch pit is 4um.It is observed that aluminum oxide film layer
It is middle to there is the similar double-deck stereo hollow structure of structure as shown in Figure 1, there is connectivity structure in nanometer micropore and etch pit.Aluminium is obtained
Alloy resin complex.
Embodiment 3
Aluminum alloy resin complex is prepared using method same as Example 1, the difference is that surface treatment 1 is will be above-mentioned
Aluminum alloy sheet is put into the H2SO4 anodizing tanks containing 20wt% or so concentration as anode, in electricity at 40V voltages, 18 DEG C
Solution 10min, drying.The thick oxidations of 5um are obtained using the aluminum alloy sheet surface after electrolysis is measured with claim 1 identical method
Aluminum membranous layer, aluminum oxide film layer is contained within the nanometer micropore that aperture is 60-80nm.Measuring the aluminum alloy sheet surface after immersion has 300-
The etch pit in 1000nm apertures, the hole depth of etch pit is 4um, and the hole depth of nanometer micropore is 1um.It is observed that aluminum oxide film layer
It is middle to there is the similar double-deck stereo hollow structure of structure as shown in Figure 1, there is connectivity structure in nanometer micropore and etch pit.Aluminium is obtained
Alloy resin complex.
Embodiment 4
Aluminum alloy resin complex is prepared using method same as Example 1, the difference is that surface treatment 1 is will be above-mentioned
Aluminum alloy sheet is put into the H2SO4 anodizing tanks containing 20wt% or so concentration as anode, in electricity at 20V voltages, 18 DEG C
Solution 15min, drying.The thick oxidations of 7um are obtained using the aluminum alloy sheet surface after electrolysis is measured with claim 1 identical method
Aluminum membranous layer, aluminum oxide film layer is contained within the nanometer micropore that aperture is 40-60nm.Measuring the aluminum alloy sheet surface after immersion has 300-
The etch pit in 1000nm apertures, the hole depth of etch pit is 4um, and the hole depth of nanometer micropore is 3um.It is observed that aluminum oxide film layer
It is middle to there is the similar double-deck stereo hollow structure of structure as shown in Figure 1, there is connectivity structure in nanometer micropore and etch pit.Aluminium is obtained
Alloy resin complex.
Embodiment 5
Aluminum alloy resin complex is prepared using method same as Example 1, the difference is that surface treatment 1 is will be above-mentioned
Aluminum alloy sheet is put into the H2SO4 anodizing tanks containing 20wt% or so concentration as anode, in electricity at 15V voltages, 18 DEG C
Solution 15min, drying.The thick oxidations of 7um are obtained using the aluminum alloy sheet surface after electrolysis is measured with claim 1 identical method
Aluminum membranous layer, aluminum oxide film layer is contained within the nanometer micropore that aperture is 20-40nm.Measuring the aluminum alloy sheet surface after immersion has 300-
The etch pit in 1000nm apertures, the hole depth of etch pit is 4um, and the hole depth of nanometer micropore is 3um.It is observed that aluminum oxide film layer
Middle to there is the similar double-deck stereo hollow structure of structure as shown in Figure 1, nanometer micropore is connected with etch pit.Aluminium alloy resin is obtained to answer
It is fit.
Embodiment 6
Aluminum alloy resin complex is prepared using method same as Example 1, the difference is that surface treatment 1 is will be above-mentioned
Aluminum alloy sheet is put into the H2SO4 anodizing tanks containing 20wt% or so concentration as anode, in electricity at 40V voltages, 18 DEG C
Solution 15min, drying.The thick oxidations of 7um are obtained using the aluminum alloy sheet surface after electrolysis is measured with claim 1 identical method
Aluminum membranous layer, aluminum oxide film layer is contained within the nanometer micropore that aperture is 60-80nm.Measuring the aluminum alloy sheet surface after immersion has 300-
The etch pit in 1000nm apertures, the hole depth of etch pit is 4um, and the hole depth of nanometer micropore is 3um.It is observed that aluminum oxide film layer
Middle to there is the similar double-deck stereo hollow structure of structure as shown in Figure 1, nanometer micropore is connected with etch pit.Aluminium alloy resin is obtained to answer
It is fit.
Embodiment 7
Aluminum alloy resin complex is prepared using method same as Example 2, the difference is that surface treatment 2 is in beaker
The sodium carbonate 500ml (pH=11.9) of middle preparation 5wt%, by the immersion of gained aluminum alloy sheet wherein, is taken after 5min by 20 DEG C
Go out, be put into the beaker equipped with water and soak 1min, so circulation 5 times, after the immersion of last time water, aluminum alloy sheet is dried up, adopt
The thick aluminum oxide film layers of 5um, pellumina is obtained with the aluminum alloy sheet surface after electrolysis is measured with claim 1 identical method
Layer is contained within the nanometer micropore that aperture is 20-40nm.Measuring the aluminum alloy sheet surface after immersion has the corrosion in 300-600nm apertures
Hole, the hole depth of etch pit is 2um, and the hole depth of nanometer micropore is 3um.It is observed that existing in aluminum oxide film layer as shown in Figure 1
The similar double-deck stereo hollow structure of structure, nanometer micropore is connected with etch pit.Aluminum alloy resin complex is obtained.
