CN102330137A - Inorganic colorful electrolysis coloring technology for aluminium profile anodic oxide film - Google Patents
Inorganic colorful electrolysis coloring technology for aluminium profile anodic oxide film Download PDFInfo
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Abstract
The invention discloses an inorganic colorful electrolysis coloring technology for an aluminium profile anodic oxide film, which is characterized by comprising the following working procedures of: removing oil, etching by alkaline, oxidizing an anode, carrying out intermediate treatment and electrolysis coloring, and sealing holes, wherein the intermediate treatment working procedure is set between the working procedures of oxidizing an anode and electrolysis coloring and comprises three steps: a. DC (Direct Current) section: setting a supply voltage into a direct-current output mode, cleaning the micropores of the anodic oxide film, and reducing the thickness of a barrier layer, wherein a voltage value is 8-14V, and time is 20-50 seconds; b. AC (Alternating Current) section: setting the supply voltage into an alternating-current output mode, and generating a second layer of oxide film in the anodic oxide film; c. DC section: switching the supply voltage to the direct-current output mode, generating a third layer of film on the basis of the second layer of oxide film, wherein the voltage value is 10-20V, and operation time is controlled to 60-500s. According to the inorganic colorful electrolysis coloring technology, the existing electrolysis coloring equipment can be utilized to finish the full-color colorful electrolysis coloring aluminium or aluminium alloy in short time, and the inorganic colorful electrolysis coloring technology has the advantages of low production cost and good coloring quality.
Description
Technical field
The present invention relates to the aluminium section bar building materials technology field, relate to a kind of process method that on the anodic oxidation alloy product, proposes the polychrome electrolytic coloring in particular.
Background technology
Duraluminum is widely used in numerous areas such as automobile, aerospace, building decoration, household electrical appliances, instrument, computer, mobile phone, haberdashery and hardware, has become consumption at present and has been only second to iron and steel and occupies second structural metallic materials.In order to improve the duraluminum service life, satisfy the ornamental requirement of product appearance simultaneously, Al-alloy products is handled through anodized surface can increase substantially its surface hardness and corrosion resistance nature etc., and therefore, anode oxidation process uses extremely extensive.
In order to improve the decorate properties of alloy product, aluminium alloy anode oxide film need carry out painted processing before sealing of hole.Common coloring treatment process is electrolytic coloring and chemical staining.Common electrolytic coloring is merely able to form limited colors such as bronze-colored series, and color is single, ornamental relatively poor, but good weatherability; Organic staining can form coloury shades of colour; But the weathering resistance of Al-alloy products is poor; The organic dye easy ageing causes the alloy product efflorescence, influences the work-ing life and the military service security of product, particularly uses duraluminum to boats and ships, freight container under the ocean environment; Various automobiles, train, the subway and other modes of transport used under the industrial environment are used duraluminum, and its weathering resistance and erosion resistance require extremely strict.Therefore, how alloy product is realized good ornamental and high-weatherability simultaneously, become the aluminum alloy material surface processing and needed one of development key technology badly, cause extensive concern both domestic and external.
Summary of the invention
The object of the invention provides for the deficiency that solves prior art a kind ofly realizes good ornamental and high-weatherability simultaneously on the aluminum alloy building section product, changes that traditional electrolytic coloring color is single, the oxidation aluminium film inorganic color electrolytic colouring technology of the easy atomizing shortcoming of organic dye coloring.
The present invention adopts following technical solution to realize above-mentioned purpose: a kind of oxidation aluminium film inorganic color electrolytic colouring technology; It is characterized in that; Comprise oil removing, alkali erosion, anodic oxidation, intermediate treatment operation, electrolytic coloring and sealing of hole treatment process; Anodic oxidation need be carried out under certain conditions, and between anodic oxidation and electrolytic coloring, arranges a special intermediate treatment operation.
