CN103255458A - Forming method and structure of aluminum alloy surface interference film - Google Patents
Forming method and structure of aluminum alloy surface interference film Download PDFInfo
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- CN103255458A CN103255458A CN2012100374138A CN201210037413A CN103255458A CN 103255458 A CN103255458 A CN 103255458A CN 2012100374138 A CN2012100374138 A CN 2012100374138A CN 201210037413 A CN201210037413 A CN 201210037413A CN 103255458 A CN103255458 A CN 103255458A
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Abstract
The present invention provides a forming method and a structure of an aluminum alloy surface interference film. The forming method comprises at least the following steps: providing an aluminum alloy workpiece; carrying out a pretreatment on the aluminum alloy workpiece so as to clean the surface of the workpiece; carrying out an anode treatment on the aluminum alloy workpiece for a predetermined time until the surface forms an oxidation film with a plurality of tracheid-like micropores; adopting an acid solution to carry out a hole expansion treatment on the oxidation film of the aluminum alloy workpiece to expand the pore size of the tracheid-like micropore; carrying out an electrifying hole expansion treatment so as to expand the bottom of the tracheid-like micropore and form a deposition zone; depositing a specific metal in the deposition zone of the tracheid-like micropore to form an interference structure; carrying out a hole sealing treatment on the tracheid-like micropore with a hole sealing agent; and removing ash. With the present invention, an aluminum alloy surface interference film structure is formed by using the method.
Description
Technical field
The invention relates to a kind of formation method and structure thereof of aluminum alloy surface inteferometer coating, refer to especially a kind of with the anodizing be the basis utilize electrolysis forms the inteferometer coating structure in aluminum alloy surface method with and structure.
Background technology
Form firm decorative colors on the metal shell, by research widely and application, wherein anodizing is common method.Yet anodizing can only form a kind of color at metal shell usually, can't satisfy the appearance requirement of novel changes persuing gradually.
Moreover, the practice that has at present is to utilize the electric current over-over mode to carry out the electrolytic coloring of aluminium substrate metal base, directly add nickel salt in second time anolyte to produce color, this kind can't produce the multi-angle different colours of inteferometer coating through painted anodizing of aluminium film.
In response to market and consumer demand, how can produce the phenomenon that light is interfered in aluminum alloy surface, so that aluminum alloy surface is showed different colours in different angles, and volume production stably, be industry problem extremely to be solved.
Summary of the invention
The object of the present invention is to provide a kind of formation method and structure thereof of aluminum alloy surface inteferometer coating, can produce the phenomenon that light is interfered in aluminum alloy surface, so that aluminum alloy surface is showed different colours in different angles.
In order to solve the problems of the technologies described above, according to wherein a kind of scheme of the present invention, provide a kind of formation method of aluminum alloy surface inteferometer coating, it comprises the following step at least: an Al alloy parts is provided; This Al alloy parts of pre-treatment is to clean its surface; One predetermined time of this Al alloy parts of anodizing, form an oxide film with a plurality of test-tube baby shape micropores up to this surface; Handle this oxide film of this Al alloy parts with the acidic solution reaming, enlarge the aperture of this test-tube baby shape micropore; The energising reaming is handled to enlarge the bottom of this test-tube baby shape micropore and is formed a sedimentary province; The deposition special metal forms interference structure in this sedimentary province of this test-tube baby shape micropore; Handle this test-tube baby shape micropore with the hole sealing agent sealing of hole; And ash disposal.
In order to solve the problems of the technologies described above, the invention provides a kind of inteferometer coating structure of aluminum alloy surface, be positioned on the oxide film of this Al alloy parts, this oxide film comprises a plurality of test-tube baby shape micropores, this inteferometer coating structure comprises a plurality of sedimentary provinces that are positioned at this test-tube baby shape micropore bottom, and wherein the aperture of this sedimentary province is greater than the aperture of this test-tube baby shape micropore; A plurality of reflecting parts that are made of metal ion partly are deposited in this sedimentary province; And a sealing of hole layer is covered on this oxide film.
The present invention has following beneficial effect: the present invention can form interference in aluminum alloy surface, that is aluminum alloy surface presents different metallic luster, the appreciative value of increase aluminum alloy surface when different angles.
