CN104006560B - A kind of WOx/ZrOxHigh temperature solar energy selective absorption coating and preparation method thereof - Google Patents
A kind of WOx/ZrOxHigh temperature solar energy selective absorption coating and preparation method thereof Download PDFInfo
- Publication number
- CN104006560B CN104006560B CN201410229712.0A CN201410229712A CN104006560B CN 104006560 B CN104006560 B CN 104006560B CN 201410229712 A CN201410229712 A CN 201410229712A CN 104006560 B CN104006560 B CN 104006560B
- Authority
- CN
- China
- Prior art keywords
- sputtering
- layer
- zro
- subgrade
- vacuum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Abstract
The invention discloses a kind of WOx/ZrOxHigh temperature solar energy selective absorption coating and preparation method thereof, including trilamellar membrane, ground floor infrared reflecting layer are Cu or Ag films, and positioned at matrix surface, thickness is 100~300nm；Second layer absorbed layer includes two sublayer structures, and two subgrades are WOx+ZrOxThe thickness of film, the first subgrade and the second subgrade is 150~300nm, ZrO in the first subgradexIt is 50~75% to account for percent by volume, and remaining is WOx, the second subgrade ZrOxPercent by volume be 30~50%, remaining is WOx, wherein the first subgrade is adjacent with ground floor infrared reflecting layer, the second subgrade is adjacent with third layer antireflection layer；Third layer antireflection layer is ZrOxFilm, thickness is 120~200nm.The present invention has excellent high-temperature stability, and good thermal stability is kept under 500 DEG C~600 DEG C elevated temperature in vacuo or 400 DEG C of atmospheric conditions.
Description
Technical field
The invention belongs to technical field of solar utilization technique, and in particular to a kind of WOx/ZrOxHigh temperature solar energy selective absorbs
Coating and preparation method thereof.
Background technology
Coating for selective absorption of sunlight spectrum has high-absorbility in Visible-to-Near InfaRed wave band, has in infrared band low
The function of emissivity, is the key that photo-thermal conversion efficiency is improved for solar thermal collector.With solar thermal utilization demand and
Technology is continued to develop, and the range of application of solar energy heat collection pipe applies (100 DEG C -350 from cryogenic applications (≤100 DEG C) Xiang Zhongwen
DEG C) and (350 DEG C -500 DEG C) development of high temperature application, constantly to meet the high temperature application field such as desalinization, solar power generation
Use requirement.Coating for selective absorption needs to have good high high-temp stability, could meet thermal-collecting tube in high temperature ring
The service condition in border.
Pursuit of the mankind to efficiency promotes technology constantly to advance, and in recent years, is inhaled for high temperature solar selectively
Receive coating and do numerous studies and wide application.Conventional material mainly has Cr-Cr oxides, Ni-Al2O3、Mo-
Al2O3, Ti/Al/Si nitride or (and) oxide etc., but these materials are only used for 300 DEG C~400 DEG C of vacuum environment,
Report is had no for the coating country that 500 DEG C~600 DEG C vacuum of higher temperature and 450 DEG C~500 DEG C non-vacuum environments are used.
The content of the invention
The invention aims to solve the above problems, a kind of WO is proposedx/ZrOxHigh temperature solar energy selective absorbs and applies
Layer and preparation method thereof, i.e., in WOx/ZrOxAfter high temperature solar energy selective absorption coating has been plated, vacuum high-temperature annealing is carried out to it
Treatment, it is adaptable to high temperature (300 DEG C~600 DEG C) working vacuum thermal-collecting tube and higher than 450 DEG C of antivacuum thermal-collecting tubes, coating absorptivity
High, emissivity is low, heat endurance is good.
