CN108707941A - Anode oxide film and preparation method thereof and Al-alloy casing, mobile phone containing it - Google Patents
Anode oxide film and preparation method thereof and Al-alloy casing, mobile phone containing it Download PDFInfo
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- CN108707941A CN108707941A CN201810533865.2A CN201810533865A CN108707941A CN 108707941 A CN108707941 A CN 108707941A CN 201810533865 A CN201810533865 A CN 201810533865A CN 108707941 A CN108707941 A CN 108707941A
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- alloy casing
- oxide film
- anodic oxidation
- anode oxide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Signal Processing (AREA)
- Casings For Electric Apparatus (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a kind of anode oxide film and preparation method thereof and the Al-alloy casing containing it, mobile phone.The preparation method includes the following steps：Al-alloy casing is subjected to anodic oxidation, sealing pores, you can；Sidewall thickness >=0.85mm of the Al-alloy casing, the Al-alloy casing in a thickness direction seamlessly transit >=1:20；The condition of the anodic oxidation：Oxidation voltage is 11.5V~15V, and current density is 1.2~2A/dm2, concentration of electrolyte is 180~200g/L；The condition of the sealing pores：A concentration of 12~15g/L of pore-sealing liquid；The anodic oxidation film thickness is at 15 μm or more.For the Al-alloy casing anode oxide film consistency that the present invention is prepared 0.6 or more, hardness reaches 100HB or more, α-Al2O3Content can effectively reduce " slip layer " of falling process Anodic film 80% or more.
Description
Technical field
The present invention relates to a kind of anode oxide film and preparation method thereof and the Al-alloy casing containing it, mobile phone.
Background technology
In recent years, with the continuous innovation of intelligent mobile phone technology, the differential competition between each cell phone manufacturer also becomes
Must be more and more violent, the product of various great innovations also emerges one after another, and the intelligent mobile phone of wherein metal fuselage is mobile
One quantum jump in telephony topology part field.Appearance is often the part that consumer values the most for a mobile phone,
And material is to determine the very important one side of mobile phone appearance, the type of metallic fuselage designs has outstanding texture
And it is more and more favored by consumers.The representative of mainstream metal type has OPPO R9s, OPPO R9, HTC ONE on current market
M9, Huawei P8, iPhone6 etc..
Why the mobile phone of metal shell can show remarkable texture and gorgeous brilliant color, be due to making
Anode processing is have passed through for the raw material aluminum alloy surface of current main-stream airframe structure part, so that it is had, rich in color, color and luster is excellent
Beautiful, good insulating and hard wear resistant, corrosion resistance is high to obtain performance.
Since aluminum alloy materials itself are to the shielding of radiofrequency signal, usually wanted when a mobile phone structure designs
The thickness of Al-alloy casing is asked to do to greatest extent thin (the big face thickness 0.60mm of the limit, local thickness 0.50mm).However thickness
Thinning to cause during drop test as stress σ > σ e, aluminium alloy irreversible transformation can drive anode film to deform and hold
It splits, the expendable damage of mobile phone appearance will bring consumer experience serious negative effect.
Invention content
Technical problem to be solved by the present invention lies in solve mobile phone Al-alloy casing in falling process Anodic oxygen
Change film problem of Cracking, and at the same time while meeting the antenna performance of mobile phone, ensures that shell structure and anode oxide film are attached
It and stablizes, and provide a kind of anode oxide film and preparation method thereof and the Al-alloy casing containing it, mobile phone.System of the present invention
For standby obtained Al-alloy casing anode oxide film consistency 0.6 or more, hardness reaches 100HB or more, α-Al2O3Content exists
80% or more, it can effectively reduce " slip layer " of falling process Anodic film, the adhesive force of anode oxide film is stablized, and significantly reduces
Housing distortion rate in falling process.
The present invention provides a kind of preparation methods of Al-alloy casing anode oxide film comprising following steps close aluminium
Golden shell body carries out anodic oxidation, sealing pores, you can；
Sidewall thickness >=0.85mm of the Al-alloy casing, the Al-alloy casing seamlessly transitting in a thickness direction
≥1:20；
The anodic oxidation condition：Oxidation voltage is 11.5V~15V, and current density is 1.2~2A/dm2, electrolyte is dense
Degree is 180~200g/L；
The sealing pores condition：A concentration of 12~15g/L of pore-sealing liquid；
The anodic oxidation film thickness is at 15 μm or more.