Reach technology, method and the effect that set purpose is taked in order further to understand the present invention, see also following relevant detailed description of the present invention, graphic, believe purpose of the present invention, feature and characteristics, when being goed deep into thus and concrete understanding, yet graphic reference and the explanation usefulness of only providing is limited the present invention.
Description of drawings
Fig. 1 is the schema of the formation method of aluminum alloy surface inteferometer coating of the present invention.
Fig. 2 analyses and observe micro-enlarged view for Al alloy parts of the present invention through the oxide film that forms after the anodizing.
Fig. 3 is the micro-enlarged view of analysing and observe after Al alloy parts of the present invention is handled through reaming.
Fig. 4 is the micro-enlarged view of analysing and observe after the Al alloy parts process energising reaming of the present invention.
Fig. 5 is the micro-enlarged view of analysing and observe behind the metal refining of test-tube baby shape micropore of the present invention bottom.
Fig. 6 is the synoptic diagram that aluminum alloy surface inteferometer coating structure of the present invention and light are interfered.
Wherein, description of reference numerals is as follows:
Test-tube baby shape micropore 10,10a, 10b
Test-tube baby shape micropore upper semisection 12
Sedimentary province 14
Reflecting part 16
Sealing of hole layer 18
Light R, R ', R1, R2
Aperture D1, D2
Width D 3
Height D4
Embodiment
See also Fig. 1, be the schema of the formation method of aluminum alloy surface inteferometer coating of the present invention.The formation method of aluminum alloy surface inteferometer coating of the present invention comprises following at least main flow, will describe the correlative detail of each flow process afterwards in detail.
At first, provide an Al alloy parts, this Al alloy parts can be housing or the body of rod of any device, for example car body of electronic product shell body, bicycle or small-sized decorative metal spare etc.
Then be step 20, this Al alloy parts of pre-treatment is to clean its surface; Abbreviate " pre-treatment " flow process as, it comprises the sub-process at least five roads;
The pre-treatment program of above-mentioned steps 20 can be to comprise that step 21 takes off the pickling (first pickling) for the first time of ester (degreasing), step 22 alkali cleaning (Alkaline etching), step 23, step 24 chemical rightenning (chemical polishing), and the sub-process of step 25 pickling for the second time (second pickling) etc., and wherein the number of processes of sub-process is looked the specification of quality of Al alloy parts and determined.Comprise that at least one washing process, washing process can be one to five roads after each sub-process, be preferably two roads and get final product, to remove last road sub-process residual chemical agent or impurity.The parameter area of each sub-process please refer to following table.
Table 1, each road sub-process parameter list of pre-treatment of the present invention (step 20)
In fact look the situation of aluminium alloy itself and the occasion of application, each above-mentioned sub-process can be adjusted.The present invention is example with the housing of electronic product, through contriver's test and evaluation repeatedly, and preferable parameter such as the following table of each road sub-process of suggestion pre-treatment.
Each road sub-process preferred parameters table of table 1A, pre-treatment
By the time after cleaning Al alloy parts and finishing, this Al alloy parts namely is fit to descend one flow process, that is anodizing.Anodizing is that Al alloy parts is placed electrolyzer and is connected in anode, and negative electrode then connects carbon plate or stereotype, applies certain voltage and electric current then.The anodizing purpose is to utilize the characteristic of the easy oxidation of aluminum or aluminum alloy, by the generation of electrochemical method control zone of oxidation, to prevent the further oxidation of aluminium, increases the mechanical properties on surface simultaneously.Its chemical reaction mechanism belongs to prior art, holds and does not give unnecessary details.
Please refer to Fig. 2, for Al alloy parts of the present invention is analysed and observe micro-enlarged view through the oxide film that forms after the anodizing.After the anodizing, the surface of Al alloy parts 1 forms the oxide film with a plurality of test-tube baby shape micropores 10.Wherein the aperture D1 of test-tube baby shape micropore 10 on average be about 17nm (nanometer, nanometer), yet this size only for understanding reference, actual pore size differs, and may change because of various parameters.Anodizing parameter area of the present invention such as following table 2.
The parameter area of table 2, anodizing of the present invention (step 30)
Preferable parameter area behind the present invention after tested: be soaked in concentration and be 20% to 25% sulphuric acid soln, temperature is 15 Celsius to 25 degrees centigrade, 0.6 ampere of current density (A)/every square centimeter of (dm
2), the treatment time is at least 30 minutes.The temperature of washing is preferably about 25 degrees centigrade, and number of times is two roads.