Embodiment 8
Aluminum alloy resin complex is prepared using method same as Example 2, the difference is that surface treatment 2 is in beaker
The sodium acid carbonate 500ml (pH=10) of middle preparation 15wt%, by the immersion of gained aluminum alloy sheet wherein, is taken after 5min by 20 DEG C
Go out, be put into the beaker equipped with water and soak 1min, so circulation 5 times, after the immersion of last time water, aluminum alloy sheet is dried up, adopt
The thick aluminum oxide film layers of 5um, pellumina is obtained with the aluminum alloy sheet surface after electrolysis is measured with claim 1 identical method
Layer is contained within the nanometer micropore that aperture is 20-40nm.Measuring the aluminum alloy sheet surface after immersion has the corrosion in 300-600nm apertures
Hole, the hole depth of etch pit is 2um, and the hole depth of nanometer micropore is 3um.It is observed that existing in aluminum oxide film layer as shown in Figure 1
The similar double-deck stereo hollow structure of structure, nanometer micropore is connected with etch pit.Aluminum alloy resin complex is obtained.
Comparative example 1
1st, pre-treatment：By commercially available 1mm 5052 aluminium alloy plates of thickness, the rectangular pieces of 15mm*80mm are cut into, put it into throwing
Grinding in ray machine, after cleaned with absolute ethyl alcohol, then aluminum alloy base material is immersed in the sodium hydrate aqueous solution of 2wt%,
Taking-up is rinsed well with deionized water after 2min, is obtained by the aluminum alloy sheet of pre-treatment；
2nd, it is surface-treated：Aluminum alloy base material is immersed in the hydrazine hydrate aqueous solution (PH=11.2) that concentration is 5wt%,
Taking-up is cleaned up with deionized water after impregnating 2min at 50 DEG C, repeats this dipping process 30 times, is then taken out and is put into drying
Case, dry for standby at 60 DEG C；
3rd, it is molded：By in the aluminum alloy sheet insertion injecting molding die after drying, injection contains 30wt% glass fibres
Strong bonded aluminium alloy together is obtained after polyphenylene sulfide (PPS) resin combination, the demoulding and cooling with resin combination
Aluminum alloy resin complex.
Comparative example 2
1st, pre-treatment：By commercially available 1mm 5052 aluminium alloy plates of thickness, the rectangular pieces of 15mm*80mm are cut into, put it into throwing
Grinding in ray machine, after cleaned with absolute ethyl alcohol, then aluminum alloy base material is immersed in the sodium hydrate aqueous solution of 2wt%,
Taking-up is rinsed well with deionized water after 2min, is obtained by the aluminum alloy sheet of pre-treatment；
2nd, it is surface-treated：Above-mentioned aluminum alloy sheet is put into the H2SO4 anodic oxygens containing 20wt% or so concentration as anode
Change in groove, in 10min is electrolysed under 15V voltages, dry up；
3rd, it is molded：By in the aluminum alloy sheet insertion injecting molding die after drying, injection contains 30wt% glass fibres
Strong bonded aluminium alloy together is obtained after polyphenylene sulfide (PPS) resin combination, the demoulding and cooling with resin combination
Aluminum alloy resin complex.
Performance test：
The adhesion of aluminium alloy and resin：Aluminum alloy resin complex prepared by embodiment 1-8 and comparative example 1-2 is fixed
Product extension test is carried out in universal testing machine, maximum load can be considered the knot between aluminium alloy and resin in test result
Size with joint efforts, test result such as table 1.
Table 1
The adhesion that resin and aluminium alloy in aluminum alloy resin complex of the invention can be obtained from table can reach 1211N
More than, adhesion is excellent, and the adhesion of resin and aluminium alloy only only tens or hundreds of in existing complex, it is more existing
Aluminum alloy resin complex, performance is largely increased, and resin forming is easier, aluminium alloy be not required to by extra group with
Resin strong bonded, intensity is higher, and influences small to metallic matrix size, and heat release is small, on aluminium alloy outward appearance substantially without influence.Together
When resin be directly molded into micron-sized surface macropore, be easier to, synthetic resin is not also specially required, the scope of application
It is wider and environmentally safe, it is more suitable for large-scale production.
Those skilled in the art are readily apparent that, the foregoing is only presently preferred embodiments of the present invention, are not used to limit
The system present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., should be included in
Within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (13)
1. a kind of aluminum alloy resin complex, it is characterised in that including：Aluminum alloy base material and resin bed, the aluminum alloy base material
Anode oxidation membrane including aluminium alloy body and its surface, the anode oxidation membrane is by appearance layer segment and inner portion group
Into, etch pit is contained on the appearance layer segment, the aperture of the etch pit is 200nm-2000nm, and the inner portion contains
The nanometer micropore produced by anodic oxidation, the etch pit is connected with the nanometer micropore；Form the resin of the resin bed
Composition is filled in the nanometer micropore and etch pit.
