CN1492081A - Process for preparing solar energy colour absorption coating by aluminium three-step electrolysis - Google Patents
Process for preparing solar energy colour absorption coating by aluminium three-step electrolysis Download PDFInfo
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- CN1492081A CN1492081A CNA031507794A CN03150779A CN1492081A CN 1492081 A CN1492081 A CN 1492081A CN A031507794 A CNA031507794 A CN A031507794A CN 03150779 A CN03150779 A CN 03150779A CN 1492081 A CN1492081 A CN 1492081A
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Abstract
The present invention belongs to the field of solar energy application and the three-step electrolysis process of preparing color solar energy absorbing coating has increased electrolysis step in phosphoric acid after conventional electrolysis step in sulfuric acid so as to prepare on the pure aluminum substrate color selective solar energy absorbing coating with excellent bonding to the substrate and good optical performance. The technological process includes chemical pre-treatment, electrolysis in sulfuric acid, electrolysis in phosphoric acid, electrolysis of metal salt to colorize, and pore closing in boiling water. The coating is red and green and decorative, has absorptivity of 0.8-0.9, and is suitable for external low temperature solar heat collector.
Description
Technical field
The present invention relates to a kind of technology for preparing the colored absorber coatings of sun power, particularly a kind of aluminium three one-step electrolysis methods prepare the technology of solar colored look absorber coatings, belong to the heliotechnics Application Areas.
Background technology
The distinct issues the most that present worldwide faces are the environment and the energy, i.e. environmental degradation and energy shortage.The development of this new function material of solar energy materials both can solve the energy shortage that the mankind face, and did not cause environmental pollution again.In the solar thermal utilization of sun power, determined its range of application in order to the performance and the outward appearance of the heat collector absorption surface coating of realizing light-thermal transition.The preparation method of the absorber coatings of solar energy collector mainly contains electrochemical plating at present, the electrochemical surface conversion method, vacuum coating method, brushing paint method etc., but these traditional methods can only obtain the absorber coatings of black usually, and color is single, not attractive in appearance, lack ornamentally, can not make solar water heater and buildings harmonious on color, more can not be as the heat absorbing coating of solar energy housing.Aluminium three one-step electrolysis methods are current state-of-the-art aluminium electrolyticing coloring technology, and it can change the structure and the geometrical dimension of oxide film, obtain bright in luster, the absorber coatings that optical property is good.Find " non-ferrous metal processing " 1996:(3 by literature search): the bright people of grade of high sand will who has published Japan on 43～46 introduces the article " the polychrome electrocolor process of aluminium " of three one-step electrolysis method technologies.The technology of mentioning in this article is carried out anodic oxidation as intermediate treatment after at first anodic oxidation reaches desirable film thickness in sulfuric acid in phosphoric acid, thereby has developed the method for only changing into phosphoric acid oxide film quality in the pin hole bottom.This method is by sulphuric acid anodizing, and three operations of phosphoric acid anodizing and electrolytic coloring are formed, thereby are called as the three-step electrolytic coloring method.Yet current three-step electrolytic coloring method technology is difficult to control, and the influence of electrolytic coloring time to tonal variation significantly is able to a second meter, and the control of its tone is difficulty very.
Summary of the invention
The present invention is directed to the deficiency that exists in the above-mentioned technology, provide a kind of aluminium three one-step electrolysis methods to prepare the technology of solar colored look absorber coatings, grope a whole set of and prepared the processing parameter of colored absorber coatings, make the absorber coatings color of preparation various, ornamental strong, coating life is long, can satisfy the industrial production requirement substantially.
The present invention is achieved by the following technical solutions, the present invention utilizes three-step electrolytic coloring technology, in conventional sulfuric acid liquid, behind the one-step electrolysis, increased by two one-step electrolysis technologies in phosphoric acid, thereby prepared and the matrix good combination at the matrix surface of fine aluminium, the colored solar coating for selective absorption that optical property is good, its technical process is: 1. Chemical Pretreatment, 2. sulfuric acid one one-step electrolysis, 3. di(2-ethylhexyl)phosphate one-step electrolysis, 4. metal-salt three-step electrolytic coloring, 5. boiling water sealing hole.
Below technology of the present invention is further described, the contents are as follows:
(1) Chemical Pretreatment
Adopt alkaline cleaning fluid to remove the impurity such as grease of sample.The concentration of NaOH is 10～50g/L, is warming up to 40～70 ℃, corrosion 2～5min.
(2) sulfuric acid one one-step electrolysis
Will be through pretreated sample as anode, negative electrode is the rectangle stereotype, carries out an one-step electrolysis in sulfuric acid liquid.Wherein sulfuric acid concentration is 10～20%, and temperature is controlled at 10～30 ℃, and current density is controlled at 1.0～2.0A/dm
2, the anodizing time is 10～20min.