Through after the anodizing, then to handle for reaming, purpose is to strengthen the aperture of test-tube baby shape micropore 10 and make it more regular, in order to follow-up deposition step.Parameter area that reaming of the present invention is handled is shown in following table 3.
The parameter area of (step 40) is handled in table 3, reaming of the present invention
The present invention after tested, the preferable parameter that reaming is handled is, it is 85% phosphoric acid solution that this Al alloy parts is soaked in concentration, temperature is 20 to 25 degrees centigrade, the time is seven minutes.The temperature of washing is preferably about 25 degrees centigrade, and number of times is two roads.After handling, reaming of the present invention analyses and observe micro-enlarged view, as shown in Figure 3.Wherein the aperture D2 of test-tube baby shape micropore 10a on average be about 28nm (nanometer, nanometer), yet this size only for understanding reference, actual pore size differs, and may change because of various parameters.
After the reaming processing through step 40, then carry out the energising reaming of step 50.Energising is during reaming, and aluminium alloy is connected to anode, carbon plate or stereotype is connected to negative electrode, and power supply can be direct supply or the pulse power or AC power.See also Fig. 4, the purpose of energising reaming is further by electrolysis to form a sedimentary province 14 to enlarge the bottom of this test-tube baby shape micropore 10b with each.The shape of illustrated sedimentary province 14 only is synoptic diagram, and significant feature is to be expanded to both sides or slightly downwards by the bottom of each test-tube baby shape micropore 10b.The parameter area of energising reaming of the present invention is shown in following table 4.
The parameter area of table 4, energising reaming of the present invention (step 50)
The preferable parameter that the energising reaming of step 50 of the present invention is handled is that solution is the phosphoric acid of concentration 150g/L, and temperature is 20 to 25 degrees centigrade, feeds 10 volts direct current, and the time is 5 minutes; The water wash procedures temperature is about 25 degrees centigrade, and number of times is two roads.After tested, as shown in Figure 4, the width D 3 of sedimentary province 14 is bigger than test-tube baby shape micropore upper semisection 12, is about 35 nanometers (nm), and height D4 is about 0.5 to 1 nanometer.Aid illustration be that wherein the height of this figure sedimentary province 14 is exaggerative representation, for the usefulness of understanding easily.
Through after the energising reaming of step 50, then being the cathodic deposition of step 60, mainly is that this Al alloy parts is connected in negative electrode, and anode connects carbon plate or stereotype, solution comprises acidic solution and metallic salt, and power supply can be direct supply or the pulse power or AC power.Purpose be utilize the principle of metal ion reduce deposition in hole with the metal deposition separated out in above-mentioned sedimentary province 14.The parameter area of cathodic deposition of the present invention is shown in following table 5.
The parameter area of table 5, cathodic deposition of the present invention (step 60)
See also Fig. 5, be the micro-enlarged view of analysing and observe behind the metal refining of test-tube baby shape micropore of the present invention bottom.The present invention adds metallic salt with acid electrolyte, with metal deposition in hole.The result of cathodic deposition makes metal deposition in above-mentioned sedimentary province 14 and forms a reflecting part 16, with the light after the reflected refraction.
The preferable parameter of step 60 cathodic deposition is, is soaked in the amido nickel sulphonic acid [Ni (SO of the sulfuric acid of concentration 20% and concentration 5 grams/every liter
3NH
2)
2.4H
2O] solution, temperature is 20 to 25 degrees centigrade, feeds 10 volts direct current, the time is 5 minutes.Afterwards, washing still is about 25 degrees centigrade in temperature, and number of times is two roads.Characteristics such as the present invention uses the advantage of amido nickel sulphonic acid to be that it is fast to have sedimentation velocity, and the nickel metal layer internal stress is low, and the solution dispersive ability is good.In addition, it is careful that nickel metal layer also has crystal grain, the advantage that porosity is low.
What specify is that the present invention is by the concentration of the concentration, particularly amido nickel sulphonic acid of control solution, and the time of energising, make the height of deposition be no more than sedimentary province 14, wherein the height D4 of this sedimentary province 14 is 0.5nm to 1nm, and the height of this reflecting part is less than about half of this sedimentary province height.If the excessive height of reflecting part then can't be suitable for forming interference.
