Vanadium base high temperature solar energy selective absorption coating and preparation method thereof
Technical field
The present invention relates to groove type solar elevated temperature heat technical field of power generation, particularly a kind of vanadium base high temperature solar energy selective absorption coating and preparation method thereof.
Background technology
Solar energy thermal-power-generating is an important technology approach that large-scale develops and utilizes sun power, tower, slot type, dish formula system are arranged at present, wherein more with slot type and tower system commercial applications, trough type solar power generation particularly, be unique mature technology through commercialized running in 20 years in the world up to now, its cost is far below photovoltaic generation.The accumulator system of slot light collection heat generating system can be realized operation in 24 hours, and along with the increase of scale, cost of electricity-generating also has very strong competitive power.At present, Europe and the U.S. are building a collection of improved trough type solar power generation system, and its application of temperature is higher, and performance is more superior.
Gordian technique is high temperature solar energy selective absorption coating in the trough type solar power generation.For solar selectively absorbing coating, though after deliberation and be extensive use of black chromium, anode oxidation coloration Ni-Al
2O
3And the SS-C/SS(stainless steel with composition gradual change feature) and film such as Al-N/Al system, but all be to belong to lower temperature application, application of temperature is in 200 ℃.For improving application of temperature, developed the coating for selective absorption under the warm service condition in being fit to, as Mo-Al
2O
3Material system such as/Cu, SS-AlN/SS, its use temperature can reach 200 ℃-450 ℃.But process deposits rates such as two targets or many target co-sputterings, radio-frequency sputtering are low, and the production cycle is long, and complex process and cost are higher.
In order to cooperate trough type solar power generation to higher temperature, the trend of high-level efficiency development more, widen the material system of high temperature groove type solar coating for selective absorption, need research and development Heat stability is good, specific absorption height and the simple coating for selective absorption of technology and technology of preparing.
Summary of the invention
Based on this, be necessary the problem at the shortcoming of prior art, a kind of vanadium base high temperature solar energy selective absorption coating and preparation method thereof is provided, described coating for selective absorption is good to specific absorption height, the thermal stability of solar spectrum, its preparation technology is simple, and easy to operate, with short production cycle, sputter operating mode is stablized.
A kind of vanadium base high temperature solar energy selective absorption coating and preparation method thereof, described coating for selective absorption is made up of trilamellar membrane, described trilamellar membrane comprises bottom infrared reflecting layer, intermediate absorption layer and top layer anti-reflection layer, described bottom infrared reflecting layer is deposited on matrix surface, described intermediate absorption layer is deposited on the bottom infrared reflecting layer, and described top layer anti-reflection layer is deposited on the intermediate absorption layer; Described bottom infrared reflecting layer is made up of metal V film, and described intermediate absorption layer comprises first subgrade and second subgrade, and described first subgrade and second subgrade are by V+SiO
2Film is formed, and described top layer anti-reflection layer is by SiO
2Film is formed;
The preparation method of described coating for selective absorption may further comprise the steps:
1., at first handle matrix:
At first described matrix is carried out surface treatment, polish successively, alcohol and acetone ultrasonic cleaning, the deionized water ultrasonic cleaning is dried after to be cleaned the finishing and is handled and insert in the magnetron sputtering cavity; And then the surface of using the described matrix of ion bombardment, strengthen the bonding force of described matrix and described bottom infrared reflecting layer;
2., at matrix deposition bottom infrared reflecting layer:
Adopt metal V target to prepare the bottom infrared reflecting layer by medium frequency magnetron sputtering or magnetically controlled DC sputtering mode at described matrix surface, in the preparation, prepare the V film with Ar gas as sputter gas, the thickness of described bottom infrared reflecting layer is 100~400nm;
3., at bottom infrared reflecting layer deposition intermediate absorption layer:
When the V target carries out medium frequency magnetron sputtering or magnetically controlled DC sputtering, adopt SiO
2Target deposits SiO by the rf magnetron sputtering mode
2, form V+SiO
2Film has namely formed first subgrade of described intermediate absorption layer, and the thickness of described first subgrade is 30~150nm; After described first subgrade is finished, increase rf magnetron sputtering SiO
2The power of target simultaneously, reduces the power of medium frequency magnetron sputtering or magnetically controlled DC sputtering V target, prepares the V+SiO of second subgrade
2Film, the thickness of described second subgrade are 30~150nm;
4., at intermediate absorption layer deposition top layer anti-reflection layer:
Stop medium frequency magnetron sputtering or magnetically controlled DC sputtering V target, continue rf magnetron sputtering SiO
2Target forms SiO
2Film has namely formed the top layer anti-reflection layer, and the thickness of described top layer anti-reflection layer is 30~100nm.