In the present invention, the Al-alloy casing in a thickness direction seamlessly transit >=1:20 refer to Al-alloy casing in thickness
Degree direction is formed by tangent value >=1 of angle:20.
In the present invention, the oxidation voltage is preferably 11.5~12.5V, such as 11.5V, 12.5V.The oxidation voltage range
Under the anode oxide film consistency compared to 9.0~11.5V promoted 12%.
In the present invention, the current density is preferably 1.2~1.5A/dm2, such as 1.2A/dm2、1.5A/dm2。
In the present invention, the thickness of the anode oxide film is preferably 15~18 μm.
In the present invention, the electrolyte can be the electrolyte of this field routine, preferably chemical polishing mixed acid.Describedization
Optical polishing mixed acid can be common commercially available or obtain in conventional manner, such as the chemical polishing mixed acid is purchased from the glad source in Shenzhen
Noboru Chemical Co., Ltd..
In the present invention, the concentration of electrolyte generally refers to the mass volume ratio of all solutes and solvent in electrolyte, excellent
It is selected as 200g/L.
In the present invention, the electrolyte temperature is preferably 18~21 DEG C, and the anode film thickness is uniform under the temperature range,
Thickness can control within 1 μm.Anode film can uniformly reduce " slip layer " problem of falling process Anodic film.
In the present invention, the time of the anodic oxidation can be the oxidization time of this field routine, preferably 30min.
In the present invention, the pore-sealing liquid can be common commercially available or obtain in conventional manner, such as the pore-sealing liquid is purchased from
Shenzhen sea fine chemistry industry processing factory of TongYuan.
In the present invention, the pore-sealing liquid concentration generally refers to the mass volume ratio of all solutes and solvent in pore-sealing liquid, excellent
It is selected as 13~14g/L, under the pore-sealing liquid concentration, the hardness of the anode oxide film can reach 100HB or more.
In the present invention, the time of the sealing pores is preferably 15~20min.
In the present invention, the temperature of the sealing pores is preferably 80~85 DEG C.
Those skilled in the art know that the anodic oxidation carries out generally in electrolytic cell, it is preferable that the anodic oxidation
The replacement frequency of middle electrolytic cell deionized water is≤24 hours primary.
In the present invention, it is preferable that before the anodic oxidation, the Al-alloy casing is with conductivity≤35us/cm's
Deionized water is cleaned.
In the present invention, it is preferable that the Al-alloy casing cleans after the anodic oxidation；It is highly preferred that the aluminium alloy
Shell is cleaned with deionized water after the anodic oxidation.
In a preferred embodiment of the invention, the oxidation voltage is 11.5~12.5V, and the current density is 1.2
~1.5A/dm2, the concentration of electrolyte is 180~200g/L, a concentration of 13~14g/L of pore-sealing liquid.
In a preferred embodiment of the invention, the oxidation voltage is 11.5V, and the current density is 1.2A/dm2,
The concentration of electrolyte is 200g/L, a concentration of 13g/L of pore-sealing liquid.
In a preferred embodiment of the invention, the oxidation voltage is 12.5V, and the current density is 1.5A/dm2,
The concentration of electrolyte is 200g/L, a concentration of 14g/L of pore-sealing liquid.
In a preferred embodiment of the invention, the oxidation voltage is 13.5V, and the current density is 1.8A/dm2,
The concentration of electrolyte is 180g/L, a concentration of 12g/L of pore-sealing liquid.
In a preferred embodiment of the invention, the oxidation voltage is 15V, and the current density is 2A/dm2, described
Concentration of electrolyte is 180g/L, a concentration of 15g/L of pore-sealing liquid.
The present invention also provides a kind of anode oxide films that above-mentioned preparation method is prepared.
Wherein, the consistency of the anode oxide film is preferably 0.6 or more.The consistency refers to atom itself in structure cell
Shared percentage by volume, the i.e. ratio of atomic volume and unit cell volume included in structure cell.