As further specifying of such scheme: the technology of said anodic oxidation operation is to adopt the water cooling temperature reduction way; Make temperature be controlled at 18-22 ℃; Tank liquor is that concentration is the sulphuric acid soln of 10-200 grams per liter, and anodizing time is 20-60 minute, and current density is controlled at 1.1-1.8A/dm
2
Saidly between anodic oxidation and electrolytic coloring, arrange a special intermediate treatment operation, this operation specifically was divided into for 3 steps:
A, DC section: make voltage of supply be arranged to the direct current output mode, the purpose of this part is the micropore of anode purge sull and the thickness that reduces the blocking layer, and magnitude of voltage is at 8-14V, and the time was at 20-50 seconds;
B, AC section: make voltage of supply be arranged to exchange output mode, this part is for regeneration second layer sull in anode oxide film; This part is divided into three small steps again:
B1, used power supply wave shape are alternating-current, and its magnitude of voltage is between 1-9v, and the running time is controlled at 10-50s;
B2, used power supply wave shape are alternating-current, and its voltage is between 1-5v, and the running time is controlled at 10-170s;
B3, used power supply wave shape are alternating-current, and its voltage is between 1-4v, and the running time is controlled at 200-380s;
C, DC section: make voltage of supply switch to the direct current output mode; This part is for regeneration trilamellar membrane on the basis of second tunic; Which kind of color is this part determining, as long as change this part voltage and time parameter, just can obtain any colour system in the full spectral range; Its magnitude of voltage is between 10-20v, and the running time is controlled at 60-500s, and it is fixed to need to come according to concrete color.
In the said electrolytic coloring stage, this part is the deposition process of painted main salt, and its magnitude of voltage is between 12-20v, and the running time is controlled at 150-300s.
After electrolytic coloring, arrange an operation again, increase the trickle color adjusting stage, can prepare same colour system, deep mixed shades of colour; This stage is called the DC section, promptly passes to suitable direct current, and voltage range is at 5-18v; In addition, also comprise following pattern, i.e. repeating step a-c, i.e. DC-AC-DC-AC-DC-AC-DC again after electrolysis is accomplished.
The intermediate treatment operation of between said anodic oxidation and electrolytic coloring, arranging all is to carry out at painted groove, promptly only needs to prepare a painted groove, and the tin nickel mixing salt that mainly consists of of its tank liquor adds color additive, colour temperature and is controlled at 20～25 ℃.
Said color additive, it is formed as follows:
Sulfuric acid: 15-30g/L
Weibull: 3-15g/L
Hydrocerol A: 3-15g/L
Dihydroxy-benzene: 1-3g/L
DMSO 99.8MIN.: add doubly by the 2-4 of Sn2+ concentration and to add
Water: surplus.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
1, wide colour system only needs appropriate change electrical parameter or time parameter just can obtain nearly all colour system.
2, technology is simple, paintedly need not change electrolyzer, is convenient to realize producing in batches.
3, power supply wave shape is simple, only needs a simple power output apparatus, uses common direct current and common sinusoidal waveform, only requires to control the rise time of voltage or electric current well, and can be stabilized to expected value and get final product.
4, coloring stabilized, aberration is little, as long as control desired parameters well, the color reproducibility is fine, and the aberration of painted sull is little.
5, be convenient to realize producing in batches, available existing electrolytic coloring production line embodiment of the present invention, reduced investment, instant effect is easy to apply.
6, cell liquid good stability, painted fast, raw material consumption is few, and production cost is low.
Embodiment
A kind of oxidation aluminium film of the present invention inorganic color electrolytic colouring technology; Comprise oil removing, alkali erosion, anodic oxidation, intermediate treatment operation, electrolytic coloring and sealing of hole treatment process; Anodic oxidation need be carried out under certain conditions, and between anodic oxidation and electrolytic coloring, arranges a special intermediate treatment operation.The technology of anodic oxidation operation is to adopt the water cooling temperature reduction way, makes temperature be controlled at 18-22 ℃, and tank liquor is that concentration is the sulphuric acid soln of 10-200 grams per liter, and anodizing time is 20-60 minute, and current density is controlled at 1.1-1.8A/dm
2
Between anodic oxidation and electrolytic coloring, arrange a special intermediate treatment operation, this operation specifically was divided into for 3 steps:
A, DC section: make voltage of supply be arranged to the direct current output mode, the purpose of this part is the micropore of anode purge sull and the thickness that reduces the blocking layer, and magnitude of voltage is at 8-14V, and the time was at 20-50 seconds;
B, AC section: make voltage of supply be arranged to exchange output mode, this part is for regeneration second layer sull in anode oxide film; This part is divided into three small steps again:
B1, used power supply wave shape are alternating-current, and its magnitude of voltage is between 1-9v, and the running time is controlled at 10-50s;
B2, used power supply wave shape are alternating-current, and its voltage is between 1-5v, and the running time is controlled at 10-170s;
B3, used power supply wave shape are alternating-current, and its voltage is between 1-4v, and the running time is controlled at 200-380s;
C, DC section: make voltage of supply switch to the direct current output mode; This part is for regeneration trilamellar membrane on the basis of second tunic; Which kind of color is this part determining, as long as change this part voltage and time parameter, just can obtain any colour system in the full spectral range; Its magnitude of voltage is between 10-20v, and the running time is controlled at 60-500s, and it is fixed to need to come according to concrete color.
