CN104593786B - The method that a kind of metal surface microporous are processed - Google Patents
The method that a kind of metal surface microporous are processed Download PDFInfo
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Abstract
The invention belongs to material process technical field, the method processing particularly to a kind of metal surface microporous, comprise the steps：1）Metal base through pre-treatment is obtained, by anodic oxidation, the metal base that anode oxidation membrane is contained on surface, 2）By step 1）Process in gained metal base immersion etching liquid；3）By step 2）Gained metal base is put into sulfur acid, is modified in ammonium chloride anodizing tank processing；4）By step 3）Gained metal base is put in phosphate radical solution and is soaked, and washing is clean, then puts it in cleaning adjustment, soaks at room temperature, washing is clean, toasts 0.5 ~ 1 hour.Reach the purpose of borehole enlargement by the controlled AAO film mode of production of condition, solve the problems, such as that conventional pore forming method can not obtain controlled micropore in order, avoid to the many-side rigors such as product size, structure from macroscopical angle.
Description
Technical field
The invention belongs to material process technical field, the method processing particularly to a kind of metal surface microporous.
Background technology
In fields such as mobile communication equipment, electronic and electrical equipment, automobile mechanicals it is often necessary to spray to metal surface
Apply, bond, being molded etc., in order to improve the bond strength of surface attachments, it usually needs surface is processed, as common phosphorus
Change, passivation and manufacture hole, the processing method such as back-off, in brief, be all by increase corrosion resistance of surface and roughness Lai
Improve metal and attachment bond strength.Traditional be using phosphatization, passivation by the way of be by chemical solution immersion treatment
Method metal surface is corroded, reach not only metal surface is carried out protect but also surface is carried out roughening to improve metal
With the purpose of attachment bond strength, it is uneven irregular that this method obtains matsurface, is suitable only for the rough letter of comparison
Single protection, its surface attachments bond strength of metal after treatment is relatively low, and the conventional micropore that manufactures makes rough surface
Method species is more, and such as patent CN102537066A, CN102145331A, CN1584119A, CN101578018A etc. propose
Laser micromachining process, assembling coating, the design method such as fillet back-off is embedded, all referred to raising metal from all angles
The method of surface and attachment bond strength, however all different degrees of presence complex operation of such method, relatively costly, applicable
The each side problem such as face is narrow is so as to application receives certain limitation.
Content of the invention
Present invention aims to the deficiencies in the prior art, and a kind of side of metal surface microporous process is provided
Method, the present invention proposes makes metal surface produce controllability micropore, micro- by the way of electrochemistry and chemical method combine
See level and reach the purpose improving metal surface attachment bond strength.Specifically, it is the anodic oxygen by specific form
Change and make metal form the nanometer three-dimensional set pore structure with certain rule, then nano aluminium oxide is passed through to the nanometer micropore being formed
The growth pattern of AAO film carries out controllability reaming, so that metal surface is reached and has the controlled roughness of size, thus reaching metal
Surface microporeization improves the purpose of attachment bond strength.
In order to realize above-mentioned purpose, the present invention employs the following technical solutions：
The method that a kind of metal surface microporous are processed, comprises the steps：1）Anodic oxidation：By the gold through pre-treatment
Belong to base material and the metal base that anode oxidation membrane is contained on surface is obtained by anodic oxidation, described metal base is aluminum alloy base material
Or aluminium base.
2）Move back anode oxide film：By step 1）Locate in the metal base immersion etching liquid that gained contains anode oxidation membrane
Reason, the metal base of the anode oxidation membrane that is removed, H in described etching liquid+/OH-Concentration is 0.55 ~ 5.5mol/L, described erosion
Carve in liquid and contain fluorion and/or phosphate anion, and described etching solution also contains aluminium corrosion inhibiter.
