CN107190184A - A kind of mirror-like anodic oxidation Aluminum Plate and Strip and preparation method thereof - Google Patents

A kind of mirror-like anodic oxidation Aluminum Plate and Strip and preparation method thereof Download PDF

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Publication number
CN107190184A
CN107190184A CN201710548317.2A CN201710548317A CN107190184A CN 107190184 A CN107190184 A CN 107190184A CN 201710548317 A CN201710548317 A CN 201710548317A CN 107190184 A CN107190184 A CN 107190184A
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anodic oxidation
mirror
ingot
strip
aluminium
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CN201710548317.2A
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Chinese (zh)
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CN107190184B (en
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江钟宇
黄瑞银
吴建新
张宸玮
刘华春
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中铝瑞闽股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08Alloys based on aluminium with magnesium as the next major constituent with silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/047Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent

Abstract

The invention discloses a kind of mirror-like anodic oxidation Aluminum Plate and Strip and preparation method thereof, its ingredient percentage is:Si≤0.03%, Fe≤0.03%, Cu 0.03 ~ 0.08%, Mn 0.06 0.1%, Mg 4.0 5.0%, Zn 0.16 0.25%, Zr 0.05 ~ 0.08%, Ti 0.02 ~ 0.03%, surplus are Al and inevitable impurity;It is, using aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot as raw material, to be made through the step such as founding, hot rolling, cold rolling, heat treatment.Aluminum Plate and Strip of the present invention is after anodic oxidation through mild mechanical polishing grinding, it can reach the mirror effect of high reflecting rate, meet the highlighted outward appearances of electronic product Logo and metal material wishes the demand of glass appearance surface is made, effectively overcome that traditional 5 line aluminium alloy plate face micropore after anodic oxidation is more, shortcoming without mirror effect.

Description

A kind of mirror-like anodic oxidation Aluminum Plate and Strip and preparation method thereof

Technical field

The invention belongs to aluminum and aluminum alloy mateial preparation field, and in particular to a kind of mirror-like anodic oxidation Aluminum Plate and Strip And preparation method thereof.

Background technology

In recent years, aluminium after anodic oxidation because with anti-fingerprint pollution, case hardness is high the features such as, on phone housing It is widely used in a variety of applications, but the hand that shell is brilliant black minute surface is produced in the change with people to aesthetic, especially iPhone7 Machine starts, and increasing mobile phone brand wishes the phone housing of the similar effect of Development and Production.But because tradition 5 is alloy through sun After the oxidation of pole, hexagonal columnar micropore complicated, that arrangement is unordered can be formed on anodic oxide coating, and growth thickness is uneven, makes gold There is rough phenomenon in the anode surface of category shell, surface roughness is larger, in the different situation of influence light refraction angle degree The lower final effect that cannot get minute surface when visually observing.

So far, the research for making it have mirror effect through anodic oxidation to aluminium is less, and proposes by controlling aluminium Compound and finish to gauge grain size in plate base, realize that optimization region of the optimization aluminium after anodic oxidation be heterochromatic or anodic oxidation The uniformity of film it is more, even if in this way, the heterochromatic interface that can not allow aluminum substrate and anode oxide film in good region is put down Directly, the anode oxide film hexagonal prism high-sequential formed on this interface, thickness can not be allowed uniform, cause product surface can not Mirror effect is presented.Primary handset brand manufacturers is using the aluminum products after anodic oxidation as handset shell and added in native land When work is mirror effect or highlighted LOGO, Chinese wax, colored varnish etc. need to be also used to block what anodic oxidation was formed after anodic oxidation Hexagonal prism micropore, then surface polishing grinding is carried out, to reduce surface roughness, reach the effect of minute surface.

The content of the invention

It is an object of the invention to provide a kind of mirror-like anodic oxidation Aluminum Plate and Strip and preparation method thereof, it is in anode After oxidation surface can be in mirror effect, effectively overcome traditional 5 line aluminium alloy plate face micropore after anodic oxidation it is many, without minute surface effect The shortcoming of fruit.

To achieve the above object, the present invention is adopted the following technical scheme that:

A kind of mirror-like anodic oxidation Aluminum Plate and Strip, its ingredient percentage is:Si≤0.03%, Fe≤ 0.03%, Cu 0.03 ~ 0.08%, Mn 0.06-0.1%, Mg 4.0-5.0%, Zn 0.16-0.25%, Zr 0.05 ~ 0.08%, Ti 0.02 ~ 0.03%, remaining is Al and inevitable impurity.