The present invention provides a kind of WOx/ZrOxSolar selectively absorbing coating：Under the conditions of air quality factors A M1.5,
Coating absorptivity is 96.2%, and normal emittance is 0.04.Vacuum annealing treatment is carried out, 5 × 10-3Under Pa vacuums, through 550
After DEG C vacuum annealing 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.04,5 × 10-3Under Pa vacuums, warp
After 600 DEG C of vacuum annealings 2 hours, coating absorptivity is 97.6%, and normal emittance is 0.04.Under atmospheric conditions, through 350 DEG C of guarantors
After 2 hours, coating absorptivity is 97.5% to temperature, and normal emittance is 0.04；Under atmospheric conditions, after being incubated 2 hours through 400 DEG C,
Coating absorptivity is 97.1%, and normal emittance is 0.05.
The present invention proposes a kind of WOx/ZrOxHigh temperature solar energy selective absorption coating, including trilamellar membrane, from bottom to surface
It is followed successively by infrared reflecting layer, absorbed layer and antireflection layer；Ground floor infrared reflecting layer is Cu or Ag films, thick positioned at matrix surface
It is 100~300nm to spend；Second layer absorbed layer includes two sublayer structures, and two subgrades are WOx+ZrOxFilm, the first subgrade and
The thickness of the second subgrade is 150~300nm, ZrO in the first subgradexIt is 50~75% to account for percent by volume, and remaining is WOx, the
Two subgrade ZrOxPercent by volume be 30~50%, remaining is WOx, wherein the first subgrade is adjacent with ground floor infrared reflecting layer,
Second subgrade is adjacent with third layer antireflection layer；Third layer antireflection layer is ZrOxFilm, thickness is 120~200nm.
The present invention proposes a kind of WOx/ZrOxThe preparation method of high temperature solar energy selective absorption coating, including it is following
Step：
Step one：Ground floor infrared-emitting layer is prepared on matrix；
Using simple metal target direct current or medium frequency magnetron sputtering method, for Cu targets or Ag targets, (purity is simple metal target
99.99%), prepared as sputter gas using Ar gas, matrix uses high-speed steel, is evacuated to vacuum chamber base vacuum in advance before sputtering
4.0×10-3~5.0 × 10-3Pa, is passed through inert gas Ar gas as sputtering atmosphere, and Ar throughputs are 1000~1400sccm,
Adjustment sputtering distance is 130~150mm, and regulation sputtering pressure is 2 × 10-1~4 × 10-1Pa, opens the sputtering target of simple metal target
Power supply, adjustment sputtering voltage is 380~450V, and sputtering current is 45~65A, is prepared using magnetically controlled DC sputtering mode, is sputtered
Coating layer thickness is 100~300nm, obtains ground floor infrared-emitting layer；
Step 2：Second layer absorbed layer is prepared on ground floor infrared-emitting layer；
Using medium frequency magnetron sputtering method, with metal W target and Zr targets (purity 99.99%) as sputtering target material, first will be true
Empty room takes out base vacuum to 4 × 10 in advance-3~5 × 10-3Pa, then passes to Ar, O2Gaseous mixture, the flow of Ar for 800~
1400sccm, O2Flow be 120~150sccm, regulation sputtering pressure be 2 × 10-1~4 × 10-1Pa, is separately turned on W and Zr
Target power supply, during sputtering, adjustment W targets sputtering voltage is 600~750V, and sputtering current is 50~60A, and Zr targets sputtering voltage is 650
~800V, sputtering current is 20~30A, and the first subgrade WO is prepared on ground floor infrared reflecting layerx+ZrOxFilm, thickness is 150
~200nm；
Adjust sputtering pressure to 4 × 10-1~6 × 10-1Pa, increases O2Flow be 150~190sccm, regulation W targets sputtering
Electric current is 40~50A, and other parameters are constant, in the first subgrade WOx+ZrOxContinue sputtering on film and obtain the second subgrade WOx+
ZrOxFilm, thickness is 150~200nm；
Step 3：Third layer antireflection layer is prepared on second layer absorbed layer；
Using Zr targets (purity 99.99%) as sputtering target material, vacuum chamber is taken out into base vacuum to 4 × 10 in advance before sputtering-3
~5 × 10-3Pa, using Ar gas as sputter gas, O2As reacting gas, O2Flow is 300~400sccm, adjusts Ar and O2Stream
Amount is than being 2.5:1~4:1, regulation sputtering pressure is 4 × 10-1~6 × 10-1Pa, during sputtering, adjustment sputtering voltage be 300~
400V, sputtering current is 25~30A, and the ZrO that thickness is 50~150nm is obtained using medium frequency magnetron sputtering modexFilm, i.e., the 3rd
Layer antireflection layer.
