CN100503884C - Production method of solar energy optical-thermal conversion material - Google Patents
Production method of solar energy optical-thermal conversion material Download PDFInfo
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- CN100503884C CN100503884C CNB2007100670499A CN200710067049A CN100503884C CN 100503884 C CN100503884 C CN 100503884C CN B2007100670499 A CNB2007100670499 A CN B2007100670499A CN 200710067049 A CN200710067049 A CN 200710067049A CN 100503884 C CN100503884 C CN 100503884C
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Abstract
The invention discloses a manufacturing method of solar energy switching material, which comprises the following steps: adopting chromium alloy steel as base; predisposing; polishing the steel; oxidizing; coloring; allocating chemical coloring solution with sulfuric acid, nitrate, ammonium sulfate and hydroxy benzoic acid; proceeding chemical closing deposal for steel with black transmitting film on the surface; drying to obtain the product.
Description
Technical field
The present invention relates to the preparation field of solar energy absorbing coating material, specifically a kind of production method of solar energy optical-thermal conversion material.
Background technology
Sun power is human inexhaustible renewable energy source, also is clean energy, does not produce any environmental pollution.Twentieth century fifties, two major technological breakthroughs have appearred in field of solar energy utilization, and these two technological breakthroughs have been established technical foundation period for the sun power utilization enters modern development.One is that U.S.'s Bell Laboratory in 1954 is developed 6% practical monocrystalline silicon battery, the 2nd, and nineteen fifty-five Israel Tabor proposes selective absorption surface notion and theoretical basis and is developed into practical black nickel optical-thermal conversion material.Solar energy optical-thermal conversion material is very big to the technical and economic performance influence of solar thermal utilization, for improving solar thermal utilization efficient, reducing cost, various countries sun power scientific worker attaches great importance to research, exploitation solar energy optical-thermal conversion material, develop many kinds of selectivity and absorb the black coating optical-thermal conversion material: (1) black chrome coating optical-thermal conversion material, the existing electroplating black chromium technology of Cai Yonging, current density big (15～200A/dm2), solution conductivity is poor, can produce a large amount of joule heatings during plating, need cooling and vented exhaust just can keep ordinary production.In addition, black chromium is plated on the non-copper spare, needs earlier pre-copper facing, bright nickel plating again, last black chromium plating; This technology will be produced relatively difficulty of solar energy in large area optical-thermal conversion material, and cost is higher, and is seriously polluted.(2) black nickel coating optical-thermal conversion material, black nickel coating is very thin, solidity to corrosion is relatively poor, for bonding force and the solidity to corrosion that improves coating and matrix, need inter coat (as Ni, Cu, Cd) or double-deck nickel coating, so production cost is than higher; The thermostability of black nickel coating is relatively poor, only is applicable to the low-temperature solar energy thermal utilization usually.(3) black cobalt coating optical-thermal conversion material, the main component of black cobalt coating is CoS, has the honeycomb type reticulated structure, and its specific absorption α can reach 0.94～0.96, and emittance ∈ is 0.12～0.14, and α/∈ is 6.7～8.But this technology will be produced relatively difficulty of solar energy in large area optical-thermal conversion material, and technology is not mature enough, and technology is difficult to be grasped, and production cost is also high.(4) coating type PbS coating optical-thermal conversion material, this coating preparation is simple, optical property is better, but complicated and confused shape PbS gradually oxidation become white PbSO4, thereby lose the photo-thermal transition function.The antirust ability of PbS is also relatively poor simultaneously, only is applicable to the low-temperature solar energy thermal utilization usually.(5) compound transition metal oxide coating optical-thermal conversion material, this coating type coating preparation is simple, and optical property is better, and cost is lower, but the coating tack is relatively poor, easily peels off.Usually only be applicable to the low-temperature solar energy thermal utilization.(6) stainless steel black rete optical-thermal conversion material, has good spectral selectivity, thermostability and high temperature resistant property are also fine, but adopt the chromic acid and the sulfuric acid of high density, need operation at high temperature, have production unit requirement height, production environment is abominable, seriously polluted, operational difficulty, solution instability, problems such as color control difficulty.(7) the vacuum plating coating optical-thermal conversion material of China's widespread use, adopt the preparation of vacuum-evaporation and magnetron sputtering technique to select absorber coatings, performance is very good, but body material adopts glass tube with vacuum, glass tube with vacuum is applied to have difficulties in the building structure, and the area of collection sun power is less.