Move back anode oxide film step to its object is to make metal surface form " hole core " by chemical attack oxide-film, be two
Secondary anode micro porous metallic matrix growth provides basic point, because the hole of the nano metal matrix micropore of anodic oxidation generation has
Sequence degree is not high, pore size is inconsistent, with the formation of " hole core ", makes the electric field intensity being originally distributed in surface concentrate on hole
Bottom, leads to the rate of dissolution of hole bottom barrier and oxidation rate to greatly improve, final rate of dissolution and growth rate reach one
Individual dynamic equilibrium, nanometer micropore metallic matrix is stabilized growth, during subsequent treatment process attachment can even into micropore,
Improve the bond strength purpose consistent with ensureing each position bond strength to reach.
The basic procedure that anodic oxidation can produce micropore is metallic matrix（As aluminum）Lose electronics under applied voltage to become
Al3+, it is to external migration, O2-And OH-Inward migration, metal/oxide interface constantly forms new barrier layer, thick with aluminium oxide
Degree increases voltage and increases, and electrochemical reaction slows down, and now temperature raises, and electrolyte produces dissolved corrosion to aluminium oxide, due to corruption
The dispersibility of erosion liquid, to recessed, resistance reduction, voltage reduces at aluminium oxide relatively thin position, and aluminium oxide continues to generate, with reaction
Carrying out, the aluminium oxide of recess generates and dissolving reaches balance, and reaction is carried out always, and thickness of aluminum alloy does not increase, and recess
Gradually recessed ultimately form nano-pore.Because producing the position that recessed position is aluminum oxide film, the position of aluminum oxide film at first
It is because aluminium base surface microscopic uneven distribution, and aluminium base surface microscopic thin and thick and size are uneven in itself, therefore produce
Raw nanometer micropore is uneven, by moving back the rough polishing of anode oxide film, makes surface only remain atomic little " hole core ", from
And the nano-pore that basic guarantee secondary anode produces has preferable uniformity.
3）Modified anodic oxidation：By step 2）Gained metal base is put into sulfur acid, is carried out in ammonium chloride anodizing tank
Modification, obtains the metal base of modified anode oxidation membrane.
Wherein said modified anodic oxidation is to introduce aluminum alloy surface can be produced in conventional anodizing solution
The anion of spot corrosion；Described modified anodic oxidation is to introduce metal surface can be produced in conventional anodizing solution
The anion of spot corrosion, makes in anode oxidation process, produces little anode hole and produces big etch pit, and now
The micropore producing is growth upper in first time anodic oxidation residual " hole core ", and thus grow nanometer level microporous has preferably
Order, and because the presence of spot corrosion generates big micropore, both are interweaved, and ultimately form the three of big borehole jack aperture
Dimension topological structure.
4）Surface adjusts：By step 3）Described in gained, metal base puts into H+Concentration is that the phosphate radical of 0.1 ~ 1mol/L is molten
In liquid, soak 1 ~ 30 minute at 40 ~ 60 DEG C, washing is clean, then put it into during cleaning adjusts, soak 1 under section room temperature ~
30 minutes, washing was clean, toasted 0.5 ~ 1 hour at a temperature of 65 DEG C.Wherein special micro- described in the adjustment of surface
Hole control methods are the growth rhythm control methods using nanometer anodised aluminium AAO film, specifically, be by phosphoric acid corrosion method Lai
Control the aperture of nano-pore.
The present invention is to generate in improved method using the micropore that short time anodic oxidation produces to have suitable spatial hole
The porous oxygen film of gauge structure, then through reaming to required aperture, using micropore crab-bolt effect it is ensured that having between metal and attachment
Higher bond strength.
Carry out two-step anodization, including conventional anodes oxidation, move back anode oxide film and modified anodic oxidation three step, in gold
Belong to carrying out aoxidizing after surface treatment in acid solution and include sulphuric acid anodizing method, phosphate anodizing, oxalic acid anode
Oxidizing process and mixed acid anodic oxidation method, its object is to metal surface generate substantial amounts of nanometer level microporous, micropore straight
Footpath about 1～15nm, then through surface adjustment, obtain making surface have a certain size three-dimensional micropore, then by the side of reaming
Formula makes surface micropore reach required aperture, can directly improve the metallic matrix on its surface and the bond strength of attachment.