Step 4：Coatings in Vacuum makes annealing treatment
The thermal-collecting tube of coating for selective absorption will be coated with carries out vacuum after annealing heat treatment, wherein, vacuum be 3.0 ×
10-3~5 × 10-3Pa, annealing temperature is 400 DEG C~650 DEG C, and annealing time is 2~5h.
The advantage of the invention is that：
Coating for selective absorption provided by the present invention is by metal infrared reflecting layer, exotic material WOx/ZrOxComposition
Double interference absorbed layers and ceramic antireflection layer composition, with visible-infrared spectrum high-absorbility, the spy of infrared spectrum low-launch-rate
Point.Due to WOx/ZrOxWith excellent high-temperature stability, while using high-temperature vacuum annealing process so that this new type high temperature
Coating for selective absorption can remain in that good heat is steady under 500 DEG C~600 DEG C elevated temperature in vacuo or 400 DEG C of atmospheric conditions
It is qualitative.
With use AlNxOx、AlNxThe coating for selective absorption of material compares, this coating by vacuum high-temperature annealing after,
Microstructure and physical property at high temperature is more stable, and coating hardness has high rigidity and good abrasion resistance properties,
Suitable for the solar vacuum heat-collecting pipe and antivacuum thermal-collecting tube of high temperature work.
Brief description of the drawings
Fig. 1：A kind of WO that the present invention is providedx/ZrOxThe structural representation of high temperature solar energy selective absorption coating；
Fig. 2：A kind of WO that the present invention is providedx/ZrOxThe preparation method flow chart of high temperature solar energy selective absorption coating.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The present invention is a kind of WOx/ZrOxHigh temperature solar energy selective absorption coating, with reference to section as shown in figure 1, coating bag
Trilamellar membrane is included, infrared reflecting layer, absorbed layer and antireflection layer are followed successively by from bottom to surface；
Ground floor infrared reflecting layer is Cu or Ag films, and positioned at matrix surface, thickness is 100~300nm；Second layer absorbed layer
Including two sublayer structures, two subgrades are WOx+ZrOxThe thickness of film, the first subgrade and the second subgrade is 150~
The thickness of 200nm, the first subgrade and the second subgrade can with it is equal can also be unequal；ZrO in first subgradexPercent by volume
It is 50~75%, remaining is WO3, the second subgrade ZrOxPercent by volume be 30~50%, remaining is WOx；Wherein the first subgrade
Adjacent with ground floor infrared reflecting layer, the second subgrade is adjacent with third layer antireflection layer；Third layer antireflection layer is ZrO2Film is thick
It is 120~200nm to spend.
A kind of WO that the present invention is providedx/ZrOxSolar selectively absorbing coating：In air quality factors A M1.5 conditions
Under, coating absorptivity is 96.2%, and normal emittance is 0.04.Vacuum annealing treatment is carried out, 5 × 10-3Under Pa vacuums, warp
After 550 DEG C of vacuum annealings 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.04,5 × 10-3Under Pa vacuums,
After 600 DEG C of vacuum annealings 2 hours, coating absorptivity is 97.6%, and normal emittance is 0.04.Under atmospheric conditions, through 350 DEG C
After insulation 2 hours, coating absorptivity is 97.5%, and normal emittance is 0.04；Under atmospheric conditions, 2 hours are incubated through 400 DEG C
Afterwards, coating absorptivity is 97.1%, and normal emittance is 0.05.