The mirror-like anodic oxidation with Aluminum Plate and Strip be using aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot as raw material, through founding, The step such as hot rolling, cold rolling, heat treatment is made;Its preparation method comprises the following steps:

(1)Aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot carry out dispensing after melting respectively through smelting furnace, then through semi-continuous casting system Obtain ingot casting;

(2)Ingot casting is sent into heating furnace behind sawing, milling face, 440 ~ 450 DEG C are warming up to≤20 DEG C/h speed, insulation 16 ~ 40h, it is to avoid low melting point phase burning, is then brought rapidly up to 530 ~ 550 DEG C, is incubated 1 ~ 12h, allows the abundant solid solutions of Zr, so that casting The thick compound formed during making fully spreads uniformly, then is cooled to 450 ~ 480 DEG C, hot rolling of coming out of the stove, hot rolling finishing temperature For 250 ~ 350 DEG C, hot rolled thickness is 3.0 ~ 10.0mm;

(3)Coiled material after hot rolling is subjected to the cold rolling of 50-80%, 360-460 DEG C, guarantor are then warming up to >=60 DEG C/h speed Warm 2-6h carries out intermediate annealing(It is preferred that continuous annealing furnace is produced), it is thick with local grain to avoid slow heating from causing crystal grain to be grown up Greatly, then it is cold rolled to finished product thickness, cold rolling reduction ratio is 40 ~ 80%, again through stretch-bending straightening after 150-280 DEG C of finished products Finished product.

After stretch-bending straightening of the present invention the tensile strength of gained Aluminum Plate and Strip be 240 ~ 300MPa, yield strength be 205 ~ 235MPa(Case hardness HV75 ~ 81), meet corner after pressing and bending deformation and the demand of cracking do not occur.

Applicant it has been investigated that, crystal grain orientation is different, the direction of growth of the upper hexagonal prism micropore of aluminium alloy anode oxide layer It is different with speed;Correspondingly, the isometric property of crystal grain is higher, and its orientation more reaches unanimity.As any 1mm2In the range of grain size When difference is no more than 3 μm, grain-oriented randomness is minimum, and the orientation uniformity of micropore is very strong after film forming;And add in the alloy Plus a certain amount of Zn, initial film forming speed increase during anodic oxidation, it can further reduce the shadow that crystal grain orientation is orientated to micropore Ring, i.e., when carrying out anodic oxidation on this condition, the interface of aluminum substrate and anode oxide film will tend to be straight.Meanwhile, aluminium alloy In intermetallic compound size can influence current density and Al ion concentrations, and then influence the uniform of anodic oxidation micropore size The thickness of property and oxide-film, if effectively controlling compound size, is beneficial to the homoepitaxial of anode oxide film.

The present invention is using aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot as raw material, after founding, hot rolling, cold rolling and necessary heat treatment In the Aluminum Plate and Strip of production, its intermetallic compound maximum length is no more than 6 μm, crystal grain after intermediate annealing in etc. shaft-like, big It is small to be no more than 30 μm, and any 1mm2In the range of any crystal grain difference in size≤3 μm, make its carry out anodic oxidation When, it is ensured that oxide thickness is uniform and oxidation micropore is High ordering, so that mirror effect is presented;And found through experiment, Under the same terms, even if by the control of intermetallic compound size to less than 6 μm, 5 be that alloy can not still be formed after anodic oxidation Anode oxide film with mirror effect.

Gained mirror-like anodic oxidation Aluminum Plate and Strip of the invention is compared with tradition 5 is, in chemical composition, casting, hot rolling Improved in heating cycle and cold rolling processing technology, make its with general 6063T6 case hardnesses, meet Pressing Deformation It is indehiscent simultaneously, also with aluminum substrate and interfacial oxide film is straight, anode oxide film feature in uniform thickness, so that it is passed through It is the mirror effect not available for alloy that gained anode oxide film, which has general 5, after anodic oxidation.

Embodiment

A kind of mirror-like anodic oxidation Aluminum Plate and Strip, its ingredient percentage is:Si≤0.03%, Fe ≤ 0.03%, Cu 0.03 ~ 0.08%, Mn 0.06-0.1%, Mg 4.0-5.0%, Zn 0.16-0.25%, Zr 0.05 ~ 0.08%, Ti 0.02 ~ 0.03%, surplus is Al and inevitable impurity(The content of every kind of impurity is no more than 0.03%);Gold in its aluminium alloy Compound maximum length is no more than 6 μm between category, crystal grain after intermediate annealing in etc. shaft-like, size be no more than 30 μm, and arbitrarily 1mm2In the range of any crystal grain difference in size≤3 μm, and can meet 205 ~ 235MPa of yield strength in mechanical property, rush The demand that compressive strain is not ftractureed.