Be the structure pollution resistance of oxidation reinforced film, the present invention carries out sealing of hole (Sealing) flow process of step 70, and the operating method of the sealing of hole behind the general anode place is for using the nickel acetate sealing of hole.The feasible parameter area of sealing of hole flow process of the present invention is shown in following table 6.
The parameter area of table 6, sealing of hole flow process of the present invention (step 70)
Above-mentioned sealing of hole advises that preferable parameter is, this Al alloy parts is soaked in the hole sealing agent that concentration is 7g/L, and temperature is 90 ± 5 degrees centigrade, and the time is 30 minutes.
At last, the present invention is the flow process of ash disposal, to remove the grey shape thing of Al alloy parts surface attachment, normally cleans with acidic solution, washing again.Ash disposal flow process parameter area of the present invention is shown in following table 7.
Table 7, ash disposal flow process of the present invention (step 80) parameter area
The present invention is the shell characteristics that is suitable for electronic product, and wherein ash disposal flow process is preferably the nitric acid with concentration 20ml/L, the about 25 degrees centigrade of processing of temperature.Be still afterwards with about 25 degrees centigrade washing at least two roads of temperature.
Please refer to Fig. 6, formation method through aluminum alloy surface inteferometer coating of the present invention, the invention provides a kind of inteferometer coating structure 1 of aluminum alloy surface, this inteferometer coating structure 1 is positioned on the oxide film of this Al alloy parts, this oxide film comprises a plurality of test-tube baby shape micropore 10a through reaming, this inteferometer coating structure comprises a plurality of sedimentary provinces 14 that are positioned at this test-tube baby shape micropore 10a bottom, wherein the aperture of this sedimentary province 14 is greater than the aperture of this test-tube baby shape micropore 10a, and a plurality of reflecting parts 16 that are made of metal ion partly are deposited in this sedimentary province 14; And one sealing of hole layer 18 be covered on this oxide film.
Inteferometer coating structure by aluminum alloy surface of the present invention has characteristics described as follows.Light R is incident in the aluminium alloy hole, and the portion 16 that is reflected after light refraction enters in the aluminum anode hole 18 reflects, and is reflected into light R1, and another light R ' is incident in and forms light R2 in the aluminium alloy hole.Because therefore light R2 and R1 reflection wavelength difference form interference, that is aluminum alloy surface presents different metallic luster, the appreciative value of increase aluminum alloy surface when different angles.
But the above only is preferable possible embodiments of the present invention, and is non-so namely limit to claim of the present invention, so the equivalence techniques that uses specification sheets of the present invention and graphic content to do such as changes, in like manner all is contained in the scope of the present invention, closes and gives Chen Ming.
Claims (11)
1. the formation method of an aluminum alloy surface inteferometer coating is characterized in that, comprising:
One Al alloy parts is provided;
This Al alloy parts of pre-treatment is to clean its surface;
One predetermined time of this Al alloy parts of anodizing, form an oxide film with a plurality of test-tube baby shape micropores up to this surface;
Handle this oxide film of this Al alloy parts with the acidic solution reaming, enlarge the aperture of this test-tube baby shape micropore;
The energising reaming is handled to enlarge the bottom of this test-tube baby shape micropore and is formed a sedimentary province;
The deposition special metal forms interference structure in this sedimentary province of this test-tube baby shape micropore;
Handle this test-tube baby shape micropore with the hole sealing agent sealing of hole; And ash disposal.
2. the formation method of aluminum alloy surface inteferometer coating as claimed in claim 1 is characterized in that, this pre-treatment comprises takes off ester, alkali cleaning, pickling for the first time, chemical rightenning, and pickling for the second time.
3. the formation method of aluminum alloy surface inteferometer coating as claimed in claim 1, it is characterized in that this anodizing comprises that being soaked in concentration is 20% to 25% sulphuric acid soln, temperature is 15 to 25 degrees centigrade, 1.4 amperes/every square centimeter of current density, the treatment time is at least 30 minutes.
4. the formation method of aluminum alloy surface inteferometer coating as claimed in claim 1, it is characterized in that, above-mentionedly handle this oxide film with the acidic solution reaming and comprise that it is 85% phosphoric acid solution that this Al alloy parts is soaked in concentration, temperature is 20 to 25 degrees centigrade, and the time is 7 minutes.