In a word, the solar energy optical-thermal conversion material that prior art is produced exists thermostability, anti-ultraviolet property, solidity to corrosion relatively poor, and daylighting area is little, can not realize the defective such as integrated of Solar Energy Heat Utilization System and building structure.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, a kind of production method of novel solar energy optical-thermal conversion material is provided, this method is simple to operate, suitable for producing solar energy in large area optical-thermal conversion material is realized the integrated of Solar Energy Heat Utilization System and building structure.
For this reason, the present invention adopts following technical scheme: a kind of production method of solar energy optical-thermal conversion material, adopting the low chrome steel is matrix, has the optical-thermal conversion material of selecting to absorb black film by the chemical oxidation preparation, its concrete steps are as follows: 1) chromium alloyed steel is carried out pre-treatment, it comprises sandblast, oil removing, hot water wash, running water wash, activation, running water wash; 2) chromium alloyed steel through pre-treatment carries out the chemical rightenning processing; 3) chromium alloyed steel after will polishing carries out the painted processing of chemical oxidation, and its used chemical stain solution is made up of sulfuric acid, nitrate, ammonium sulfate and hydroxy-benzoic acid; 4) will go up the surface that obtains of step has the chromium alloyed steel of black conversion film to carry out chemical sealing treatment; 5) will seal good black surface chromium alloyed steel oven dry, become a kind of novel solar energy optical-thermal conversion material.
The body material that the present invention selects for use belongs to the low chrome steel, and solidity to corrosion is relatively poor.High Chrome Alloy Steel is because chromium content height in the steel, and etch resistant properties is good, and this is because chromium can reduce the oxidizing electrode current potential effectively, and the electropotential that makes original pure iron (or soft steel) is by on the occasion of becoming negative value; The solidity to corrosion of High Chrome Alloy Steel is good, and handle with the coloring liquid of high temperature, strong acid, strong oxidizer on its surface.Utilize existing High Chrome Alloy Steel chemical pigmenting liquid to handle low chrome steel, the conversion film that can only obtain not having light, there is corrosion tendency on the surface.The present invention adopts low temperature, lower concentration acid and general oxygenant that low chrome is carried out surface treatment, the oxidation rate of the iron on low chrome surface is higher than chromium widely in chemical stain solution, make the content of alloy surface chromium enrichment occur, be equivalent to improve the content of chromium like this at alloy surface, can make the low chrome surface produce outward appearance densification, glossiness conversion film, and reach the same effect of High Chrome Alloy Steel solidity to corrosion.
It is that the sulfuric acid of 1-10 grams per liter and hydrogen peroxide that concentration is the 100-200 grams per liter are formed by concentration that the production method of described solar energy optical-thermal conversion material, chemical rightenning are handled solutions employed, and polishing time is at 5-10 minute, polish temperature 25-45 ℃.Because the erosion resistance of low chrome steel is relatively poor, selects for use the chemical polishing soln of low-concentration sulfuric acid to polish, and can reach good effect.
The production method of described solar energy optical-thermal conversion material, sulfuric acid concentration is the 10-200 grams per liter in the chemical stain solution, described nitrate concentration is the 1-35 grams per liter, and described ammonium sulfate concentrations is the 3-60 grams per liter, and described hydroxy-benzoic acid concentration is the 0.03-1 grams per liter; Sulfuric acid can make solution keep certain acidity, can increase the solution activity, and sulfuric acid is too low, and speed of response is slower, black film improvement time retardation, and sulfuric acid content is too high, the black film gloss difference; Nitrate is the oxygenant in the chemical pigmenting liquid, and content is too low, easily causes excessive erosion, and content is too high, black film improvement time retardation; Ammonium sulfate is the stablizer in the chemical pigmenting liquid, can complexing dissolves the metal ion that gets off, and makes chemical pigmenting liquid stable; Hydroxy-benzoic acid is the brightening agent in the chemical pigmenting liquid; The sulfuric acid in the chemical pigmenting liquid and the concentration of other composition, select according to chromium alloyed steel chemical ingredients and coloring process condition, the coloring process condition specifically is meant which kind of alr mode of volume, temperature and selection of workpiece profile, size, weight and the chemical pigmenting liquid of chromium alloyed steel.