Below to the content progress numerical definiteness of each composition the reasons why, is illustrated:

Mg:Mg in alloy is to ensure addition element necessary to sheet alloy intensity, if content is less than 4.0%, finished product surrender Intensity index can not be met, if content is more than 5.0%, on the one hand influenceed Fe, Si, Cu, Mn diffusion in fusion-casting process, made Phase containing Fe forms thick compound during solidification, and then influences finished anode oxide thickness uniformity, is unfavorable for finished product and obtains low The anodized surface of roughness, another aspect Mg contents increase will improve aluminium intensity, cause rolling difficult;

Fe:Fe is conducive to suppressing the roughening of heat treatment process crystal grain, and provides partial reinforment effect, but Fe contents are more than 0.03% When, β can be formed(AlFeSi)Phase, even AL is promoted during more than 0.2%6Fe phases increase, and such compound is in bar-shaped or strip, It is non-breakable in follow-up rolling deformation process, and the formation of oxide-film is hindered in anode oxidation process, aggravation region is heterochromatic.

Si:Si in alloy is mainly impurity, and the quantity and size of the content compound of the composition are directly proportional, and make anodic oxygen Surface after change is muddy, therefore need to be strict controlled within 0.03%.

Ti:Ti is the essential element for suppressing cast sturcture's roughening, and preferred content is 0.025%, can form thick when content is higher Large compound, promotes forming region heterochromatic.

Cu、Mn:Cu, Mn are conducive to improving the intensity of material, and addition within the specific limits can solid solution enter AlFe phases, Improve the structure of AlFe phases, the dissolving of compound during the high temperature section insulation of promotion ingot homogenization;And during excessive addition Cu, will be formed Al2Cu compounds, make oxide-film become muddy and no longer thoroughly white, need to be strict controlled in less than 0.08%.

Zn:After Zn additions are more than 0.16%, the pore-forming efficiency of hexagonal prism micropore in anode oxidation process can be improved, is reduced The pore-forming efficiency difference caused by crystal grain orientation is different, it is to avoid micropore uneven thickness after subsequent growth, and addition exceedes 0.25%, the corrosion resistance of oxide-film will be influenceed, therefore less than 0.25% need to be strict controlled in.

Zr:A small amount of addition Zr is beneficial to improve recrystallization temperature, suppresses crystal grain and grows up, it is ensured that the uniformity of crystal grain;And When addition is more than 0.08%, it will continue to improve recrystallization temperature, easily cause batch annealing process crystal grain uneven.

In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention Technical scheme is described further, but the present invention is not limited only to this.

Embodiment 1

A kind of mirror-like anodic oxidation Aluminum Plate and Strip, its ingredient percentage is:Si 0.024%, Fe 0.025%, Cu 0.05%, Mn 0.07%, Mg 4.5%, Zn 0.18%, Zr 0.05%, Ti 0.023%, surplus is Al and can not kept away The impurity exempted from.

Its preparation method comprises the following steps:

(1)Aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot carry out dispensing after melting respectively through smelting furnace, then semicontinuous through low liquid level Ingot casting is made in casting;

(2)Ingot casting is sent into heating furnace behind sawing, milling face, 440 DEG C are warming up to≤20 DEG C/h speed, 40h is incubated, then It is brought rapidly up to 550 DEG C, is incubated 1h, then be cooled to 480 DEG C, hot rolling of coming out of the stove, hot rolling finishing temperature is 350 DEG C, hot rolled thickness is 8.0mm;

(3)By the cold rolling of the coiled material progress 60% after hot rolling, 400 DEG C then are warming up to >=60 DEG C/h speed, insulation 2h is carried out Intermediate annealing, then finished product thickness is cold rolled to, cold rolling reduction ratio is 60%, again through stretch-bending straightening system after 270 DEG C of finished products Obtain finished product.

Gained aluminium alloy strips thickness 1.0mm, tensile strength 270MPa, yield strength is 220MPa, elongation percentage 10.8%, Intermetallic compound maximum length contained by its inside is 5.6 μm;Sampled after moderate heat and com-parison and analysis carried out to the crystal grain of longitudinal section, It is per 1mm2In the range of any crystal grain difference in size be 2.2 μm, after the polished rear anodic oxidation in surface, finished product plate face be in mirror Face effect.

