CN107177875A - A kind of coppery aluminium electrolytic coloring tank liquor - Google Patents
A kind of coppery aluminium electrolytic coloring tank liquor Download PDFInfo
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- CN107177875A CN107177875A CN201710325792.3A CN201710325792A CN107177875A CN 107177875 A CN107177875 A CN 107177875A CN 201710325792 A CN201710325792 A CN 201710325792A CN 107177875 A CN107177875 A CN 107177875A
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- coppery
- additive
- tank liquor
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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
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a kind of coppery aluminium electrolytic coloring tank liquor, including cupric sulfate pentahydrate, seven water nickel sulfates, sulfuric acid, additive and water；The mass concentration of the cupric sulfate pentahydrate is 10 15g/L, and the mass concentration of the seven water nickel sulfate is 2 4g/L, and the mass concentration of the sulfuric acid is 16 22g/L, and the mass concentration of the additive is 10 15g/L.Using the present invention, can on aluminium uniform coloring, and firm coloration is stable.
Description
Technical field
The present invention relates to field of metal surface treatment, more particularly to a kind of coppery aluminium electrolytic coloring tank liquor.
Background technology
With oxygen slow redox reaction occurs for aluminium in large natural environment, in aluminium material surface formation aluminum oxide
Film, but this pellumina is loosely organized, is unfavorable for protecting aluminum or aluminum alloy.In existing aluminium material surface treatment process steps
General elder generation's anodic oxidation, rear electrolytic coloring can improve the weatherability of aluminium, wearability, light resistance and heat resistance.
The colored aluminum alloy for being presently used for architectural shape is mainly bronze colour system and bronze colour system, electrolyte used
The usually series such as pink salt, nickel salt or cobalt salt, the dispersibility lover of tank liquor is less sensitive to impurity, film layer uniform hue, steady
Fixed, aberration is small, and the influence of environmental pollution is relatively small.And electrolyte rosy typically use copper sulphate, still
Copper ion rests on the top layer of pellumina hole in electrolysis, and coloring is loosely；In addition, the larger reduction generation copper atom of hole
Aggregation is more, causes irregular colour even, it is necessary to which a kind of new red colour system electrolytic coloring tank liquor solves above-mentioned technical problem.
The content of the invention
The technical problems to be solved by the invention are there is provided a kind of coppery aluminium electrolytic coloring tank liquor, can be in aluminium
Upper uniform coloring.
The technical problems to be solved by the invention are also resided in there is provided a kind of coppery aluminium electrolytic coloring tank liquor, and coloring is firm
Gu it is stable.
In order to solve the above-mentioned technical problem, the invention provides a kind of coppery aluminium electrolytic coloring tank liquor, including five water
Copper sulphate, seven water nickel sulfates, sulfuric acid, additive and water；The mass concentration of the cupric sulfate pentahydrate is 10-15g/L, described seven
The mass concentration of water nickel sulfate is 2-4g/L, and the mass concentration of the sulfuric acid is 16-22g/L, the mass concentration of the additive
For 10-15g/L.
As the optimal technical scheme of the coppery aluminium electrolytic coloring tank liquor, the additive is by weight percentage
Including following raw material：
Tartaric acid 8-15%；
Citric acid 5-10%；
Boric acid 5-10%；
Catechol 1-5%；
Methyl hydroquinone 1-5%；
Water surplus.
As the optimal technical scheme of the coppery aluminium electrolytic coloring tank liquor, the colouring slot liquid needs reality when in use
When monitoring cupric sulfate pentahydrate and additive concentration, when less than cupric sulfate pentahydrate and additive concentration scope, by cupric sulfate pentahydrate：
Additive=1：1 concentration proportioning is added to the colouring slot liquid.
As the optimal technical scheme of the coppery aluminium electrolytic coloring tank liquor, the temperature in use of the colouring slot liquid is
18-20℃。
As the optimal technical scheme of the coppery aluminium electrolytic coloring tank liquor, using power of alterating and direct current electrolytic coloring,
Coloration voltage is 14-18V.
Implement the present invention, have the advantages that：
Coppery aluminium electrolytic coloring tank liquor of the present invention, which adds seven water nickel sulfates, can effectively improve the electrical conductivity of tank liquor, have
Copper atom is reduced into beneficial to copper ion, is also easy to occur redox reaction even in porous layer bore hole size smaller part,
It is more equal in the top layer coppery for macroscopically showing as aluminium so as to improve in porous layer bore hole size smaller part copper atom content
It is even；On the other hand, it is also more closer compared to the position of generation copper atom than existing similar formula because the electrical conductivity of tank liquor is improved
The active layer of pellumina, copper atom is difficult to backing out, the Adhesion enhancement of copper atom, and firm coloration is stable.