The production method of described solar energy optical-thermal conversion material, the temperature of painted processing are 45-85 ℃, the electrolysis of need not switching on, and the energy energy efficient, subzero treatment can reduce solution evaporation and help operator's health; The painted time is 20-300 minute, and in the coloring process, colour-change is slow; Coloring solution can make the concentration of chemical pigmenting liquid even through stirring, and has a narrow range of temperature.
The production method of described solar energy optical-thermal conversion material contains manganese element in the Chemical Composition of chromium alloyed steel, and manganese content is at 0.5%-17%.Manganese element in the chromium alloyed steel is to obtain the necessary a kind of composition of black coloring film, when painted processing, manganese element in the chromium alloyed steel is by chemical pigmenting liquid dissolving becoming mn ion, mn ion can participate in film forming, and can accelerate the formation (promptly playing katalysis) of black film, be the key that obtains chromium alloyed steel surface ater.If lack manganese element, can only obtain grey black or black-and-blue conversion film.
The solar energy optical-thermal conversion material that utilizes the present invention to obtain has following characteristics:
1, chemical conversion film surface even compact, blackness is dark, and the ability of anti-fingerprint or dirt is strong; Its specific absorption is high and emittance is low, has good spectral selectivity.
2, chemical conversion film has the good performance that shapes, and can bear general mold pressing processing, deep-drawing, bending machining and work hardening.The equal not damaged of black film shows good workability.
3, chemical conversion film has good abrasion resistance, and the bonding force of black colorant film and body material is good, has well wear-resisting and anti-delineation performance.
4, chemical conversion film has excellent corrosion resisting performance, 24 hours color and luster no changes of neutral salt spray test (Nacl 5% temperature 35 degree); Neutral salt spray test reached more than 48 hours.
5, chemical conversion film has good heat-resistant.
6, chemical conversion film has good anti-ultraviolet property, long-term irradiation under the sun, and its surface color has no significant change.
The production method of described solar energy optical-thermal conversion material, adopting the low chrome steel to carry out acidic chemical painted is a kind of novel process for treating surface, filled up a blank of field of surface treatment, have following beneficial effect: 1, chemical pigmenting liquid can make low chrome steel surface chromium content enrichment occur, the raising of surface chromium content, the surface corrosion resistance just strengthens, and can reach the same effect of High Chrome Alloy Steel solidity to corrosion; 2, component concentrations is low in the chemical pigmenting liquid, does not contain sexavalent chrome and so on toxic substance, and is easy to operate, can reach requirement on environmental protection; 3, the color of chemical conversion film is relevant with chromium, the manganese content of chemical ingredients in the chromium alloyed steel, the chromium alloyed steel of identical material, and its color to pitch black, does not have color distortion, favorable reproducibility by somber along with the increase of painted time basically; 4, chemical pigmenting liquid is depressed fabulous result of use at the standard atmosphere that is lower than 70 ℃, and solution evaporation is few, helps operator's health; 5, chemical pigmenting liquid is solution-stabilized, and component concentration ranges is big, the use temperature wide ranges; 6, in the chemical stain process, colour-change is slow, and favorable reproducibility makes the special suitable for producing solar energy in large area of the present invention optical-thermal conversion material, has realized the integrated of Solar Energy Heat Utilization System and building structure.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment
Preparation work:
(1) production test equipment: 1 single groove ultrasonic cleaning machine (the most handy 316 stainless steels of work nest or titanium plate are reinforced and encrypted welding).