Embodiment 2

A kind of mirror-like anodic oxidation Aluminum Plate and Strip, its ingredient percentage is:Si 0.02%, Fe 0.02%, Cu 0.03%, Mn 0.06%, Mg 4.0%, Zn 0.16%, Zr 0.06%, Ti 0.025%, surplus is Al and can not kept away The impurity exempted from.

Its preparation method comprises the following steps:

(1)Aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot carry out dispensing after melting respectively through smelting furnace, then semicontinuous through low liquid level Ingot casting is made in casting;

(2)Ingot casting is sent into heating furnace behind sawing, milling face, 440 DEG C are warming up to≤20 DEG C/h speed, 20h is incubated, then It is brought rapidly up to 540 DEG C, is incubated 3h, then be cooled to 460 DEG C, hot rolling of coming out of the stove, hot rolling finishing temperature is 300 DEG C, hot rolled thickness is 3.0mm;

(3)By the cold rolling of the coiled material progress 80% after hot rolling, 360 DEG C then are warming up to >=60 DEG C/h speed, insulation 6h is carried out Intermediate annealing, then finished product thickness is cold rolled to, cold rolling reduction ratio is 40%, again through stretch-bending straightening system after 150 DEG C of finished products Obtain finished product.

Gained aluminium alloy strips thickness 0.36mm, tensile strength 240MPa, yield strength is 205MPa, elongation percentage 12.8%, Intermetallic compound maximum length contained by its inside is 5.5 μm;Sampled after moderate heat and com-parison and analysis carried out to the crystal grain of longitudinal section, It is per 1mm2In the range of any crystal grain difference in size be 2.7 μm, after the polished rear anodic oxidation in surface, finished product plate face be in mirror Face effect.

Embodiment 3

A kind of mirror-like anodic oxidation Aluminum Plate and Strip, its ingredient percentage is:Si 0.027%, Fe 0.027%, Cu 0.08%, Mn 0.1%, Mg 5.0%, Zn 0.25%, Zr 0.08%, Ti 0.028%, surplus is Al and can not kept away The impurity exempted from.

Its preparation method comprises the following steps:

(1)Aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot carry out dispensing after melting respectively through smelting furnace, then semicontinuous through low liquid level Ingot casting is made in casting;

(1)Ingot casting is sent into heating furnace behind sawing, milling face, 450 DEG C are warming up to≤20 DEG C/h speed, 16h is incubated, then It is brought rapidly up to 530 DEG C, is incubated 12h, then be cooled to 450 DEG C, hot rolling of coming out of the stove, hot rolling finishing temperature is 250 DEG C, hot rolled thickness is 10.0mm;

(3)By the cold rolling of the coiled material progress 50% after hot rolling, 460 DEG C then are warming up to >=60 DEG C/h speed, insulation 2h is carried out Intermediate annealing, then finished product thickness is cold rolled to, cold rolling reduction ratio is 80%, again through stretch-bending straightening system after 280 DEG C of finished products Obtain finished product.

Gained aluminium alloy strips thickness 1.0mm, tensile strength 300MPa, yield strength is 235MPa, elongation percentage 10.2%, Intermetallic compound maximum length contained by its inside is 5.3 μm;Sampled after moderate heat and com-parison and analysis carried out to the crystal grain of longitudinal section, It is per 1mm2In the range of any crystal grain difference in size be 2.0 μm, after the polished rear anodic oxidation in surface, finished product plate face be in mirror Face effect.

The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (5)