In addition, under the cooperation of other additives so that colouring slot liquid has anti-precipitation, reducing agent oxidation characteristic is prevented
Stable tank liquor.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, it will make further detailed to the present invention below
Description.
Aluminium forms one layer of pellumina after anodized on surface, and pellumina surface is porous layer,
The bottom of pellumina is connected with aluminum substrate, then is fine and close oxide-film thin layer, also referred to as active layer or barrier layer.And incite somebody to action
In the electrolyte for immersing certain metal salt, and as an electrode (because with alternating current), and another it can extremely use and electrolyte
Institute's metalline identical simple metal plate or graphite, stainless steel plate etc..When the two poles of the earth pass to alternating current simultaneously, (typically in low electricity
Under conditions of pressure and low current density), aluminum products just automatically become negative electrode, and face discharges hydrogen from it, while golden
It is poor that metal ion in category solution is formed about strong ion concentration in aluminum products, and is deep into active layer by porous layer
On, alternately bear violent reduction and slow oxidation, namely active layer consumingly attracts metal ion, and with
The negative electrostatic charge produced there repeated electric discharge and precipitating metal particulate or metal oxide, and it is fine to be deposited on oxide-film
At 3-6 μm of the bottom in hole.These particulates are generally in hair-like, spherical or granular, these metal particles generation under the effect of light
Diffraction, just makes oxide-film that a variety of colors is presented, and this is electrolytic coloring.
Main salt is electrolysed in the electrolytic coloring tank liquor of conventional red copper colour system for copper sulphate, in aoxidizing fenestra in aluminium section bar
The mode of electro-deposition of metal copper obtains coppery aluminium section bar, and coppery aluminium section bar is widely used in the interior decoration of top-grade building
Material.But there are following two problems in the electrolytic coloring tank liquor of existing red copper colour system：（1）Copper atom is in porous layer aperture big
Hole deposition is more, and bore hole size is less, is difficult to deposit, and bore hole size smaller part copper atom deposit thickness is also not so good as hole
Hole size larger part copper atom deposit thickness, causes coloring uneven；（2）Copper atom deposition position is shallower, it is difficult to reach activity
Layer, easily comes off, causes to colour insecure stabilization.
To solve existing technical problem, the present invention provides a kind of coppery aluminium electrolytic coloring tank liquor, including five water sulphur
Sour copper, seven water nickel sulfates, sulfuric acid, additive and water；The mass concentration of the cupric sulfate pentahydrate is 10-15g/L, seven water
The mass concentration of nickel sulfate is 2-4g/L, and the mass concentration of the sulfuric acid is 16-22g/L, and the mass concentration of the additive is
10-15g/L.Wherein the concentration proportioning of cupric sulfate pentahydrate and seven water nickel sulfates is 2.5-7.5:1, reagent dosage is small, and color is uniform,
It is coloring stabilized.The inventors discovered that under when the mass concentration of seven water nickel sulfates exceeds 2-4g/L scopes, electrical conductivity all occurs substantially
Drop, therefore the scope is to preferably select.
Seven water nickel sulfate of the present invention is the accelerator that copper ion is reduced into copper atom.Seven water sulfuric acid are added in tank liquor
Nickel can effectively improve the electrical conductivity of tank liquor, be conducive to copper ion to be reduced into copper atom, even in porous layer bore hole size compared with
Small place is also easy to occur redox reaction, so as to improve in porous layer bore hole size smaller part copper atom content, grand
The top layer coppery of aluminium is shown as in sight evenly；On the other hand, because the electrical conductivity of tank liquor is improved, similar match somebody with somebody than existing
Side compares the position of generation copper atom also closer to the active layer of pellumina, and copper atom is difficult to backing out, test discovery copper
The adhesive force of atom becomes strong, and firm coloration is stable.
It should be noted that the additive includes following raw material by weight percentage：
Tartaric acid 8-15%；
Citric acid 5-10%；
Boric acid 5-10%；
Catechol 1-5%；
Methyl hydroquinone 1-5%；
Water surplus.
Wherein, additive mesotartaric acid and citric acid are complexing agent, can stablize the concentration of metal ions in tank liquor, play anti-
The effect of precipitation.And boric acid is buffer, catechol and methyl hydroquinone can prevent that reducing agent from aoxidizing, anti-aging.