(3) di(2-ethylhexyl)phosphate one-step electrolysis
In order to increase deposition ionic content in the rete, improve film layer structure, in sulfuric acid liquid, behind the one-step electrolysis, in phosphoric acid, carry out two one-step electrolysis.Phosphoric acid concentration is one of significant parameter of this process.Suitable phosphoric acid weight percent concentration of the present invention is 1%～15%.When the phosphoric acid of selecting high weight percent concentration for use (＞15%) carried out reaming, the dust phenomenon appearred in specimen surface in the reaming process, and solution becomes muddy in the short period of time; And when the phosphoric acid reaming of low weight percentage concentration (＜1%), very little to the optical property influence of back colored film.
The electrolysis voltage of phosphoric acid liquid and time also are to influence the painted important factor of alumite.Brownout, the time, too short painted difficulty was big, irregular colour; Overtension, overlong time then rete color are dark excessively.At 10～30V, the time is controlled at 5min～20min, has obtained effect preferably with the voltage control of di(2-ethylhexyl)phosphate one-step electrolysis in the present invention.
Therefore the processing parameter of this electrolytic process is: phosphoric acid concentration is 1wt%～15wt%; Electrolysis voltage is 10～30V; Electrolysis time 5min～20min, temperature is controlled at about 20 ℃.
(4) metal-salt three-step electrolytic coloring
To put into metal-salt through the sample behind the di(2-ethylhexyl)phosphate one-step electrolysis and carry out three-step electrolytic coloring.Metal salt concentrations, electrolysis voltage, the time, temperature is still major influence factors.Electrolytic colouring technology: red colour system coating concentration of electrolyte: CuSO
45H
2O (5～30g/L); Green is coating concentration of electrolyte: NiSO
47 H
2O (10～40g/L), boric acid (10～25g/L) ammonium sulfate (5～20g/L); Impressed voltage 10～30V, painted time 0.5～5min, temperature is controlled at about 20 ℃.
(5) sealing of hole
In order to improve the work-ing life of coating, carry out boiling water sealing hole 15～30min behind the electrolytic coloring.
The present invention has substantive distinguishing features and marked improvement, and the solar energy absorbing coating of traditional process for modifying surface preparation is black, and is extremely inharmonious with the outward appearance of buildings.The present invention adopts the method for three one-step electrolysis, behind the one-step electrolysis, has increased by two one-step electrolysis technologies in phosphoric acid in conventional sulfuric acid liquid, has changed the structure of oxidation film layer.Parameters such as concentration, electrolysis voltage and time to three one-step electrolysis liquid are adjusted, and it is single to have overcome two one-step electrolysis colored film colors, the shortcoming of poor optical properties.It is various that the absorber coatings that utilizes the present invention to prepare has color, and the life-span is long, the advantage that optical property is good.The gained coating is red, green system, and ornamental strong, specific absorption can reach 0.8～0.9, relatively is applicable to the low-temperature solar energy heat collector that is exposed to the outside, beautifies the environment, and is expected to promote the incorporate process of solar energy heat collector and buildings.
Embodiment
The present invention adopts three one-step electrolysis methods of aluminium to prepare the colored solar absorber coatings.Institute's coating color that obtains is evenly firm, can use more than 10 years and does not fade and come off; Optical property is good, and its specific absorption α can reach 0.8～0.9, and thermal emissivity ε is 0.45～0.6.
Embodiment 1
At first carry out Chemical Pretreatment: adopt alkaline cleaning fluid to remove the impurity such as grease of sample.The concentration of NaOH is 10g/L, is warming up to 70 ℃, corrosion 5min.Adopt common sulphuric acid anodizing technology to carry out an one-step electrolysis, processing parameter is: sulfuric acid concentration is 20%, and temperature is controlled at 10 ℃, and current density is 1.0A/dm
2, the anodizing time is 10min.In phosphoric acid liquid, carry out two one-step electrolysis then.The phosphoric acid electrolyte parameter of preparation is: phosphatase 11 %, and electrolysis voltage 30V, time 20min, temperature is controlled at about 20 ℃.The parameter of three-step electrolytic coloring is in metal-salt: CuSO
45H
2O 5g/L, electrolysis voltage 30V, painted time 0.5min, 20 ℃ of temperature.The gained coating is an incarnadine behind the 15min boiling water sealing hole, and α is 0.8, and ε is 0.5.