A kind of WO that the present invention is providedx/ZrOxThe preparation method of high temperature solar energy selective absorption coating, as shown in Fig. 2
Including following steps：
Step one：Ground floor infrared-emitting layer is prepared on matrix；
Using simple metal target direct current or medium frequency magnetron sputtering method, for Cu targets or Ag targets, (purity is simple metal target
99.99%), prepared as sputter gas using Ar gas, matrix uses high-speed steel, and vacuum chamber base vacuum is evacuated into 4 in advance before sputtering
×10-3~5 × 10-3Pa, is passed through inert gas Ar gas as sputtering atmosphere, and Ar throughputs are 1000~1400sccm, and adjustment is splashed
Distance is penetrated for 130~150mm, regulation sputtering pressure is 2 × 10-1~4 × 10-1Pa, opens the sputtering target power supply of simple metal target,
Adjustment sputtering voltage is 380~450V, and sputtering current is 8~10A, is prepared using magnetically controlled DC sputtering mode, and splash coating is thick
It is 100~300nm to spend, and obtains ground floor infrared-emitting layer, and the layer has high reflection characteristic, emissivity to infrared band spectrum
It is low；
Step 2：Second layer absorbed layer is prepared on ground floor infrared-emitting layer；
Using medium frequency magnetron sputtering method, with metal W target and target Zr (purity 99.99%) as sputtering target material, first will be true
Empty room takes out base vacuum to 4 × 10 in advance-3~5 × 10-3Pa, then passes to Ar, O2Gaseous mixture, the flow of Ar for 800~
1400sccm, O2Flow be 120~150sccm, regulation sputtering pressure be 2 × 10-1~4 × 10-1Pa, is separately turned on W and Zr
Target power supply, during sputtering, adjustment W targets sputtering voltage is 600~750V, and sputtering current is 50~60A, and Zr targets sputtering voltage is 650
~800V, sputtering current is 20~30A, and the first subgrade WO is prepared on ground floor infrared reflecting layerx+ZrOxFilm, thickness is 150
~200nm；
Adjust sputtering pressure to 4 × 10-1~6 × 10-1Pa, increases O2Flow be 150~190sccm, regulation W targets sputtering
Electric current is 40~50A, and other parameters are constant, in the first subgrade WOx+ZrOxContinue sputtering on film and obtain the second subgrade WOx+
ZrOxFilm, thickness is 150~200nm；First subgrade and the second subgrade are gone back in addition to itself inherent absorption characteristic to solar spectrum
Interference sink effect is formed, the optical absorption of coating is strengthened；
Step 3：Third layer antireflection layer is prepared on second layer absorbed layer；
Using Zr targets (purity 99.99%) as sputtering target material, vacuum chamber is taken out into base vacuum to 4 × 10 in advance before sputtering-3
~5 × 10-3Pa, using Ar gas as sputter gas, O2As reacting gas, O2Flow is 300~400sccm, adjusts Ar and O2Stream
Amount is than being 2.5:1~4:1, regulation sputtering pressure is 4 × 10-1~6 × 10-1Pa, during sputtering, adjustment sputtering voltage be 300~
400V, sputtering current is 25~30A, and the ZrO that thickness is 120~200nm is obtained using medium frequency magnetron sputtering modexFilm, i.e.,
Three layers of antireflection layer.Third layer antireflection layer has increases transmissivity, wear-resisting, oxidation resistant effect.
Step 4：Coatings in Vacuum makes annealing treatment
The thermal-collecting tube of coating for selective absorption will be coated with carries out vacuum after annealing heat treatment, wherein, vacuum be 3.0 ×
10-3~5 × 10-3Pa, annealing temperature is 400 DEG C~650 DEG C, and annealing time is 2~5h.