As a modification of the present invention, described step 1) in, the metal base of pre-treatment is, by some pieces of metal bases
It is soaked in 300 seconds in degreasing agent, temperature is set to 60 DEG C；It is soaked in the sodium hydrate aqueous solution of 20 ~ 80g/l after washing is clean again
40 seconds, temperature was set to 65 DEG C；It is soaked under room temperature after washing totally 40 seconds in the aqueous solution of nitric acid that concentration is 25% and be obtained again.
As a modification of the present invention, described step 1）In, the metal base through pre-treatment is put into containing 190g/
In the sulphuric acid anodizing groove of l, temperature is maintained at 17 DEG C, the lower oxidation of voltage 18V 8 minutes.
As a modification of the present invention, described step 2）Including by step 2）Gained contains the metal of anode oxidation membrane
Base material repeatedly immerses in etching liquid and processes, and the time processing in immersion etching liquid every time is 2 ~ 10min, every time in immersion etching liquid
Wash after process.
As a modification of the present invention, the number of times of described immersion is 2 to 10 times.
As a modification of the present invention, described step 3）In, enter including to the metal base of modified anode oxidation membrane
Row surface clean, described cleaning is adjusted and is made up of alkalescence salt, organic amine and surfactant, the cleaning 1 ~ 10 every time of cleaning micropore
Minute.
Described surface clean to be neutralized cleaning using the weakly alkaline solution being easier to rinse and to remain in the moon in micropore
Ion, can be using alkalescence salt perforated membrane being acted on almost without corrosion failure in room temperature, organic amine, table as its settling mode
Face activating agent cleans 1-10 minute every time cleaning micropore, cleans 1-10 time.Because anode oxidation process is cloudy in doped solution
The process of ionic adsorption, wherein have is then to adsorb on the hole wall of perforated membrane, and have is then presented in chemical bond, and
And the distribution of its concentration in gradient, the process of cleaning is for preventing the anion remaining from attachment can invade and receive in subsequent technique
During meter Wei Kong, its binding ability is produced and destroy.
As a modification of the present invention, described organic amine is by triethanolamine, triethylene diamine, dimethyl amine, pyridine, piperazine
One or more compositions of pyridine and quinoline.
As a modification of the present invention, described alkalescence salt is by sodium gluconate, sodium benzoate, sodium glutamate, winestone
One or more compositions of sour potassium sodium and sodium bicarbonate.
As a modification of the present invention, described surfactant is by hexadecyltrimethylammonium chloride, octyl trimethyl
Ammonium chloride, one or more compositions of dihydroxy ethyl oleic imidazolinone.
As a modification of the present invention, by step 1）~4）The surface of the metallic matrix of preparation forms big borehole jack aperture
Three dimensional structure, 0.1-1 μm of macropore diameter, small aperture 1-15nm, and reaming speed substantially meets the linear pass of Y=a*X+b
System, wherein：Y represents the aperture of aluminium oxide micropore, X represents etching time, a and b is constant, variable concentrations, at a temperature of constant
Value is different.
Beneficial effects of the present invention：Using with upper type anodic oxidation, so that the micropore of generation is had preferably has the present invention
Sequence, and the micropore that ion forms set well format is added by introducing, solve conventional chemical corrosion and passivation method and combine by force
The not high problem of degree, then the purpose of borehole enlargement is reached by the controlled aluminium oxide AAO film mode of production of condition, often solve
Rule pore forming method can not obtain the problem of controlled micropore in order, avoids to many-sides such as product size, structures from macroscopical angle
Rigors.
Brief description
Fig. 1 is the linear relationship chart when 5%, temperature is 40 DEG C to nano aluminium oxide reaming for the phosphoric acid quality concentration.
Fig. 2 be the present invention anodic oxidation after through 100,000 times of electron microscope observations to picture.
Fig. 3 is to picture after the embodiment of the present invention 1 methods described is processed through 100,000 times of electron microscope observations.
Fig. 4 is to picture after the embodiment of the present invention 2 methods described is processed through 100,000 times of electron microscope observations.
Specific embodiment
Below in conjunction with the accompanying drawings 1 to 4 and specific embodiment, the present invention will be described.