1. a kind of mirror-like anodic oxidation Aluminum Plate and Strip, it is characterised in that:Its ingredient percentage is:Si ≤ 0.03%, Fe≤0.03%, Cu 0.03 ~ 0.08%, Mn 0.06-0.1%, Mg 4.0-5.0%, Zn 0.16-0.25%, Zr 0.05 ~ 0.08%, Ti 0.02 ~ 0.03%, surplus is Al and inevitable impurity.
2. a kind of method for preparing mirror-like anodic oxidation Aluminum Plate and Strip as claimed in claim 1, it is characterised in that:With aluminium Ingot, aluminium intermediate alloy ingot, magnesium ingot are raw material, and the mirror-like anodic oxidation aluminium is made through founding, hot rolling, cold rolling, heat treatment Strip.
3. the preparation method of mirror-like anodic oxidation Aluminum Plate and Strip according to claim 2, it is characterised in that:Including following Step:
(1)Aluminium ingot, aluminium intermediate alloy ingot, magnesium ingot carry out dispensing after melting respectively through smelting furnace, then through semi-continuous casting system Obtain ingot casting;
(2)Ingot casting is sent into heating furnace behind sawing, milling face, 440 ~ 450 DEG C are warming up to≤20 DEG C/h speed, insulation 16 ~ 40h, is then brought rapidly up to 530 ~ 550 DEG C, is incubated 1 ~ 12h, then be cooled to 450 ~ 480 DEG C, hot rolling of coming out of the stove, hot rolling finishing temperature For 250 ~ 350 DEG C, hot rolled thickness is 3.0 ~ 10.0mm;
(3)By the coiled material after hot rolling by 50-80% it is cold rolling after carry out intermediate annealing, intermediate anneal temperature is 360-460 DEG C, Soaking time is 2-6h, is then cold rolled to finished product thickness, cold rolling reduction ratio is 40 ~ 80%, by 150-280 DEG C of finished products Afterwards again through stretch-bending straightening finished product.
4. the preparation method of mirror-like anodic oxidation Aluminum Plate and Strip according to claim 3, it is characterised in that:Step 1) Described semi-continuous casting method is low liquid level semi-continuous casting.
5. the preparation method of mirror-like anodic oxidation Aluminum Plate and Strip according to claim 3, it is characterised in that:Step 3) Rate of heat addition during intermediate annealing is >=60 DEG C/h.
CN201710548317.2A 2017-07-06 2017-07-06 A kind of mirror-like anodic oxidation Aluminum Plate and Strip and preparation method thereof CN107190184B (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN108149171A (en) * 2017-12-14 2018-06-12 中铝材料应用研究院有限公司 Excellent aluminium of a kind of surface quality and preparation method thereof
CN108149091A (en) * 2017-12-06 2018-06-12 浙江永杰铝业有限公司 A kind of high surface anodization appearance aluminium alloy strips of high intensity and preparation method thereof
CN108277403A (en) * 2018-01-31 2018-07-13 中铝瑞闽股份有限公司 A kind of mirror-like anodized aluminum alloy calendering plate and preparation method thereof
CN109097641A (en) * 2018-09-19 2018-12-28 东莞市灿煜金属制品有限公司 It is a kind of suitable for mobile phone battery cover and edges of boards frames one it is high-intensitive can mirror surface aluminium oxide manufacturing method

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WO2015022734A1 (en) * 2013-08-13 2015-02-19 日本軽金属株式会社 Aluminum alloy plate for high-strength alumite material and method for producing same, and aluminum alloy plate having high-strength alumite coating film attached thereto
CN105543520A (en) * 2015-12-31 2016-05-04 广西南南铝加工有限公司 Preparing method of aluminum alloy base material for electronic product shell
CN105695821A (en) * 2016-02-05 2016-06-22 中铝瑞闽股份有限公司 High-strength aluminium alloy strip for anodic oxidation, and preparation method thereof

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JP2008190021A (en) * 2007-02-07 2008-08-21 Kobe Steel Ltd Al-Mg BASED ALLOY HOT ROLLED SHEET, AND METHOD FOR PRODUCING THE SAME
CN103572112A (en) * 2012-08-08 2014-02-12 住友轻金属工业株式会社 Aluminum alloy sheet that exhibits excellent surface quality after anodizing and method for producing the same
WO2015022734A1 (en) * 2013-08-13 2015-02-19 日本軽金属株式会社 Aluminum alloy plate for high-strength alumite material and method for producing same, and aluminum alloy plate having high-strength alumite coating film attached thereto
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CN108149091A (en) * 2017-12-06 2018-06-12 浙江永杰铝业有限公司 A kind of high surface anodization appearance aluminium alloy strips of high intensity and preparation method thereof
CN108149171A (en) * 2017-12-14 2018-06-12 中铝材料应用研究院有限公司 Excellent aluminium of a kind of surface quality and preparation method thereof
CN108277403A (en) * 2018-01-31 2018-07-13 中铝瑞闽股份有限公司 A kind of mirror-like anodized aluminum alloy calendering plate and preparation method thereof
CN108277403B (en) * 2018-01-31 2019-09-17 中铝瑞闽股份有限公司 A kind of mirror-like anodized aluminum alloy calendering plate and preparation method thereof
CN109097641A (en) * 2018-09-19 2018-12-28 东莞市灿煜金属制品有限公司 It is a kind of suitable for mobile phone battery cover and edges of boards frames one it is high-intensitive can mirror surface aluminium oxide manufacturing method

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