Further illustrated below by specific experiment：
1st, experimental subjects：
Sample 1：Using the aluminium after polishing fluid electrolytic coloring of the present invention；
Sample 2：Polishing fluid lacks addition nickel sulfate than the polishing fluid of sample 1, using the aluminium after the polishing fluid electrolytic coloring.
2nd, electrolytic condition
The aluminium of sample 1 and sample 2 is electrolysed 3 minutes in the case where temperature is 18-20 DEG C, 16V alternating current.
3rd, test event
The electrical conductivity of colouring slot liquid, copper atom particle diameter, copper atom are in pellumina Porous before test sample 1 and sample 2 are electrolysed
The position of layer.
4th, experimental result
As can be known from the above table, the colouring slot liquid electrical conductivity after a small amount of nickel sulfate has been added to significantly improve, and copper atom and pellumina
The beeline of active layer is reduced to 1.3 μm from 5.2 μm, and retention of color is significantly improved.
The application method of coloring cell liquid of the present invention：Aluminium is placed in electrolytic coloring tank liquor, is 18-20 in temperature
DEG C, it is electrolysed 1-5 minutes under 14-18V alterating and direct current, specific electrolysis time is depending on plating shade, light product electricity
The solution time is short, and dark product electrolysis time is long.
Copper sulphate and additive can be lost in the coloring cell liquid in electrolytic process, change coloring cell liquid ion
Concentration, is to need the concentration of monitoring cupric sulfate pentahydrate and additive in real time during this use so as to influence coloring effect, when less than
Cupric sulfate pentahydrate and additive concentration scope, by cupric sulfate pentahydrate：Additive=1：1 concentration proportioning is added to the coloring groove
Liquid.Cupric sulfate pentahydrate and the additive concentration scope is initial burnishing liquid concentration ratio.
Further illustrated below by specific embodiment：
Embodiment 1
Coppery aluminium electrolytic coloring tank liquor includes cupric sulfate pentahydrate, seven water nickel sulfates, sulfuric acid, additive and water；Five water
The mass concentration of copper sulphate is 12g/L, and the mass concentration of the seven water nickel sulfate is 3g/L, and the mass concentration of the sulfuric acid is
18g/L, the mass concentration of the additive is 12g/L；The additive includes following raw material by weight percentage：9% winestone
Acid, 7% citric acid, 8% boric acid, 2% catechol, 3% methyl hydroquinone, surplus is water.
Embodiment 2
Coppery aluminium electrolytic coloring tank liquor includes cupric sulfate pentahydrate, seven water nickel sulfates, sulfuric acid, additive and water；Five water
The mass concentration of copper sulphate is 14g/L, and the mass concentration of the seven water nickel sulfate is 2g/L, and the mass concentration of the sulfuric acid is
20g/L, the mass concentration of the additive is 13g/L；The additive includes following raw material by weight percentage：10% wine
Stone acid, 6% citric acid, 7% boric acid, 1% catechol, 2% methyl hydroquinone, surplus is water.
Embodiment 3
Coppery aluminium electrolytic coloring tank liquor includes cupric sulfate pentahydrate, seven water nickel sulfates, sulfuric acid, additive and water；Five water
The mass concentration of copper sulphate is 11g/L, and the mass concentration of the seven water nickel sulfate is 4g/L, and the mass concentration of the sulfuric acid is
17g/L, the mass concentration of the additive is 11g/L；The additive includes following raw material by weight percentage：12% wine
Stone acid, 8% citric acid, 6% boric acid, 3% catechol, 1% methyl hydroquinone, surplus is water.
Embodiment 4
Coppery aluminium electrolytic coloring tank liquor includes cupric sulfate pentahydrate, seven water nickel sulfates, sulfuric acid, additive and water；Five water
The mass concentration of copper sulphate is 12g/L, and the mass concentration of the seven water nickel sulfate is 3g/L, and the mass concentration of the sulfuric acid is
21g/L, the mass concentration of the additive is 14g/L；The additive includes following raw material by weight percentage：13% wine
Stone acid, 6% citric acid, 9% boric acid, 4% catechol, 2% methyl hydroquinone, surplus is water.