Therein among embodiment, in the described absorption layer in first subgrade volume percent of V greater than the volume percent of V in second subgrade; The volume percent of V is 40%~70% in described first subgrade, and the volume percent of V is 10%~30% in described second subgrade.
Among embodiment, described matrix is stainless steel tube therein.
Therein among embodiment, the purity of described V target 〉=99.99%, described SiO
2The purity of target 〉=99.99%.
The present invention prepares by concrete preparation method on the basis of Macleod optics software simulation optimization vanadium based selective absorber coatings.Vanadium belongs to refractory metal, and fusing point have good high-temperature stability, and the vanadium metal film is higher at the reflectivity of infrared band up to 1919 ℃, satisfies preparation high temperature low-launch-rate solar selectively absorbing coating characteristic.Optics software simulation optimization method is:
1), at first determine the film layer structure of coating for selective absorption:
Coating for selective absorption is to be made of three parts: bottom infrared reflecting layer, intermediate absorption layer and top layer antireflection layer.Along with the optical analogy development of technology, more and more successful to the application of interference effect, proposed absorption layer and constituted by two subgrade film structures of different metal packing factor, the optical constant difference of its two subgrade, when absorbing, can also produce the interference effect that disappears mutually, the raising specific absorption.Select vanadium metal as the bottom infrared reflecting layer, the intermediate absorption layer is V+SiO for this reason
2Or V+ Al
2O
3Two subgrades that material is formed, the top layer anti-reflection layer is SiO
2Or Al
2O
3Material.
2), determine the optical constant of each tunic of coating for selective absorption:
Adopt multiple preparation method to prepare the vanadium metal film earlier, again by Fourier infrared spectrograph test vanadium film reflectivity in 2~25 micron wave lengths, select the highest preparation technology of vanadium film infrared external reflection, test out the optical constant of vanadium metal simultaneously by ellipsometer, measure the SiO of preparation again by ellipsometer
2Or Al
2O
3The optical constant of unitary film.
The optical constant of two subgrades of intermediate absorption layer is calculated by EFFECTIVE MEDIUM Maxwell Garnett theory and Bruggeman theory, calculates the optical constant that sintering metal absorbs subgrade by following formula:
The expression formula of Maxwell Garnett theory is:
The expression formula of Bruggeman theory is:
Wherein, ε
MGAnd ε
BRBe respectively the specific inductivity of the subgrade absorption layer of and BG theory theoretical with MG, ε
ABe the specific inductivity of vanadium metal, ε
BBe SiO
2Or Al
2O
3Specific inductivity,
f A Be vanadium metal volume packing factor,
f A <0.3 o'clock, use the MG Theoretical Calculation, otherwise just use the BR Theoretical Calculation.
3), the simulation of Macleod optics software and optimization:
In Macleod software, calculate specific absorption α and the high temperature emissivity of coating for selective absorption by following formula;
Wherein, λ is optical wavelength,
Be the wavelength reflective function,
Be the solar radiation strength function,
Be that temperature is the blackbody radiation intensity of T.
Calculate the photo-thermal conversion efficiency of solar selectively absorbing coating again by following formula, function f comprises specific absorption α and the high temperature emissivity of rete;
The optical property of bottom infrared reflecting layer, intermediate absorption layer and top layer anti-reflection layer difference Input Software, come the thickness in monolayer of each rete of simulative optimization at last.By simulation and the optimization of Macleod software, draw vanadium metal aspect optical property, can good and SiO
2Or Al
2O
3Material is in conjunction with preparation interfere type solar selectively absorbing coating.This coating for selective absorption has the specific absorption height to solar spectrum, the low characteristics of emission of high temperature blackbody radiation.