Embodiment 2
Chemical Pretreatment: adopt alkaline cleaning fluid to remove the impurity such as grease of sample.The concentration of NaOH is 30g/L, is warming up to 50 ℃, corrosion 3min.Adopt common sulphuric acid anodizing technology to carry out an one-step electrolysis, processing parameter is: sulfuric acid concentration is 10%, and temperature is controlled at 30 ℃, and current density is 1.5A/dm
2, the anodizing time is 20min.In phosphoric acid liquid, carry out two one-step electrolysis then.The phosphoric acid oxidation liquid parameter of preparation is: phosphatase 11 5%, and electrolysis voltage 10V, time 5min, temperature is controlled at about 20 ℃.The parameter of three-step electrolytic coloring is in metal-salt: CuSO
45H
2O 30g/L, electrolysis voltage 10V, painted time 5min, 20 ℃ of temperature.The gained coating is a dark red behind the 30min boiling water sealing hole, and α is 0.9, and ε is 0.6.
Embodiment 3
Chemical Pretreatment: adopt alkaline cleaning fluid to remove the impurity such as grease of sample.The concentration of NaOH is 50g/L, is warming up to 40 ℃, corrosion 2min.Adopt common sulphuric acid anodizing technology to carry out an one-step electrolysis, processing parameter is: sulfuric acid concentration is 15%, and temperature is controlled at 20 ℃, and current density is 2.0A/dm
2, the anodizing time is 12min.In phosphoric acid liquid, carry out two one-step electrolysis then.The phosphoric acid oxidation liquid parameter of preparation is: phosphatase 11 0%, and electrolysis voltage 22V, time 15min, temperature is controlled at about 20 ℃.The parameter of three-step electrolytic coloring is in metal-salt: CuSO
45H
2O 15g/L, electrolysis voltage 22V, painted time 3min, 20 ℃ of temperature.The gained coating is a maroon behind the 20min boiling water sealing hole, and α is 0.86, and ε is 0.53.
Embodiment 4
Chemical Pretreatment: adopt alkaline cleaning fluid to remove the impurity such as grease of sample.The concentration of NaOH is 10g/L, is warming up to 70 ℃, corrosion 5min.Adopt common sulphuric acid anodizing technology to carry out an one-step electrolysis, processing parameter is: sulfuric acid concentration is 20%, and temperature is controlled at 10 ℃, and current density is 1.0A/dm
2, the anodizing time is 10min.In phosphoric acid liquid, carry out two one-step electrolysis then.The phosphoric acid electrolyte parameter of preparation is: phosphatase 11 %, and electrolysis voltage 30V, time 20min, temperature is controlled at about 20 ℃.The parameter of three-step electrolytic coloring is in metal-salt: NiSO
47H
2O (10g/L) boric acid (10g/L) ammonium sulfate (5g/L), electrolysis voltage 30V, painted time 0.5min, 20 ℃ of temperature.The gained coating is a light green behind the 15min sealing of hole, and α is 0.8, and ε is 0.45.
Embodiment 5
Chemical Pretreatment: adopt alkaline cleaning fluid to remove the impurity such as grease of sample.The concentration of NaOH is 30g/L, is warming up to 50 ℃, corrosion 3min.Adopt common sulphuric acid anodizing technology to carry out an one-step electrolysis, processing parameter is: sulfuric acid concentration is 10%, and temperature is controlled at 30 ℃, and current density is 1.5A/dm
2, the anodizing time is 20min.In phosphoric acid liquid, carry out two one-step electrolysis then.The phosphoric acid oxidation liquid parameter of preparation is: phosphatase 11 5%, and electrolysis voltage 10V, time 5min, temperature is controlled at about 20 ℃.The parameter of three-step electrolytic coloring is in metal-salt: NiSO
47H
2O (40g/L) boric acid (25g/L) ammonium sulfate (20g/L), electrolysis voltage 18V, painted time 2min, 20 ℃ of temperature.The gained coating is a blackish green behind the 30min sealing of hole, and α is 0.87, and ε is 0.51.
Embodiment 6
Chemical Pretreatment: adopt alkaline cleaning fluid to remove the impurity such as grease of sample.The concentration of NaOH is 50g/L, is warming up to 40 ℃, corrosion 2min.Adopt common sulphuric acid anodizing technology to carry out an one-step electrolysis, processing parameter is: sulfuric acid concentration is 15%, and temperature is controlled at 20 ℃, and current density is 2.0A/dm
2, the anodizing time is 12min.In phosphoric acid liquid, carry out two one-step electrolysis then.The phosphoric acid oxidation liquid parameter of preparation is: phosphatase 11 0%, and electrolysis voltage 22V, time 15min, temperature is controlled at about 20 ℃.The parameter of three-step electrolytic coloring is in metal-salt: NiSO
47H
2O (20g/L) boric acid (15g/L) ammonium sulfate (10g/L), electrolysis voltage 30V, painted time 3min, 20 ℃ of temperature.The gained coating is blackish green behind the 20min sealing of hole, and α is 0.84, and ε is 0.48.