Wherein, the hardness of the anode oxide film is preferably 100HB or more.
Wherein, the composition of the anode oxide film is preferably α-Al2O3Content is 80% or more, and percentage refers to anodic oxygen
Change α-Al in film2O3Shared mass percent.
The present invention also provides it is a kind of include above-mentioned anode oxide film Al-alloy casing.
The present invention also provides it is a kind of include above-mentioned Al-alloy casing mobile phone.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：
(1) the Al-alloy casing anodic oxidation film thickness that is prepared of the present invention is at 15 μm or more, consistency 0.6 with
On, hardness reaches 100HB or more, α-Al2O3Content can effectively reduce " slip layer " of falling process Anodic film 80% or more,
The adhesive force of anode oxide film is stablized, and the housing distortion rate and anode film cracking rate in falling process are significantly reduced.
(2) in the present invention, sidewall thickness >=0.85mm of Al-alloy casing can both adjust satisfaction on the basis of this thickness
Antenna performance can guarantee structural strength again, reduce the deformation of falling process middle casing.
(3) include the mobile phone Al-alloy casing of anode oxide film that the present invention is prepared, in a thickness direction
Seamlessly transit >=1:20, can effectively avoid falling stress concentration causes housing distortion to tear anode film.
(4) in the present invention, after mobile phone Al-alloy casing anodic oxidation, make handset color and luster grace, insulating properties
Good, hard wear resistant, corrosion resistance are good.
Description of the drawings
Fig. 1 is the structural schematic diagram of Al-alloy casing thickness direction, and wherein a figures are Al alloy shell body thickness in the prior art
The structural schematic diagram in direction, it is 90 ° to indicate that Al-alloy casing is formed by angle in thickness direction at arrow；B figures are embodiment 1
The structural schematic diagram of Al-alloy casing thickness direction in~4 refers to that Al-alloy casing is formed by folder in thickness direction at arrow
Angle, tangent value, i.e. line segment are 1.：Value >=1 of line segment 2.:20；
Fig. 2 is mobile phone anode oxide film cracking schematic diagram；Wherein c figures are the global figure of anode oxide film cracking；A schemes
It is partial enlarged view with b figures；Wherein a figures are that membrane plane is vertical shoots with oxidation, and b figures are and oxidation membrane plane is in 45 ° of shootings.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
Fig. 1 is the structural schematic diagram of Al-alloy casing thickness direction；Wherein a figures are Al alloy shell body thickness in the prior art
The structural schematic diagram in direction, it is 90 ° to indicate that Al-alloy casing is formed by angle in thickness direction at arrow；B figures are embodiment 1
The structural schematic diagram of Al-alloy casing thickness direction in~4 refers to that Al-alloy casing is formed by folder in thickness direction at arrow
Angle, tangent value, i.e. line segment are 1.：Value >=1 of line segment 2.:20.
In following embodiments, in the mold such as Fig. 1 of used Al-alloy casing shown in b figures.
Embodiment 1
(1) polishing machine uses the model of different sand paper, Al-alloy casing of polishing from coarse to fine, the side thickness of Al-alloy casing
Degree >=0.85mm seamlessly transits >=1 on thickness direction:20.
(2) Al-alloy casing is rinsed well with deionized water, then aluminium alloy is immersed and removes oil solution (P3Almeco
36) in, 10min is impregnated at 65 DEG C；Aluminium alloy is rinsed well again with deionized water, aluminium flake is then immersed into strong alkali solution
In (TURCO Aluminetch), bubble 2min is invaded at 60 DEG C；After aluminium substrate is rinsed well by deionized water, it is placed in acid solution
In (TURCO Liquid Smut Go NC), bubble 10min is invaded at 50 DEG C；It is rinsed well with conductivity≤35us/cm deionized waters
Aluminium substrate obtains pretreated Al-alloy casing.