Embodiment 5
Coppery aluminium electrolytic coloring tank liquor includes cupric sulfate pentahydrate, seven water nickel sulfates, sulfuric acid, additive and water；Five water
The mass concentration of copper sulphate is 13g/L, and the mass concentration of the seven water nickel sulfate is 4g/L, and the mass concentration of the sulfuric acid is
19g/L, the mass concentration of the additive is 14g/L；The additive includes following raw material by weight percentage：10% wine
Stone acid, 3% citric acid, 8% boric acid, 4% catechol, 4% methyl hydroquinone, surplus is water.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (5)
1. a kind of coppery aluminium electrolytic coloring tank liquor, it is characterised in that including cupric sulfate pentahydrate, seven water nickel sulfates, sulfuric acid, add
Plus agent and water；The mass concentration of the cupric sulfate pentahydrate is 10-15g/L, and the mass concentration of the seven water nickel sulfate is 2-4g/
L, the mass concentration of the sulfuric acid is 16-22g/L, and the mass concentration of the additive is 10-15g/L.
2. coppery aluminium electrolytic coloring tank liquor as claimed in claim 1, it is characterised in that the additive is by weight percentage
Meter includes following raw material：
Tartaric acid 8-15%；
Citric acid 5-10%；
Boric acid 5-10%；
Catechol 1-5%；
Methyl hydroquinone 1-5%；
Water surplus.
3. coppery aluminium electrolytic coloring tank liquor as claimed in claim 1, it is characterised in that the colouring slot liquid is needed when in use
The concentration of cupric sulfate pentahydrate and additive is monitored in real time, when less than cupric sulfate pentahydrate and additive concentration scope, by five water sulfuric acid
Copper：Additive=1：1 concentration proportioning is added to the colouring slot liquid.
4. coppery aluminium electrolytic coloring tank liquor as claimed in claim 1, it is characterised in that the temperature in use of the colouring slot liquid
For 18-20 DEG C.
5. coppery aluminium electrolytic coloring tank liquor as claimed in claim 1, it is characterised in that be electrolysed using power of alterating and direct current
Color, coloration voltage is 14-18V.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710325792.3A CN107177875B (en) | 2017-05-10 | 2017-05-10 | A kind of coppery aluminium electrolytic coloring tank liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710325792.3A CN107177875B (en) | 2017-05-10 | 2017-05-10 | A kind of coppery aluminium electrolytic coloring tank liquor |
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| CN107177875A true CN107177875A (en) | 2017-09-19 |
| CN107177875B CN107177875B (en) | 2018-08-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101215A (en) * | 1986-02-28 | 1986-07-16 | 北京有色金属研究总院 | The coloring process of aluminum or aluminum alloy |
| US5587063A (en) * | 1992-12-24 | 1996-12-24 | Henkel Kommanditgesellschaft Auf Aktien | Method for electrolytic coloring of aluminum surfaces using alternating current |
| CN104988556A (en) * | 2015-08-11 | 2015-10-21 | 马鞍山市华冶铝业有限责任公司 | Electrolytic coloring liquid of aluminum profile and preparation method, application and application method thereof |
| CN105821461A (en) * | 2016-05-19 | 2016-08-03 | 广东伟业铝厂集团有限公司 | Aluminum alloy copper salt coloring electrophoresis process |
-
2017
- 2017-05-10 CN CN201710325792.3A patent/CN107177875B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101215A (en) * | 1986-02-28 | 1986-07-16 | 北京有色金属研究总院 | The coloring process of aluminum or aluminum alloy |
| US5587063A (en) * | 1992-12-24 | 1996-12-24 | Henkel Kommanditgesellschaft Auf Aktien | Method for electrolytic coloring of aluminum surfaces using alternating current |
| CN104988556A (en) * | 2015-08-11 | 2015-10-21 | 马鞍山市华冶铝业有限责任公司 | Electrolytic coloring liquid of aluminum profile and preparation method, application and application method thereof |
| CN105821461A (en) * | 2016-05-19 | 2016-08-03 | 广东伟业铝厂集团有限公司 | Aluminum alloy copper salt coloring electrophoresis process |
Non-Patent Citations (3)
| Title |
|---|
| 何湘柱等: "铝阳极氧化膜的复合金属盐电解着色的研究", 《山东矿业学院学报》 * |
| 桂诗亮等: "紫铜色建筑铝型材生产工艺的研究", 《LW2010铝型材技术（国际）论坛文集》 * |
| 胡中爱等: "阳极氧化铝在Cu-Ni混合浴中的电解着色", 《西北师范大学学报（自然科学版）》 * |
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Inventor after: Pan Weijin Inventor after: Guan Jinfu Inventor after: Liang Meichan Inventor before: Pan Weijin |
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