Embodiment 1
The method that a kind of metal surface microporous are processed, comprises the steps：1）Anodic oxidation：By the gold through pre-treatment
Belong to base material and the metal base that anode oxidation membrane is contained on surface is obtained by anodic oxidation, described metal base is aluminum alloy base material
Or aluminium base；2）Move back anode oxide film：By step 1）Locate in the metal base immersion etching liquid that gained contains anode oxidation membrane
Reason, the metal base of the anode oxidation membrane that is removed, H in described etching liquid+/OH-Concentration is 0.55 ~ 5.5mol/L, described erosion
Carve in liquid and contain fluorion and/or phosphate anion, and described etching solution also contains aluminium corrosion inhibiter；3）Modified anodic oxidation：
By step 2）Gained metal base is put into sulfur acid, is modified in ammonium chloride anodizing tank processing, and obtains modified anodic oxygen
Change the metal base of film layer；4）Surface adjusts：By step 3）Described in gained, metal base puts into H+Concentration is 0.1 ~ 1mol/L
Phosphate radical solution in, soak 1 ~ 30 minute at 40 ~ 60 DEG C, washing is clean, then put it into during cleaning adjusts, in section room
The lower immersion of temperature 1 ~ 30 minute, washing is clean, toasts 0.5 ~ 1 hour at a temperature of 65 DEG C.
Specifically, a. pre-treatment：6063 thick for commercially available 1.0mm Aluminum Cuttings are become the small pieces of many 15mm × 50mm,
Ten are taken firmly to hang over it on titanium alloy hanger at random；Then it is soaked in 300 seconds in aluminium degreasing agent, temperature is set to 60 DEG C；
It is soaked in 40 seconds in the sodium hydrate aqueous solution of 70g/l after washing is clean, temperature is set to 65 DEG C again；Soak after washing totally again
In volumetric concentration be 25% aqueous solution of nitric acid in 40 seconds, room temperature；
B. anodic oxidation：Will（1）Step aluminum alloy sheet is put in the sulphuric acid anodizing groove containing 190g/l, in 18 DEG C, 18V
Oxidation at voltages 8 minutes, washing is clean；
C. move back anode oxide film：Will（2）The volumetric concentration that step aluminium flake is put into is 5% phosphoric acid and the water of 3g/l chromic anhydride
Soak 20 minutes at 70 DEG C in solution, washing is clean；
D. modified anodic oxidation：Will（3）Step aluminum alloy sheet puts into sulphuric acid containing 190g/l, 0.5g/l ammonium chloride anodic oxygen
Change in groove, in 18 DEG C, the oxidation at voltages of 18V 8 minutes, washing is clean；
E. surface adjustment：Will（4）Step aluminium alloy is put in the phosphate aqueous solution of 50g/l, soaks 6 minutes at 40 DEG C,
Washing is clean；
F. surface clean：Will（5）Walk the aluminium alloy obtaining to put in the sodium gluconate solution of 5g/l, soak at room temperature
Bubble 6 minutes, washing is clean, toasts 30 minutes at a temperature of 65 DEG C, you can.
And the aluminium flake crossed using SU-70 thermal field emission scanning electron microscopic observation surface treated is it was observed that surface is uniformly distributed
Average pore size（Macropore diameter is average with small aperture）For 40nm（R2=0.9941）Aluminium oxide micropore, according to using phosphorus
Acid corrosion method growing the experience of nano aluminium oxide AAO film, its concentration and temperature-resistant when, change when soaking in the adjustment of surface
Between（I.e. etching time）, select 3 ~ 21 minutes, every sampling in three minutes once, using SU-70 thermal field emission scanning electron microscopic observation
The aluminium flake that surface treated is crossed, obtains with aperture as vertical coordinate, the concrete numerical value with etching time as abscissa, as shown in figure 1,
The reaming speed of phosphoric acid substantially meets Y=a*X+b, wherein, a=3.369, b=11, such as Fig. 1 linear relationship, its reaming speed is about
3.369nm/min, it can be seen that it is only necessary to adjustment etching time can get the nano oxygen of desired aperture footpath size from trendgram
Change aluminum micropore.Because the concentration of phosphoric acid, temperature, time all have controllability operation to aluminium alloy micropore.