(3) electrolyte is the mixed liquor (being purchased from Shenzhen Xin Yuan Noboru Chemical Co., Ltd.) of the concentrated sulfuric acid and tartaric acid, electrolyte
A concentration of 200g/L, for above-mentioned pretreated Al-alloy casing as anode, cathode is fine aluminium, is powered on, and prepares anodic oxidation
Film；Tank liquor temperature is 18 DEG C, oxidation voltage 11.5V, current density 1.2A/dm2, oxidization time 30min.In electrolytic cell
The replacement frequency of deionized water is 24 hours primary.
(4) Al-alloy casing after step (3) Anodic Oxidation is subjected to sealing of hole, a concentration of 13g/L of pore-sealing liquid, sealing of hole
Liquid (is purchased from Shenzhen sea fine chemistry industry processing factory of TongYuan), in 80~85 DEG C of 15~20min of sealing of hole.
Al-alloy casing anodic oxidation film thickness made from the present embodiment is at 18 μm, and consistency is 0.70 or more, oxidation film
Hardness is 100HB or more, the α-Al in anode oxide film2O3Content is 85%.
Embodiment 2
The preparation condition that anode oxide film is prepared in step (3) is：Concentration of electrolyte is 200g/L, tank liquor temperature 19
DEG C, oxidation voltage 12.5V, current density 1.5A/dm2.A concentration of 14g/L of pore-sealing liquid in step (4).Remaining operation and
Condition is the same as embodiment 1.
Al-alloy casing anodic oxidation film thickness made from the present embodiment is at 18 μm, and consistency is 0.80 or more, oxidation film
Hardness is 100HB or more.α-Al in anode oxide film2O3Content is 80%.
Embodiment 3
The preparation condition that anode oxide film is prepared in step (3) is：Concentration of electrolyte is 180g/L, tank liquor temperature 20
DEG C, oxidation voltage 13.5V, current density 1.8A/dm2.A concentration of 12g/L of pore-sealing liquid in step (4).Remaining operation and
Condition is the same as embodiment 1.
Al-alloy casing anodic oxidation film thickness made from the present embodiment is at 15 μm or more, and consistency is 0.6 or more, oxidation
Film hardness is 100HB or more.α-Al in anode oxide film2O3Content is 80% or more.
Embodiment 4
The preparation condition that anode oxide film is prepared in step (3) is：Concentration of electrolyte is 180g/L, tank liquor temperature 21
DEG C, oxidation voltage 15V, current density 2A/dm2.A concentration of 15g/L of pore-sealing liquid in step (4).Remaining operation and condition
With embodiment 1.
Al-alloy casing anodic oxidation film thickness made from the present embodiment is at 15 μm or more, and consistency is 0.6 or more, oxidation
Film hardness is 100HB or more.α-Al in anode oxide film2O3Content is 80% or more.
Comparative example 1
The preparation condition that anode oxide film is prepared in step (3) is：Tank liquor temperature is 25 DEG C, oxidation voltage 9V, electric current
Density is 1.5A/dm2.A concentration of 10g/L of pore-sealing liquid in step (4).Remaining operation and condition are the same as embodiment 1.
Al-alloy casing anodic oxidation film thickness made from this comparative example is 12 μm, and consistency 0.52 aoxidizes film hardness
For 92HB.α-Al in anode oxide film2O3Content is 60% or more.
Effect example 1
(1) drop test is tested
Mobile phone is assembled using the Al-alloy casing after anodic oxidation and sealing pores, respectively from apart from ground 1.5m's
Freely falling body at height observes the anode oxide film cracking situation and housing distortion situation of sample, anode oxide film cracking signal
Figure is as shown in Fig. 2, wherein c figures are the global figure of anode oxide film cracking；A schemes and b figures are partial enlarged view；Wherein a figures be with
Oxidation membrane plane is vertically shot, and b figures are with oxidation membrane plane in 45 ° of shootings.
(2) anode oxide film adhesive force is tested
Using hundred lattice methods of testing, anode oxide film adhesive force, reference standard are measured《GBT9286-1998 paint and varnish paints
The scratch experiment of film》.
10 × 10 (100) 1mm × 1mm small grids are drawn on test sample surface with cross-cut tester, each scribing line should be deep
And the bottom of anode film；The fragment of test zone is cleaned down with hairbrush；Firmly with the gummed paper of 3M600 gummed papers or equal efficiency
Tested small grid is clung, erasing rubber is used in combination to wipe adhesive tape；Adhesive tape one end is held, is shut down rapidly in vertical direction (90 °)
Gummed paper, same position carry out 2 this identical test.Measure the area that falls off (%) of anode film.