(2) the preparation chemical polishing soln is 500 liters.
(3) 500 liters of preparation chemical stain solution are in the work nest of Ultrasonic Cleaners.
(4) the preparation saturated sodium silicate solution, which is 500 liters.
(5) prepare the low chrome steel plate.
Embodiment 1
The first step selects that chromium content is 12.5% for use, manganese content is 16.28% Chrome metal powder steel plate, and it is carried out pre-treatment, passes through sandblast, oil removing, hot water wash, running water wash, activation, running water wash successively;
In second step, the Chrome metal powder steel plate that pre-treatment is good immerses in the chemical polishing soln and carries out polished finish, and chemical polishing soln is made up of 5 grams per liter sulfuric acid and hydrogen peroxide 150 grams per liters, polishing time 10 minutes, 35 ℃ of polish temperatures.The polishing back is taken out and is used hot water wash, washes down with flowing water again.
The 3rd step, will carry out painted processing in the polished Chrome metal powder steel plate immersion chemical stain solution, the coloring solution prescription is sulfuric acid 50 grams per liters, nitrate 5 grams per liters, ammonium sulfate 20 grams per liters, hydroxy-benzoic acid 0.1 grams per liter; Adopt the ultrasonic stirring mode, the volume of chemical pigmenting liquid: 500 liters; Carry out the area of the Chrome metal powder steel plate of chemical stain: 0.4 square metre; 60 ℃ of colour temperatures.40 minutes beginning improvement obtained bright light black in 60 minutes, obtained bright ater in 90 minutes.
In the 4th step, the Chrome metal powder steel plate of painted good surface black carries out cold wash, carries out sealing treatment again, and confining liquid is water glass 20 grams per liters, 70 ℃ of closure temperatures, 10 minutes off-periods.
In the 5th step, the chromium alloyed steel blackboard hot water wash after the sealing is used running water wash again, and 150 ℃ of hot air seasonings obtain having the Chrome metal powder steel plate of black chemical conversion coating, i.e. solar energy optical-thermal conversion material.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface even compact, blackness do not become easily infected by fingerprint or dirt deeply.
Embodiment 2
Processing step by embodiment 1 carries out painted processing, select that chromium content is 12.6% for use, manganese content is 14.37% Chrome metal powder steel plate, to carry out painted processing in its immersion chemical stain solution, the coloring solution prescription is sulfuric acid 100 grams per liters, nitrate 5 grams per liters, ammonium sulfate 20 grams per liters, hydroxy-benzoic acid 0.1 grams per liter; The volume of chemical pigmenting liquid: 500 liters; Carry out the area of the Chrome metal powder steel plate of chemical stain: 0.4 square metre; 70 ℃ of colour temperatures; 30 minutes beginning improvement obtained bright light black in 50 minutes, obtained bright ater in 80 minutes.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface even compact, blackness do not become easily infected by fingerprint or dirt deeply.
Embodiment 3
Processing step by embodiment 1 carries out painted processing, select that chromium content is 12.4% for use, manganese content is 12.48% Chrome metal powder steel plate, to carry out painted processing in its immersion chemical stain solution, the coloring solution prescription is sulfuric acid 150 grams per liters, nitrate 10 grams per liters, ammonium sulfate 40 grams per liters, hydroxy-benzoic acid 0.1 grams per liter; The volume of chemical pigmenting liquid: 500 liters; Carry out the area of the chromium alloyed steel of chemical stain: 0.4 square metre; 70 ℃ of colour temperatures; 20 minutes beginning improvement obtained bright light black in 35 minutes, obtained bright ater in 60 minutes.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface even compact, blackness do not become easily infected by fingerprint or dirt deeply.
Embodiment 4
Processing step by embodiment 1 carries out painted processing, select that chromium content is 12.7% for use, manganese content is 8.95% Chrome metal powder steel plate, to carry out painted processing in its immersion chemical stain solution, the coloring solution prescription is sulfuric acid 180 grams per liters, nitrate 10 grams per liters, ammonium sulfate 40 grams per liters, hydroxy-benzoic acid 0.1 grams per liter; The volume of chemical pigmenting liquid: 500 liters; Carry out the area of the Chrome metal powder steel plate of chemical stain: 0.4 square metre; 80 ℃ of colour temperatures; 15 minutes beginning improvement obtained bright light black in 28 minutes, obtained bright ater in 50 minutes.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface even compact, blackness do not become easily infected by fingerprint or dirt deeply.