Above-mentioned vanadium base high temperature solar energy selective absorption coating and preparation method thereof, described coating for selective absorption is by metal V(vanadium) film the bottom infrared reflecting layer, the V+SiO that form
2Intermediate absorption layer and SiO that film is formed
2The top layer anti-reflection layer that film is formed constitutes, and has high-temperature stability, and metal V(vanadium) film is higher at the reflectivity of infrared band, and to the specific absorption height of solar spectrum, emittance is low.
The fusing point of vanadium metal (V) is higher, and described intermediate absorption layer is by V+SiO
2Film is formed two absorption layer, V+SiO of interfering
2Film has high-melting-point and high stability, and the long term operation temperature reaches 600 ℃.Owing to adopted two interference intermediate absorption layer structure, utilize the interference effect of film to strengthen the absorption effect of coating, make described coating for selective absorption have the solar spectrum high-absorbility, the characteristics of infrared spectra low-launch-rate.The preparation technology of described coating for selective absorption is simple, easy to operate, be easy to control, sputter rate is fast, can shorten the production cycle, and process stabilizing can reduce equipment cost and production cost greatly.
Description of drawings
Figure 1 shows that the diagrammatic cross-section of coating for selective absorption of the present invention.
Below be component sign flag explanation of the present invention:
Coating for selective absorption 100, matrix 110, bottom infrared reflecting layer 120, intermediate absorption layer 130, first subgrade 131, second subgrade 132, top layer anti-reflection layer 140.
Embodiment
Embodiment one, and a kind of high temperature solar energy selective absorption coating 100 is made up of trilamellar membrane, and described trilamellar membrane comprises bottom infrared reflecting layer 120, intermediate absorption layer 130 and top layer anti-reflection layer 140.Described bottom infrared reflecting layer 120 is deposited on matrix 110 surfaces, and described matrix 110 is stainless steel tube.Described intermediate absorption layer 130 is deposited on the bottom infrared reflecting layer 120, and described top layer anti-reflection layer 140 is deposited on the intermediate absorption layer 130.
Described bottom infrared reflecting layer 120 is by metal V(vanadium) film forms, and the thickness of described bottom infrared reflecting layer 120 is 100~400nm.
Described intermediate absorption layer 130 comprises first subgrade 131 and second subgrade 132, and described first subgrade 131 and second subgrade 132 are by V+SiO
2Film is formed, in the described absorption layer in first subgrade 131 volume percent of V greater than the volume percent of V in second subgrade 132.The volume percent of V is 40%-70% in described first subgrade 131, and the volume percent of V is 10%-30% in described second subgrade 132.The thickness of described first subgrade 131 and second subgrade 132 is 30~150nm.
Described top layer anti-reflection layer 140 is by SiO
2Film is formed, and the thickness of described top layer anti-reflection layer 140 is 30~100nm.
The preparation method of described coating for selective absorption 100 may further comprise the steps:
1., at first handle matrix 110:
At first described matrix 110 is carried out the surface and carry out pre-treatment, with stainless steel base 110 surface finish, in alcohol and acetone, pass through ultrasonic cleaning 20~30min more respectively, and then by deionized water ultrasonic cleaning 5~10min, after cleaning finishes, dry processing, treat to insert in the magnetron sputtering cavity after oven dry is finished dealing with.Magnetron sputtering cavity base vacuum is extracted into 3 * 10
-3~ 5 * 10
-3Pa charges into Ar gas as sputter gas, adjusts sputter cavity internal gas pressure to 1.5
-3Pa bombards the surface 20 ~ 30min of described matrix 110 with grid bias power supply or with ion source, to strengthen the bonding force of described matrix 110 and described bottom infrared reflecting layer 120.