Embodiment one
With 6063-T5 duraluminum test piece (its specification is the rectangle thin flat plate of 200mm * 15mm) through conventional oil removing; Carry out in 60 ℃ the NaOH solution alkali erosion, in and after the bright dipping, washing; Be in the sulphuric acid soln of 190 grams per liters in concentration then; 2 ℃ of controlled temperature 18 scholars, 15 volts of volts DSs, current density 1.3 peace/decimetres
2, carry out 25 minutes anodize, obtain the sull of about 12um, at last washing, subsequent use.
Then in electrolytic colouring liquid, carry out electrolytic coloring and handle, the electrolytic coloring tank liquor form and painted after colour index list in table one. this part operation will be experienced following four steps, as follows:
1.DC section: make voltage of supply be arranged to the direct current output mode, make voltage rise to 11V at 0-10 in the time of second then, kept 20 seconds at this magnitude of voltage of 11V then from 0V.
2.AC section, this part is divided into 3 small steps again, respectively as follows:
A.AC (6V) section, this part in second, makes voltage rise to 6V from 0V at 0-5 with common sinusoidal ac, on this 6V magnitude of voltage, keeps 25 seconds then;
B.AC (4V) section, this part is same in 3 seconds, to make voltage drop to 4V from 6V with common sinusoidal ac, on this 4V magnitude of voltage, keeps 90 seconds then;
C.AC (2.8V) section, this part is same in 3 seconds, to make voltage drop to 2.8V from 4V with common sinusoidal ac, on this 2.8V magnitude of voltage, keeps 280 seconds then;
3.DC section: make voltage of supply switch to the direct current output mode; (determining which kind of color,, just can obtain any colour system in the whole body system) in 25 seconds then as long as change this part; Make voltage rise to 13V, on this magnitude of voltage, kept 60 seconds then from 0V;
4.AC section: in the electrolytic coloring stage, this part is the deposition process of painted main salt, makes voltage of supply switch to common interchange output mode, in 25 seconds, in 25 seconds, makes voltage rise to 16V from 0V, on this magnitude of voltage, keeps 210 seconds then.
Through after the above step, can adopt conventional middle temperature sealing of hole then so that workpiece surface obtains the color of light slate gray, in pore-sealing liquid, soak 30min.Test through each item; Show: the color reproducibility of painted sull is good, aberration deviation little (Δ E≤3.5); And the light slate gray aluminium alloy type section product over-all properties index of preparation all meets the GB5237.2-2008 request of national standard; Adopt 313B fluorescent ultraviolet lamp artificial accelerated aging test test, aberration reaches 1 grade after the 300h irradiation, and ageing-resistant performance is superior to the spray-on coating aluminium section bar.
Embodiment two
Concrete step is basically with embodiment one; Just step 3 is done suitably adjustment: changing 355 seconds into from 60 seconds in the galvanic hold-time of 13V, through after the above step, can be so that workpiece surface obtains bottle-green color; Adopt conventional middle temperature sealing of hole then; In pore-sealing liquid, soak 30min, through each item test, show: the color reproducibility of painted sull is good, aberration deviation little (Δ E≤3.5); And the deep green aluminium alloy type section product over-all properties index of preparation all meets the GB5237.2-2008 request of national standard; Adopt 313B fluorescent ultraviolet lamp artificial accelerated aging test test, aberration reaches 1 grade after the 300h irradiation, and ageing-resistant performance is superior to the spray-on coating aluminium section bar.
Embodiment three
Concrete step is basically with embodiment one; Just step 3 is done suitably to revise: changing 425 seconds into from 60 seconds in the galvanic hold-time of 13V, through after the above step, can be so that workpiece surface obtains mauve color; Adopt conventional middle temperature sealing of hole then; In pore-sealing liquid, soak 30min, through each item test, show: the color reproducibility of painted sull is good, aberration deviation little (Δ E≤3.5); And the red-purple aluminium alloy type section product over-all properties index of preparation all meets the GB5237.2-2008 request of national standard; Adopt 313B fluorescent ultraviolet lamp artificial accelerated aging test test, aberration reaches 1 grade after the 300h irradiation, and ageing-resistant performance is superior to the spray-on coating aluminium section bar.