Embodiment 5
Processing step by embodiment 1 carries out painted processing, select that chromium content is 12.3% for use, manganese content is 8.95% Chrome metal powder steel plate, to carry out painted processing in its immersion chemical stain solution, the coloring solution prescription is sulfuric acid 100 grams per liters, nitrate 5 grams per liters, ammonium sulfate 40 grams per liters, hydroxy-benzoic acid 0.1 grams per liter; The volume of chemical pigmenting liquid: 500 liters; Carry out the area of the Chrome metal powder steel plate of chemical stain: 0.4 square metre; 65 ℃ of colour temperatures; 45 minutes beginning improvement obtained bright light black in 90 minutes, obtained bright ater in 120 minutes.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface even compact, blackness do not become easily infected by fingerprint or dirt deeply.
Embodiment 6
Processing step by embodiment 1 carries out painted processing, select that chromium content is 12.8% for use, manganese content is 7.95% Chrome metal powder steel plate, to carry out painted processing in its immersion chemical stain solution, the coloring solution prescription is sulfuric acid 180 grams per liters, nitrate 10 grams per liters, ammonium sulfate 40 grams per liters, hydroxy-benzoic acid 0.3 grams per liter; The volume of chemical pigmenting liquid: 500 liters; Carry out the area of the Chrome metal powder steel plate of chemical stain: 0.4 square metre; 80 ℃ of colour temperatures; 30 minutes beginning improvement obtained bright light black in 60 minutes, obtained bright black in 90 minutes.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface even compact, blackness do not become easily infected by fingerprint or dirt deeply.
Embodiment 7
Processing step by embodiment 1 carries out painted processing, selecting chromium content for use is 12.2%, manganese content is 0.64% Chrome metal powder steel plate, to carry out painted processing in its immersion chemical stain solution, the coloring solution prescription is sulfuric acid 120 grams per liters, nitrate 8 grams per liters, ammonium sulfate 40 grams per liters, hydroxy-benzoic acid 0.3 grams per liter; The volume of chemical pigmenting liquid: 500 liters; Carry out the area of the Chrome metal powder steel plate of chemical stain: 0.4 square metre; 70 ℃ of colour temperatures; 90 minutes beginning improvement, it is black-and-blue to obtain light in 200 minutes, and it is black-and-blue to obtain light in 280 minutes.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface has the black-and-blue inteferometer coating of all even light, and rete is thin.
Embodiment 8
Processing step by embodiment 1 carries out painted processing, selecting chromium content for use is 12.1%, manganese content is 0.64% Chrome metal powder steel plate, to carry out painted processing in its immersion chemical stain solution, the coloring solution prescription is sulfuric acid 150 grams per liters, nitrate 5 grams per liters, ammonium sulfate 40 grams per liters, hydroxy-benzoic acid 0.3 grams per liter; The volume of chemical pigmenting liquid: 500 liters; Carry out the area of the Chrome metal powder steel plate of chemical stain: 0.4 square metre; 80 ℃ of colour temperatures; 60 minutes beginning improvement obtained bright black-and-blue in 150 minutes.
Solar energy optical-thermal conversion material to the present embodiment gained is observed, and material surface has the black-and-blue inteferometer coating of all even light, and rete is thin.
The present invention also is applicable to the surface treatment of chromium content less than 12% low chrome steel.
Protection scope of the present invention is not limited to the foregoing description, and technical scheme all and of the present invention technology contents identical or that be equal to all falls in its protection domain.