2., at matrix 110 deposition bottom infrared reflecting layers 120:
Cleaned after the substrate, adjusting sputter cavity internal gas pressure is 3 * 10
-1~ 5 * 10
-1Pa opens the V target power supply, and adopting purity is 99.99% metal V target, by medium frequency magnetron sputtering or magnetically controlled DC sputtering mode at described matrix 110 surface preparation bottom infrared reflecting layers 120.If adopt the medium frequency magnetron sputtering mode, then adjusting the intermediate frequency power supply electric current is 8 ~ 10A; If adopt the magnetically controlled DC sputtering mode, then adjusting direct supply voltage is 370 ~ 450V.During preparation, prepare the V film with Ar gas as sputter gas, the thickness for preparing described bottom infrared reflecting layer 120 is 100~400nm, and 120 pairs of infrared band spectrum of described bottom infrared reflecting layer have high reflection characteristic.
3., at bottom infrared reflecting layer 120 deposition intermediate absorption layers 130:
When the V target carried out medium frequency magnetron sputtering or magnetically controlled DC sputtering, selecting purity for use was 99.99 SiO
2Target deposits SiO by the rf magnetron sputtering mode
2Open SiO
2Target power supply is adjusted radio-frequency sputtering deposition SiO
2Power be 3~4KW, formed the first subgrade 131V+SiO of described intermediate absorption layer 130
2Film, the thickness of described first subgrade 131 are 30~150nm.
After described first subgrade 131 is finished, increase rf magnetron sputtering SiO
2The power to 5 of target~6KW simultaneously, reduces supply current to the 5 ~ 6A of V target medium frequency magnetron sputtering, or reduces V target magnetically controlled DC sputtering voltage of supply to 300 ~ 360V, continues the preparation second subgrade 132V+SiO
2Film, the thickness of described second subgrade 132 are 30~150nm.
4., at intermediate absorption layer 130 deposition top layer anti-reflection layer 140:
In add absorption layer preparation and finish after, stop medium frequency magnetron sputtering or magnetically controlled DC sputtering V target, continuing with rf magnetron sputtering power is that 5 ~ 6KW carries out sputter SiO
2Target forms SiO
2Film has namely formed top layer anti-reflection layer 140, and the thickness of described top layer anti-reflection layer 140 is 30~100nm.
Embodiment two, and a kind of high temperature solar energy selective absorption coating 100 is made up of trilamellar membrane, and described trilamellar membrane comprises bottom infrared reflecting layer 120, intermediate absorption layer 130 and top layer anti-reflection layer 140.Described bottom infrared reflecting layer 120 is deposited on matrix 110 surfaces, and described matrix 110 is stainless steel tube.Described intermediate absorption layer 130 is deposited on the bottom infrared reflecting layer 120, and described top layer anti-reflection layer 140 is deposited on the intermediate absorption layer 130.
Described bottom infrared reflecting layer 120 is by metal V(vanadium) film forms, and the thickness of described bottom infrared reflecting layer 120 is 100~400nm.
Described intermediate absorption layer 130 comprises first subgrade 131 and second subgrade 132, and described first subgrade 131 and second subgrade 132 are by V+ Al
2O
3Film is formed, in the described absorption layer in first subgrade 131 volume percent of V greater than the volume percent of V in second subgrade 132.The volume percent of V is 40%-70% in described first subgrade 131, and the volume percent of V is 10%-30% in described second subgrade 132.The thickness of described first subgrade 131 and second subgrade 132 is 30~150nm.
Described top layer anti-reflection layer 140 is by Al
2O
3Film is formed, and the thickness of described top layer anti-reflection layer 140 is 30~100nm.
The preparation method of described coating for selective absorption 100 may further comprise the steps:
1., at first handle matrix 110:
At first described matrix 110 is carried out the surface and carry out pre-treatment, with stainless steel base 110 surface finish, in alcohol and acetone, pass through ultrasonic cleaning 20~30min more respectively, and then by deionized water ultrasonic cleaning 5~10min, after cleaning finishes, dry processing, treat to insert in the magnetron sputtering cavity after oven dry is finished dealing with.Magnetron sputtering cavity base vacuum is extracted into 3 * 10
-3~ 5 * 10
-3Pa charges into Ar gas as sputter gas, adjusts sputter cavity internal gas pressure to 1.5
-3Pa bombards the surface 20 ~ 30min of described matrix 110 with grid bias power supply or with ion source, to strengthen the bonding force of described matrix 110 and described bottom infrared reflecting layer 120.