2. aluminum alloy resin complex according to claim 1, it is characterised in that the aperture of the etch pit is 200-
1000nm。
3. aluminium alloy aluminum alloy resin complex according to claim 2, it is characterised in that the aperture of the etch pit is
400-1000nm。
4. aluminum alloy resin complex according to claim 1, it is characterised in that the depth of the etch pit is 0.5-
9.5um。
5. aluminum alloy resin complex according to claim 1, it is characterised in that the thickness of the anode oxidation membrane is
1-10um。
6. aluminum alloy resin complex according to claim 1, it is characterised in that the depth of the nanometer micropore is 0.5-
9.5um。
7. aluminum alloy resin complex according to claim 1, it is characterised in that the resin combination is thermoplastic resin
Oil/fat composition.
8. aluminum alloy resin complex according to claim 7, it is characterised in that the thermoplastic resin is to contain main body
The blend of resin and vistanex.
9. aluminum alloy resin complex according to claim 8, it is characterised in that the matrix resin be polyphenylene oxide with it is poly-
The mixture of diphenyl sulfide, the fusing point of the vistanex is 65 DEG C -105 DEG C.
10. aluminum alloy resin complex according to claim 9, it is characterised in that in the matrix resin polyphenylene oxide with
The weight ratio of polyphenylene sulfide is 3：1-1：3.
11. aluminum alloy resin complexes according to claim 8, it is characterised in that the matrix resin be polyphenylene oxide with
The mixture of polyamide, the fusing point of the vistanex is 65 DEG C -105 DEG C.
12. aluminum alloy resin complexes according to claim 11, it is characterised in that in the matrix resin polyphenylene oxide with
The weight ratio of polyamide is 3：1-1：3.
13. aluminum alloy resin complexes according to claim 8, it is characterised in that the matrix resin is makrolon,
The fusing point of the vistanex is 65 DEG C -105 DEG C.
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| CN105506703A (en) * | 2015-11-25 | 2016-04-20 | 广东长盈精密技术有限公司 | Preparation method of metal plastic compound |
| CN108265323B (en) * | 2016-12-30 | 2019-11-05 | 比亚迪股份有限公司 | Al-alloy casing and preparation method thereof and personal electronic equipments |
| CN108265321B (en) * | 2016-12-30 | 2019-11-08 | 比亚迪股份有限公司 | Al-alloy casing and preparation method thereof and personal electronic equipments |
| CN108995127B (en) * | 2018-06-25 | 2023-07-04 | 无锡市恒利弘实业有限公司 | Aluminum or aluminum alloy metal surface treatment method |
| CN110358989A (en) * | 2019-06-25 | 2019-10-22 | 忠旺(辽阳)铝模板制造有限公司 | A kind of manufacturing method of aluminium-resin composite materials |
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| CN1436122A (en) * | 2000-04-12 | 2003-08-13 | 三菱树脂株式会社 | Metal sheet coated with resin and method for its production |
| CN1706992A (en) * | 2004-06-04 | 2005-12-14 | 中国科学院化学研究所 | Preparation of solid surfaces with micro- and nanostructures |
| CN101607446A (en) * | 2008-06-17 | 2009-12-23 | 邓子平 | A kind of manufacturing method of aluminum alloy and thermoplastic resin combination |
| US20110287281A1 (en) * | 2009-02-02 | 2011-11-24 | Corona Kogyo Corporation | Composite component of clad material and synthetic resin part and manufacturing method of the same |
| CN102268183A (en) * | 2010-06-04 | 2011-12-07 | 鸿富锦精密工业（深圳）有限公司 | Aluminum or aluminum alloy and plastic composite and manufacturing method thereof |
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|---|---|---|---|---|
| CN1436122A (en) * | 2000-04-12 | 2003-08-13 | 三菱树脂株式会社 | Metal sheet coated with resin and method for its production |
| CN1706992A (en) * | 2004-06-04 | 2005-12-14 | 中国科学院化学研究所 | Preparation of solid surfaces with micro- and nanostructures |
| CN101607446A (en) * | 2008-06-17 | 2009-12-23 | 邓子平 | A kind of manufacturing method of aluminum alloy and thermoplastic resin combination |
| US20110287281A1 (en) * | 2009-02-02 | 2011-11-24 | Corona Kogyo Corporation | Composite component of clad material and synthetic resin part and manufacturing method of the same |
| CN102268183A (en) * | 2010-06-04 | 2011-12-07 | 鸿富锦精密工业（深圳）有限公司 | Aluminum or aluminum alloy and plastic composite and manufacturing method thereof |
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