Embodiment 1：
The present embodiment provides a kind of WOx/ZrOxSolar selectively absorbing coating, the coating includes three coatings, is divided into the
One layer of infrared reflecting layer, second layer absorbed layer, third layer antireflection layer, ground floor Cu film thicknesses are 170nm, second layer gross thickness
It is 360nm, wherein the first subgrade WOx+ZrOxFilm thickness is 200nm, the second subgrade WOx+ZrOxFilm thickness is 160nm, and first is sub-
ZrO in layerxPercent by volume be 60%, remaining is WOx；Second subgrade ZrOxPercent by volume be 40%, remaining is WOx；
Third layer Zr OxFilm thickness is 120nm.Prepare above-mentioned WOx/ZrOxThe method of solar selectively absorbing coating, including it is following
Several steps：
Step one：Ground floor infrared-emitting layer is prepared on matrix；
From the Cu targets of purity 99.99%, base material uses high-speed steel.Vacuum chamber is taken out into base vacuum to 4.5 in advance before sputtering
×10-3, inert gas Ar is passed through as sputtering atmosphere, Ar throughputs are 1300sccm, and adjustment sputtering distance is 140mm, regulation
Sputtering pressure is 2.0 × 10-1Pa.Cu targets are opened, adjustment sputtering voltage is 440V, and sputtering current is 10A, using d.c. sputtering side
Formula prepares the thick Cu films of 150nm；
Step 2：Second layer absorbed layer is prepared on ground floor infrared-emitting layer；
Using metal W target and Zr target medium frequency magnetron sputtering methods, vacuum chamber is taken out into base vacuum to 4.5 × 10 in advance-3Pa, together
When be passed through Ar, O2Gaseous mixture, the flow of Ar is 1300sccm, O2Flow be 125sccm, regulation sputtering pressure be 2.0 ×
10-1Pa, is separately turned on W and Zr target power supplies, and adjustment W targets sputtering current is 60A, and voltage is 735V, and Zr targets sputtering current is 28A,
Voltage is 800V, and the first thick subgrade WO of 150nm are prepared on Cu filmsx+ZrOxFilm；
Adjustment O2Flow be 160sccm, regulation W targets sputtering current is 40A, continues to prepare that thickness is 60nm is second sub-
Layer WOx+ZrOxFilm；
Step 3：Third layer antireflection layer is prepared on the second layer；
From the Zr targets of purity 99.99%, vacuum chamber is taken out into base vacuum to 4.5 × 10 in advance before sputtering-3Pa, while being passed through
Ar、O2Gaseous mixture, adjusts Ar and O2Flow-rate ratio is 2：1, adjustment sputtering distance is 140mm, and regulation sputtering pressure is 6.0 × 10- 1Pa, during sputtering, adjustment sputtering current is 30A, and sputtering voltage is 750V, and 120nm thickness Zr is prepared using medium frequency magnetron sputtering mode
OxFilm.
Step 4：Coatings in Vacuum makes annealing treatment
The thermal-collecting tube of coating for selective absorption will be coated with carries out vacuum after annealing heat treatment, wherein, vacuum is 4 × 10- 3Pa, annealing temperature is 600 DEG C, and annealing time is 5h.
The performance of solar selectively absorbing coating manufactured in the present embodiment is as follows：In air quality factors A M1.5 conditions
Under, coating absorptivity is 96.3%, and normal emittance is 0.04.Vacuum annealing treatment is carried out, 5 × 10-3Under Pa vacuums, warp
After 550 DEG C of vacuum annealings 2 hours, coating absorptivity is 97.2%, and normal emittance is 0.05,5 × 10-3Under Pa vacuums,
After 600 DEG C of vacuum annealings 2 hours, coating absorptivity is 97.7%, and normal emittance is 0.04.Under atmospheric conditions, through 350 DEG C
After insulation 2 hours, coating absorptivity is 97.5%, and normal emittance is 0.04；Under atmospheric conditions, 2 hours are incubated through 400 DEG C
Afterwards, coating absorptivity is 97.0%, and normal emittance is 0.05.