The test record of sun power casing:
Wooden case with one 400 * 600 * 10, auxilliary all around lagging material, one 380 * 580 * 8 galvanized iron case is placed on the wooden case the inside, galvanized iron case the inside present embodiment 8 gained thick for 1mm, area be that 350 * 560 chromium alloyed steel black plate is placed on inside the galvanized iron case as solar absorber, thermometer is placed the inside and is measured the inside air themperature, covers with glass cover-plate again, and thermometer is placed on the glass cover-plate, measure outside air temperature, below what write down is data under fine sunshine.
Testing location: Jiande City, Zhejiang Province
Test duration: in March, 2006-July
Test in March, 1 2006
Test in April, 2 2006
Test in May, 3 2006
Test in June, 4 2006
Test in July, 5 2006
Show by above-mentioned sun power casing testing experiment, the solar energy optical-thermal conversion material that utilizes the present invention to obtain, its specific absorption height, emittance is low, has good spectral selectivity.
Claims (3)
1, a kind of production method of solar energy optical-thermal conversion material, adopting the low chrome steel is matrix, contain manganese element in the Chemical Composition of low chrome steel, its content is at 0.5%-17%, has the optical-thermal conversion material that sun power is selected absorber coatings by the chemical oxidation preparation, its concrete steps are as follows: 1) the low chrome steel is carried out pre-treatment, it comprises sandblast, oil removing, hot water wash, running water wash, activation, running water wash; 2) the low chrome steel through pre-treatment carries out the chemical rightenning processing; 3) the low chrome steel after will polishing carries out the painted processing of chemical oxidation, its used chemical stain solution is made up of sulfuric acid, nitrate, ammonium sulfate and hydroxy-benzoic acid, and sulfuric acid concentration is that 10-200 grams per liter, nitrate concentration are that 1-35 grams per liter, ammonium sulfate concentrations are that 3-60 grams per liter, hydroxy-benzoic acid concentration are the 0.03-1 grams per liter; 4) will go up the surface that obtains of step has the low chrome steel of black conversion film to carry out chemical sealing treatment; 5) oven dry finished product.
2, the production method of solar energy optical-thermal conversion material according to claim 1, it is characterized in that it is that the sulfuric acid of 1-10 grams per liter and hydrogen peroxide that concentration is the 100-200 grams per liter are formed by concentration that used polishing solution is handled in described chemical rightenning, the temperature of polished finish is 25-45 ℃, and the time is 5-10 minute.
3, the production method of solar energy optical-thermal conversion material according to claim 1 and 2, the temperature that it is characterized in that the painted processing of chemical oxidation is 45-85 ℃, and the time is 20-300 minute, and chemical stain solution need stir.
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| CN101818374B (en) * | 2010-05-04 | 2011-06-08 | 甘肃锦世化工有限责任公司 | Production method of solar absorber plate |
| CN102268673B (en) * | 2011-06-07 | 2014-10-29 | 广东联塑科技实业有限公司 | Method for preparing selective absorption coating of plastic solar thermal collector |
| CN103031552A (en) * | 2011-10-09 | 2013-04-10 | 张晓波 | Production method for chemically coloring low-chromium stainless steel into black |
| CN108914107B (en) * | 2018-08-07 | 2020-04-17 | 哈尔滨工业大学 | Preparation method of copper-based reticular photothermal conversion material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258760A (en) * | 1999-12-30 | 2000-07-05 | 上海交通大学 | Black inactivation process for zinc-nickel alloy coating |
| WO2001086016A3 (en) * | 2000-05-11 | 2003-08-14 | Henkel Corp | Metal surface treatment agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1258760A (en) * | 1999-12-30 | 2000-07-05 | 上海交通大学 | Black inactivation process for zinc-nickel alloy coating |
| WO2001086016A3 (en) * | 2000-05-11 | 2003-08-14 | Henkel Corp | Metal surface treatment agent |
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Assignee: Anhui Tulip New Energy Tech Co.,Ltd. Assignor: Wang Contract fulfillment period: 2009.6.28 to 2014.6.28 contract change Contract record no.: 2009340000190 Denomination of invention: Production method of solar energy optical-thermal conversion material Granted publication date: 20090624 License type: Exclusive license Record date: 2009.8.21 |
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