Embodiment 2
Using ten aluminum alloy sheets of identical step process in embodiment 1, difference is：C. move back anode oxide film,
Soaked 3 minutes at 40 DEG C using 20g/l sodium hydroxide, 2g/l vinylthiourea and 2g/l xylitol, in the adjustment of e. surface, phosphorus
Acid soak time lengthening was to 15 minutes.The aluminium flake crossed using SU-70 thermal field emission scanning electron microscopic observation surface treated it was observed that
Surface is uniform-distribution with the aluminium oxide micropore that average pore size is 70nm.Other are identical with experimental example 1, and here is omitted, and it is same
Sample obtains the linear relationship meeting Y=a*X+b.
Comparative example 1
Using ten aluminum alloy sheets of identical step process in embodiment 1, ten aluminium alloys are separately taken only to do（1）Pre-treatment walks
Suddenly, respectively last layer terminal hydroxy group acrylic acid baking vanish resin is applied to 20 aluminium alloys, after drying, adopt paint film adhesion algoscopy
（GB1720-79）Ten aluminum alloy surface paint film adhesions processing through surface microporeization of evaluation have seven to be 1 grade, and three are
2 grades, ten aluminum alloy surface paint film adhesions merely through pre-treatment of evaluation have a piece of be 1 grade, eight are 2 grades, and a piece of is 3
Level.
Comparative example 2
Using ten aluminum alloy sheets of identical step process in embodiment 1, ten aluminium alloys are separately taken only to do（1）Pre-treatment walks
Suddenly, polyphenylene sulfoether resin mixture is made to be bonded to aluminum alloy surface by the way of injection 20 aluminium alloys respectively,
Measure the standard test method of the gluing bond strength by shearing force using tensile load method（ASTM D2919-2000）Measure two
Ten aluminium alloys and the shearing force of resin-bonded thing, measure the combination of ten aluminium alloys through surface microporeization process and resin
Intensity average out to 24.6MPa, the bond strength meansigma methodss of ten aluminium alloys merely through pre-treatment and resin only have 4.6MPa.Its
, with embodiment 3, here is omitted for he.
With comparative example as can be seen that using the rule controllability micropore gained obtained by the present invention from above-described embodiment
Metallic matrix, so as to surface has some micropores, greatly improves adhesive force, can significantly improve metal and surface attachment
Thing（As paint, ink, coating, dyestuff, resin and adhesive etc.）Between bond strength.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out suitable change and modification.Therefore, the invention is not limited in specific embodiment disclosed and described above, to this
In the scope of the claims that some modifications and changes of invention should also be as fall into the present invention.Although additionally, this specification
In employ some specific terms, but these terms are merely for convenience of description, do not constitute any restriction to the present invention.
Claims (10)
1. the method that a kind of metal surface microporous are processed is it is characterised in that comprise the steps：
1）Anodic oxidation：Metal base through pre-treatment is obtained, by anodic oxidation, the gold that anode oxidation membrane is contained on surface
Belong to base material, described metal base is aluminum alloy base material or aluminium base；
2）Move back anode oxide film：By step 1）Process in the metal base immersion etching liquid that gained contains anode oxidation membrane, obtain
To the metal base removing anode oxidation membrane, H in described etching liquid+/OH-Concentration is 0.55 ~ 5.5mol/L, described etching liquid
In contain fluorion and/or phosphate anion, and described etching liquid also contains aluminium corrosion inhibiter；
3）Modified anodic oxidation：By step 2）Gained metal base is put into sulfur acid, is modified in ammonium chloride anodizing tank
Process, obtain the metal base of modified anode oxidation membrane；
4）Surface adjusts：By step 3）Described in gained, metal base puts into H+Concentration is in the phosphate radical solution of 0.1 ~ 1mol/L,
Soak 1 ~ 30 minute at 40 ~ 60 DEG C, washing is clean, then put it in cleaning adjustment, soak 1 ~ 30 minute at room temperature,
Washing is clean, toasts 0.5 ~ 1 hour at a temperature of 65 DEG C.