(3) antenna performance is tested
Mobile phone is assembled using the Al-alloy casing after anodic oxidation and sealing pores, to the antenna performance of mobile phone
It is tested.
Performance test is as shown in the table：
The experimental results showed that：
1. including the mobile phone of the Al-alloy casing of anode oxide film prepared by the present invention, fall at 1.5m height
When, anodic oxidation film surface does not deform without cracking, shell；And include the Al alloy shell of anode oxide film prepared by comparative example
The cracking rate of body is up to 83.3%.
2. anode oxide film adhesive force of the present invention is significantly higher than the attachment of comparative example (conventional method preparation) Anodic Oxide Film
Power, and adhesive force is stablized.
3. the mobile phone obtained has good antenna performance, can continue to work normally.
Claims (10)
1. a kind of preparation method of Al-alloy casing anode oxide film, which is characterized in that it includes the following steps, by Al alloy shell
Body carries out anodic oxidation, sealing pores, you can；
Sidewall thickness >=0.85mm of the Al-alloy casing, the Al-alloy casing in a thickness direction seamlessly transit >=1:
20；
The condition of the anodic oxidation：Oxidation voltage is 11.5V~15V, and current density is 1.2~2A/dm2, concentration of electrolyte is
180~200g/L；
The condition of the sealing pores：A concentration of 12~15g/L of pore-sealing liquid；
The anodic oxidation film thickness is at 15 μm or more.
2. preparation method as described in claim 1, which is characterized in that the concentration of electrolyte is 200g/L；
And/or the oxidation voltage is 11.5V~12.5V；
And/or the current density is 1.2~1.5A/dm2；
And/or a concentration of 13~14g/L of pore-sealing liquid.
3. preparation method as described in claim 1, which is characterized in that electrolyte temperature is 18 DEG C~21 in the anodic oxidation
℃；
And/or the time of the anodic oxidation is 30min；
And/or the time of the sealing pores is 15~20min；
And/or the temperature of the sealing pores is 80~85 DEG C.
4. preparation method as described in claim 1, which is characterized in that the anodic oxidation film thickness is 15~18 μm.
5. preparation method as described in claim 1, which is characterized in that the anodic oxidation carries out in electrolytic cell, the electricity
The replacement frequency for solving deionized water in slot is≤24 hours primary.
6. pressing preparation method according to any one of claims 1 to 5, which is characterized in that before the anodic oxidation, the aluminium
Alloy shell is cleaned with the deionized water of conductivity≤35us/cm；
With or, the Al-alloy casing is cleaned with deionized water after the anodic oxidation.
7. one kind is by anode oxide film made from preparation method according to any one of claims 1 to 6.
8. anode oxide film as described in claim 6, which is characterized in that the consistency of the anode oxide film is 0.6 or more,
Hardness is 100HB or more.
9. a kind of includes the Al-alloy casing of the anode oxide film described in claim 7 or 8.
10. a kind of includes the mobile phone of Al-alloy casing described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810533865.2A CN108707941B (en) | 2018-05-29 | 2018-05-29 | Anodic oxide film, preparation method thereof, aluminum alloy shell containing anodic oxide film and mobile phone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810533865.2A CN108707941B (en) | 2018-05-29 | 2018-05-29 | Anodic oxide film, preparation method thereof, aluminum alloy shell containing anodic oxide film and mobile phone |
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| Publication Number | Publication Date |
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| CN108707941A true CN108707941A (en) | 2018-10-26 |
| CN108707941B CN108707941B (en) | 2021-02-26 |
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ID=63870927
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810533865.2A Active CN108707941B (en) | 2018-05-29 | 2018-05-29 | Anodic oxide film, preparation method thereof, aluminum alloy shell containing anodic oxide film and mobile phone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112391659A (en) * | 2019-08-14 | 2021-02-23 | 浙江苏泊尔股份有限公司 | Method for preparing oxide film containing alpha-alumina and vessel |
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