Claims (6)
1, a kind of aluminium three one-step electrolysis methods prepare the technology of solar colored look absorber coatings, it is characterized in that, utilize three-step electrolytic coloring technology, in conventional sulfuric acid liquid behind the one-step electrolysis, two one-step electrolysis technologies in phosphoric acid have been increased, thereby the matrix surface at fine aluminium has prepared and the matrix good combination, the colored solar coating for selective absorption that optical property is good, its technical process is: 1. Chemical Pretreatment, 2. sulfuric acid one one-step electrolysis, 3. di(2-ethylhexyl)phosphate one-step electrolysis, 4. metal-salt three-step electrolytic coloring, 5. boiling water sealing hole.
2, aluminium three one-step electrolysis methods according to claim 1 prepare the technology of solar colored look absorber coatings, it is characterized in that, described Chemical Pretreatment, be specially: adopt alkaline cleaning fluid to remove the impurity such as grease of sample, the concentration of NaOH is 10～50g/L, be warming up to 40～70 ℃, corrosion 2～5min.
3, aluminium three one-step electrolysis methods according to claim 1 prepare the technology of solar colored look absorber coatings, it is characterized in that, described sulfuric acid one one-step electrolysis, specific as follows: will be through pretreated sample as anode, negative electrode is the rectangle stereotype, carries out an one-step electrolysis in sulfuric acid liquid, and wherein sulfuric acid concentration is 10～20%, temperature is controlled at 10～30 ℃, and current density is controlled at 1.0～2.0A/dm
2, polar plate spacing is 8～20cm, and anodic oxidation voltage is controlled at 10～30V, and the anodizing time is 0～20min.
4, aluminium three one-step electrolysis methods according to claim 1 prepare the technology of solar colored look absorber coatings, it is characterized in that, described di(2-ethylhexyl)phosphate one-step electrolysis, specific as follows: the processing parameter of electrolytic process is: the phosphoric acid weight percent concentration is 1%～15%, the voltage control of di(2-ethylhexyl)phosphate one-step electrolysis is at 10～30V, time is controlled at 5min～20min, and temperature is controlled at 20 ℃.
5, aluminium three one-step electrolysis methods according to claim 1 prepare the technology of solar colored look absorber coatings, it is characterized in that, described metal-salt three-step electrolytic coloring, specific as follows: as will to put into metal-salt through the sample behind the di(2-ethylhexyl)phosphate one-step electrolysis and carry out three-step electrolytic coloring, electrolytic colouring technology: red colour system coating concentration of electrolyte: CuSO
45H
2O5～30g/L, green is coating concentration of electrolyte: NiSO
47H
2O 10～40g/L, boric acid 10～25g/L, ammonium sulfate 5～20g/L, impressed voltage 10～30V, painted time 0.5～5min, 20 ℃ of temperature.
6, aluminium three one-step electrolysis methods according to claim 1 prepare the technology of solar colored look absorber coatings, it is characterized in that described sealing of hole is specially: carry out boiling water sealing hole 10～30min behind the electrolytic coloring.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094229A (en) * | 2010-12-03 | 2011-06-15 | 昆明恒宇惠源科技有限公司 | Integral-plate continuous anodizing and selective coating process for heat absorbing layer of heat collector plate core and prescription |
| CN102634834A (en) * | 2012-04-27 | 2012-08-15 | 江门市安诺特炊具制造有限公司 | Electrolytic coloring technique of aluminum alloy cooker |
| CN106029957A (en) * | 2014-02-28 | 2016-10-12 | 株式会社樱花彩色笔 | Colored formed aluminum body and method for manufacturing same |
| CN106068338A (en) * | 2014-02-28 | 2016-11-02 | 株式会社樱花彩色笔 | Coloring aluminium formed body and manufacture method thereof |
-
2003
- 2003-09-04 CN CNA031507794A patent/CN1492081A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094229A (en) * | 2010-12-03 | 2011-06-15 | 昆明恒宇惠源科技有限公司 | Integral-plate continuous anodizing and selective coating process for heat absorbing layer of heat collector plate core and prescription |
| CN102094229B (en) * | 2010-12-03 | 2013-03-20 | 昆明恒宇惠源科技有限公司 | Integral-plate continuous anodizing and selective coating process for heat absorbing layer of heat collector plate core |
| CN102634834A (en) * | 2012-04-27 | 2012-08-15 | 江门市安诺特炊具制造有限公司 | Electrolytic coloring technique of aluminum alloy cooker |
| CN102634834B (en) * | 2012-04-27 | 2014-12-10 | 江门市安诺特炊具制造有限公司 | Electrolytic coloring technique of aluminum alloy cooker |
| CN106029957A (en) * | 2014-02-28 | 2016-10-12 | 株式会社樱花彩色笔 | Colored formed aluminum body and method for manufacturing same |
| CN106068338A (en) * | 2014-02-28 | 2016-11-02 | 株式会社樱花彩色笔 | Coloring aluminium formed body and manufacture method thereof |
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