2. metal surface according to claim 1 microporous process method it is characterised in that：Described step 1) in, front
The metal base processing is some pieces of metal bases to be soaked in 300 seconds in degreasing agent, temperature is set to 60 DEG C；After washing is clean
It is soaked in 40 seconds in the sodium hydrate aqueous solution of 20 ~ 80g/l, temperature is set to 65 DEG C again；Soak under room temperature after washing totally again
In volumetric concentration be 25% aqueous solution of nitric acid in 40 seconds be obtained.
3. the method that metal surface according to claim 1 microporous are processed is it is characterised in that described step 1）In, will
Put in the sulphuric acid anodizing groove containing 190g/L through the metal base of pre-treatment, temperature is maintained at 17 DEG C, under voltage 18V
Oxidation 8 minutes.
4. metal surface according to claim 1 microporous process method it is characterised in that：Described step 2）Including general
Step 1）The metal base that gained contains anode oxidation membrane repeatedly immerses in etching liquid and processes, and processes every time in immersion etching liquid
Time be 2 ~ 10min, wash after processing in immersion etching liquid every time.
5. metal surface according to claim 4 microporous process method it is characterised in that：The number of times of described immersion is
2 to 10 times.
6. metal surface according to claim 1 microporous process method it is characterised in that：Described step 4）In, bag
Include the metal base to modified anode oxidation membrane and carry out surface clean, described cleaning is adjusted by alkalescence salt, organic amine and table
Face activating agent composition, cleaning micropore cleaning 1 ~ 10 minute every time.
7. metal surface according to claim 6 microporous process method it is characterised in that：Described organic amine is by three second
Hydramine, triethylene diamine, dimethyl amine, one or more compositions of pyridine, piperidines and quinoline.
8. metal surface according to claim 6 microporous process method it is characterised in that：Described alkalescence salt is by Portugal
Grape sodium saccharate, sodium benzoate, one or more compositions of sodium glutamate, sodium potassium tartrate tetrahydrate and sodium bicarbonate.
9. metal surface according to claim 6 microporous process method it is characterised in that：Described surfactant by
One or more compositions of hexadecyltrimethylammonium chloride, octyltrimethylammonium chloride and dihydroxy ethyl oleic imidazolinone.
10. metal surface according to claim 1 microporous process method it is characterised in that：By step 1）~4）System
The surface of standby metallic matrix forms the three dimensional structure of big borehole jack aperture, 0.1-1 μm of macropore diameter, small aperture 1-15nm, and
Reaming speed substantially meets the linear relationship of Y=a*X+b, wherein：Y represents the aperture of aluminium oxide micropore, and X represents etching time, a
Be constant with b, variable concentrations, at a temperature of constant value different.
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| CN105033838B (en) * | 2015-07-27 | 2018-05-15 | 郑州大学 | The forming method of mechanical lapping metal surface micro-nano hole |
| CN105603432B (en) * | 2016-01-21 | 2018-10-09 | 瑞声光电科技(常州)有限公司 | Taking off plating solution and its take off electroplating method for aluminium alloy |
| CN105648441B (en) * | 2016-01-21 | 2019-05-07 | 瑞声光电科技(常州)有限公司 | Taking off plating solution and its take off electroplating method for aluminium alloy |
| CN109338432A (en) * | 2018-11-27 | 2019-02-15 | 东莞市慧泽凌化工科技有限公司 | A kind of electroplating technology of stainless steel and aluminium alloy compound part |
| CN111549348B (en) * | 2020-05-15 | 2022-04-12 | 计锋 | Metal part surface treatment method and metal part plastic complex |
| CN112048747B (en) * | 2020-08-06 | 2021-09-21 | 浙江大华技术股份有限公司 | Surface source black body and preparation method thereof |
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| CN101037783A (en) * | 2006-03-17 | 2007-09-19 | 中国科学院半导体研究所 | Method for preparing orderly anode alumina through-hole template by using anodic oxidation bath |
| CN101838835A (en) * | 2010-03-30 | 2010-09-22 | 同济大学 | Ordered porous alumina template capable of being directly applied to electrochemical deposition and preparation method thereof |
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