5. as the formation method of claim 1 or 4 described aluminum alloy surface inteferometer coatings, it is characterized in that, above-mentioned energising reaming is handled and is comprised this Al alloy parts is connected in anode, and be soaked in the phosphoric acid solution that concentration is 150g/L, temperature is 20 to 25 degrees centigrade, feed 10 volts direct current, the time is 5 minutes.
6. the formation method of aluminum alloy surface inteferometer coating as claimed in claim 1, it is characterized in that, above-mentioned deposition special metal comprises this Al alloy parts is connected in negative electrode, and be soaked in sulfuric acid and 5 gram/every liter the amidosulfonic acid nickel solutions of concentration 20%, temperature is 20 to 25 degrees centigrade, feed 10 volts direct current, the time is 5 minutes.
7. the formation method of aluminum alloy surface inteferometer coating as claimed in claim 1 is characterized in that, above-mentioned sealing of hole comprises this Al alloy parts is soaked in the hole sealing agent that concentration is 7g/L, and temperature is 90 ± 5 degrees centigrade, and the time is 30 minutes.
8. the formation method of aluminum alloy surface inteferometer coating as claimed in claim 1 is characterized in that, this ash disposal comprises the nitric acid treatment with concentration 20ml/L.
9. the inteferometer coating structure of an aluminum alloy surface is positioned on the oxide film of this Al alloy parts, and this oxide film comprises a plurality of test-tube baby shape micropores, it is characterized in that, this inteferometer coating structure comprises:
A plurality of sedimentary provinces that are positioned at this test-tube baby shape micropore bottom, wherein the aperture of this sedimentary province is greater than the aperture of this test-tube baby shape micropore;
A plurality of reflecting parts that are made of metal ion partly are deposited in this sedimentary province; And
One sealing of hole layer is covered on this oxide film.
10. the inteferometer coating structure of aluminum alloy surface as claimed in claim 9 is characterized in that, the metal of this reflecting part is nickel.
11. the inteferometer coating structure of aluminum alloy surface as claimed in claim 9 is characterized in that, the height of this sedimentary province is 0.5nm to 1nm, and the height of this reflecting part is lower than the height of this sedimentary province.
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Cited By (5)
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| CN103862748A (en) * | 2014-02-13 | 2014-06-18 | 东莞宜安科技股份有限公司 | Aluminum alloy and polyphenylene sulfide thermal resin composite material as well as preparation method thereof |
| CN105803508A (en) * | 2014-12-31 | 2016-07-27 | 技嘉科技股份有限公司 | Metal substrate surface treatment method |
| CN105803507A (en) * | 2014-12-31 | 2016-07-27 | 技嘉科技股份有限公司 | Metal base surface treatment method |
| WO2018121200A1 (en) * | 2016-12-30 | 2018-07-05 | 比亚迪股份有限公司 | Aluminium alloy shell, preparation method therefor, and personal electronic device |
| WO2018121212A1 (en) * | 2016-12-30 | 2018-07-05 | 比亚迪股份有限公司 | Aluminum alloy housing, preparation method therefor and personal electronic device |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103862748A (en) * | 2014-02-13 | 2014-06-18 | 东莞宜安科技股份有限公司 | Aluminum alloy and polyphenylene sulfide thermal resin composite material as well as preparation method thereof |
| CN105803508A (en) * | 2014-12-31 | 2016-07-27 | 技嘉科技股份有限公司 | Metal substrate surface treatment method |
| CN105803507A (en) * | 2014-12-31 | 2016-07-27 | 技嘉科技股份有限公司 | Metal base surface treatment method |
| CN105803507B (en) * | 2014-12-31 | 2017-10-20 | 技嘉科技股份有限公司 | The surface treatment method of metal base |
| WO2018121200A1 (en) * | 2016-12-30 | 2018-07-05 | 比亚迪股份有限公司 | Aluminium alloy shell, preparation method therefor, and personal electronic device |
| WO2018121212A1 (en) * | 2016-12-30 | 2018-07-05 | 比亚迪股份有限公司 | Aluminum alloy housing, preparation method therefor and personal electronic device |
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Application publication date: 20130821 |