Embodiment four
Concrete step is basically with embodiment one; Just step 3 is done suitably to revise: changing 195 seconds into from 60 seconds in the galvanic hold-time of 13V, through after the above step, can be so that workpiece surface obtains flavous color; Adopt conventional middle temperature sealing of hole then; In pore-sealing liquid, soak 30min, through each item test, show: the color reproducibility of painted sull is good, aberration deviation little (Δ E≤3.5); And the golden yellow aluminium alloy section bar product over-all properties index of preparation all meets the GB5237.2-2008 request of national standard; Adopt 313B fluorescent ultraviolet lamp artificial accelerated aging test test, aberration reaches 1 grade after the 300h irradiation, and ageing-resistant performance is superior to the spray-on coating aluminium section bar.
Embodiment five
Concrete step is basically with embodiment one; Just step 3 is done suitably to revise: changing 305 seconds into from 60 seconds in the galvanic hold-time of 13V, through after the above step, can be so that workpiece surface obtains cyanic color; Adopt conventional middle temperature sealing of hole then; In pore-sealing liquid, soak 30min, through each item test, show: the color reproducibility of painted sull is good, aberration deviation little (Δ E≤3.5); And the cyanic colours aluminium alloy type section product over-all properties index of preparation all meets the GB5237.2-2008 request of national standard; Adopt 313B fluorescent ultraviolet lamp artificial accelerated aging test test, aberration reaches 1 grade after the 300h irradiation, and ageing-resistant performance is superior to the spray-on coating aluminium section bar.
Above-described only is preferred implementation of the present invention, should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (7)
1. oxidation aluminium film inorganic color electrolytic colouring technology; It is characterized in that; It comprises oil removing, alkali erosion, anodic oxidation, intermediate treatment operation, electrolytic coloring and sealing of hole treatment process; Between anodic oxidation and electrolytic coloring, arrange an intermediate treatment operation, this operation specifically was divided into for 3 steps:
A, DC section: make voltage of supply be arranged to the direct current output mode, the micropore of anode purge sull and the thickness that reduces the blocking layer, magnitude of voltage are at 8-14V, and the time was at 20-50 seconds;
B, AC section: make voltage of supply be arranged to exchange output mode, regeneration second layer sull in anode oxide film;
C, DC section: make voltage of supply switch to the direct current output mode, regeneration trilamellar membrane on the basis of second layer sull, magnitude of voltage is between 10-20v, and the running time is controlled at 60-500s.
2. oxidation aluminium film inorganic color electrolytic colouring technology according to claim 1; It is characterized in that; The technology of said anodic oxidation operation is to adopt the water cooling temperature reduction way, and temperature is controlled at 18-22 ℃, and it is the sulphuric acid soln of 10-200 grams per liter that anode oxidation process adopts concentration; Anodizing time is 20-60 minute, and current density is controlled at 1.1-1.8A/dm
2
3. oxidation aluminium film inorganic color electrolytic colouring technology according to claim 1 is characterized in that in the b of said intermediate treatment operation step, this part is divided into three small steps:
B1, used power supply wave shape are alternating-current, and its magnitude of voltage is between 1-9v, and the running time is controlled at 10-50s;
B2, used power supply wave shape are alternating-current, and its voltage is between 1-5v, and the running time is controlled at 10-170s;
B3, used power supply wave shape are alternating-current, and its voltage is between 1-4v, and the running time is controlled at 200-380s.
4. oxidation aluminium film inorganic color electrolytic colouring technology according to claim 1; It is characterized in that in the said electrolytic coloring stage, this part is the deposition process of painted main salt; Its magnitude of voltage is between 12-20v, and the running time is controlled at 150-300s.
5. oxidation aluminium film inorganic color electrolytic colouring technology according to claim 1 is characterized in that, after said electrolytic coloring operation, arranges an operation again; Increase the trickle color adjusting stage; This stage is the DC section, passes to direct current, and voltage range is at 5-18v; In addition, also comprise following pattern, repeating step a-c again after electrolysis is accomplished.
6. oxidation aluminium film inorganic color electrolytic colouring technology according to claim 1; It is characterized in that; The intermediate treatment operation of between said anodic oxidation and electrolytic coloring, arranging all is to carry out at same painted groove; The tin nickel mixing salt that mainly consists of of the tank liquor of painted groove adds color additive, colour temperature and is controlled at 20～25 ℃.