2., at matrix 110 deposition bottom infrared reflecting layers 120:
Cleaned after the substrate, adjusting sputter cavity internal gas pressure is 3 * 10
-1~ 5 * 10
-1Pa opens the V target power supply, and adopting purity is 99.99% metal V target, by medium frequency magnetron sputtering or magnetically controlled DC sputtering mode at described matrix 110 surface preparation bottom infrared reflecting layers 120.If adopt the medium frequency magnetron sputtering mode, then adjusting the intermediate frequency power supply electric current is 8 ~ 10A; If adopt the magnetically controlled DC sputtering mode, then adjusting direct supply voltage is 370 ~ 450V.During preparation, prepare the V film with Ar gas as sputter gas, the thickness for preparing described bottom infrared reflecting layer 120 is 100~400nm, and 120 pairs of infrared band spectrum of described bottom infrared reflecting layer have high reflection characteristic.
3., at bottom infrared reflecting layer 120 deposition intermediate absorption layers 130:
When the V target carried out medium frequency magnetron sputtering or magnetically controlled DC sputtering, selecting purity for use was 99.99 Al
2O
3Target is by rf magnetron sputtering mode depositing Al
2O
3Open Al
2O
3Target power supply is adjusted the radio-frequency sputtering depositing Al
2O
3Power be 3~4KW, formed the first subgrade 131V+ Al of described intermediate absorption layer 130
2O
3Film, the thickness of described first subgrade 131 are 30~150nm.
After described first subgrade 131 is finished, increase rf magnetron sputtering Al
2O
3The power to 5 of target~6KW simultaneously, reduces supply current to the 5 ~ 6A of V target medium frequency magnetron sputtering, or reduces V target magnetically controlled DC sputtering voltage of supply to 300 ~ 360V, continues the preparation second subgrade 132V+ Al
2O
3Film, the thickness of described second subgrade 132 are 30~150nm.
4., at intermediate absorption layer 130 deposition top layer anti-reflection layer 140:
In add absorption layer preparation and finish after, stop medium frequency magnetron sputtering or magnetically controlled DC sputtering V target, continuing with rf magnetron sputtering power is that 5 ~ 6KW carries out sputter Al
2O
3Target forms Al
2O
3Film has namely formed top layer anti-reflection layer 140, and the thickness of described top layer anti-reflection layer 140 is 30~100nm.
Draw through test, the performance of described coating for selective absorption is as follows: at air quality factors A M=1.5, temperature is that the specific absorption of coating for selective absorption is 93% under 450 ℃ the condition, and normal emittance is 15%(450 ℃); Carry out vacuum annealing again and handle, 2 * 10
-2Under the Pa vacuum tightness, after 1 hour, the coating specific absorption is 92.5% through 400 ℃ of vacuum annealings, and normal emittance is 15%(450 ℃); 2 * 10
-2Under the Pa vacuum tightness, after 1 hour, the coating specific absorption is 92.5% through 600 ℃ of vacuum annealings, and normal emittance is 16%(450 ℃).
In sum, coating for selective absorption 100 of the present invention is by metal V(vanadium) film the bottom infrared reflecting layer 120, the V+SiO that form
2Film or V+ Al
2O
3Film is formed intermediate absorption layer 130, SiO
2Film or Al
2O
3The top layer anti-reflection layer 140 that film is formed constitutes, and has high-temperature stability, and to the specific absorption height of solar spectrum, emittance is low.
The fusing point of vanadium metal (V) is higher, and described intermediate absorption layer 130 has high-melting-point and high stability, and the long term operation temperature reaches 600 ℃.Owing to adopted two interference intermediate absorption layer 130 structure, utilize the interference effect of film to strengthen the absorption effect of coating, make described coating for selective absorption 100 have the solar spectrum high-absorbility, the characteristics of infrared spectra low-launch-rate.The preparation technology of described coating for selective absorption 100 is simple, easy to operate, be easy to control, sputter rate is fast, can shorten the production cycle, and process stabilizing can reduce equipment cost and production cost greatly.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.