7. oxidation aluminium film inorganic color electrolytic colouring technology according to claim 6 is characterized in that, said color additive, and it is formed as follows:
Sulfuric acid: 15-30g/L,
Weibull: 3-15g/L,
Hydrocerol A: 3-15g/L,
Dihydroxy-benzene: 1-3g/L,
DMSO 99.8MIN.: add doubly by the 2-4 of Sn2+ concentration add,
Water: surplus.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102758235A (en) * | 2012-07-27 | 2012-10-31 | 肇庆亚洲铝厂有限公司 | Process for coloring aluminum sections with pure black pigment |
| CN103305888A (en) * | 2012-03-16 | 2013-09-18 | 苏州春兴精工股份有限公司 | Anodic oxidation treatment method for aerial aluminum alloy surface |
| CN107937962A (en) * | 2018-01-03 | 2018-04-20 | 广东坚美铝型材厂（集团）有限公司 | A kind of aluminium alloy extrusions coloring process |
| CN109468673A (en) * | 2018-12-16 | 2019-03-15 | 桂林理工大学 | A kind of aluminum alloy surface color method |
| CN109722698A (en) * | 2018-12-18 | 2019-05-07 | 佛山科学技术学院 | A kind of aluminum alloy surface bilayer microstructure film interference coloration method |
| CN109989086A (en) * | 2019-04-19 | 2019-07-09 | 河北工业大学 | A kind of preparation method of the porous aluminas photon crystal film with high saturation schemochrome |
| CN110552039A (en) * | 2019-01-23 | 2019-12-10 | 深圳市鹏福创新五金有限公司 | secondary oxidation sealing process |
| CN110565141A (en) * | 2019-01-23 | 2019-12-13 | 深圳市鹏福创新五金有限公司 | Secondary oxidation sealing process |
| CN110699731A (en) * | 2019-09-30 | 2020-01-17 | 佛山科学技术学院 | Preparation method of aluminum alloy-based colorful composite oxide film with three-layer microstructure |
| CN110983407A (en) * | 2019-12-19 | 2020-04-10 | 佛山科学技术学院 | Preparation method for in-situ patterning of colorful composite oxide film on surface of aluminum alloy |
| CN112522760A (en) * | 2020-12-18 | 2021-03-19 | 东莞市新东明科技有限公司 | Method for removing nickel from anodic aluminum oxide alloy |
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| CN103305888A (en) * | 2012-03-16 | 2013-09-18 | 苏州春兴精工股份有限公司 | Anodic oxidation treatment method for aerial aluminum alloy surface |
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| CN107937962A (en) * | 2018-01-03 | 2018-04-20 | 广东坚美铝型材厂（集团）有限公司 | A kind of aluminium alloy extrusions coloring process |
| CN109468673A (en) * | 2018-12-16 | 2019-03-15 | 桂林理工大学 | A kind of aluminum alloy surface color method |
| CN109722698A (en) * | 2018-12-18 | 2019-05-07 | 佛山科学技术学院 | A kind of aluminum alloy surface bilayer microstructure film interference coloration method |
| CN110565141A (en) * | 2019-01-23 | 2019-12-13 | 深圳市鹏福创新五金有限公司 | Secondary oxidation sealing process |
| CN110552039A (en) * | 2019-01-23 | 2019-12-10 | 深圳市鹏福创新五金有限公司 | secondary oxidation sealing process |
| CN109989086A (en) * | 2019-04-19 | 2019-07-09 | 河北工业大学 | A kind of preparation method of the porous aluminas photon crystal film with high saturation schemochrome |
| CN109989086B (en) * | 2019-04-19 | 2020-11-03 | 河北工业大学 | Preparation method of porous alumina photonic crystal film with high-saturation structural color |
| CN110699731A (en) * | 2019-09-30 | 2020-01-17 | 佛山科学技术学院 | Preparation method of aluminum alloy-based colorful composite oxide film with three-layer microstructure |
| CN110983407A (en) * | 2019-12-19 | 2020-04-10 | 佛山科学技术学院 | Preparation method for in-situ patterning of colorful composite oxide film on surface of aluminum alloy |
| CN112522760A (en) * | 2020-12-18 | 2021-03-19 | 东莞市新东明科技有限公司 | Method for removing nickel from anodic aluminum oxide alloy |
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