Embodiment 2：
The present embodiment provides a kind of WOx/ZrOxSolar selectively absorbing coating, the coating includes three coatings, is divided into the
One layer of infrared reflecting layer, second layer absorbed layer, third layer antireflection layer, ground floor Cu film thicknesses are 140nm, second layer gross thickness
It is 300nm, wherein the first subgrade WOx+ZrOxFilm thickness is 150nm, the second subgrade WOx+ZrOxFilm thickness is 150nm, and first is sub-
ZrO in layerxPercent by volume be 55%, remaining is WOx；Second subgrade ZrO2Percent by volume be 35%, remaining is
WOx；Third layer Zr O2Film thickness is 150nm.Prepare above-mentioned WOx/ZrOxThe method of solar selectively absorbing coating, including
Following steps：
Step one：Ground floor infrared-emitting layer is prepared on matrix；
From the Cu targets of purity 99.99%, base material uses high-speed steel.Vacuum chamber is taken out into base vacuum to 4.5 in advance before sputtering
×10-3, inert gas Ar is passed through as sputtering atmosphere, Ar throughputs are 1400sccm, and adjustment sputtering distance is 130mm, regulation
Sputtering pressure is 3.0 × 10-1Pa.Cu targets are opened, adjustment sputtering voltage is 400V, and sputtering current is 10A, using d.c. sputtering side
Formula prepares the thick Cu films of 140nm；
Step 2：Second layer absorbed layer is prepared on ground floor infrared-emitting layer；
Using metal W target and Zr target medium frequency magnetron sputtering methods, vacuum chamber is taken out into base vacuum to 4.0 × 10 in advance-3Pa, together
When be passed through Ar, O2Gaseous mixture, the flow of Ar is 1300sccm, O2Flow be 120sccm, regulation sputtering pressure be 2.0 ×
10-1Pa, is separately turned on W and Zr target power supplies, and adjustment W targets sputtering current is 65A, and voltage is 750V, and Zr targets sputtering current is 25A,
Voltage is 770V, and the first thick subgrade WO of 150nm are prepared on Cu filmsx+ZrOxFilm；
Adjustment O2Flow be 140sccm, regulation W targets sputtering current is 45A, continues to prepare second that thickness is 100nm
Subgrade WOx+ZrOxFilm；
Step 3：Third layer antireflection layer is prepared on the second layer；
From the Zr targets of purity 99.99%, vacuum chamber is taken out into base vacuum to 4.0 × 10 in advance before sputtering-3Pa, while being passed through
Ar、O2Gaseous mixture, adjusts Ar and O2Flow-rate ratio is 2：1, adjustment sputtering distance is 130mm, and regulation sputtering pressure is 6.0 × 10- 1Pa, during sputtering, adjustment sputtering current is 30A, and sputtering voltage is 720V, and 150nm thickness Zr is prepared using medium frequency magnetron sputtering mode
O2Film.
Step 4：Coatings in Vacuum makes annealing treatment
The thermal-collecting tube of coating for selective absorption will be coated with carries out vacuum after annealing heat treatment, wherein, vacuum be 3.0 ×
10-3, annealing temperature is 650 DEG C, and annealing time is 3h.
Embodiment 3：
The present embodiment provides a kind of WOx/ZrOxSolar selectively absorbing coating, the coating includes three coatings, is divided into the
One layer of infrared reflecting layer, second layer absorbed layer, third layer antireflection layer, ground floor Cu film thicknesses are 240nm, second layer total thickness
It is 600nm to spend, wherein the first subgrade WOx+ZrOxFilm thickness is 300nm, the second subgrade WOx+ZrOxFilm thickness is 300nm, first
ZrO in subgrade2Percent by volume be 70%, remaining is WOx；Second subgrade ZrOxPercent by volume be 50%, remaining is
WOx；Third layer Zr OxFilm thickness is 200nm.Prepare above-mentioned WOx/ZrOxThe method of solar selectively absorbing coating, including
Following steps：
Step one：Ground floor infrared-emitting layer is prepared on matrix；
From the Cu targets of purity 99.99%, base material uses high-speed steel.Vacuum chamber is taken out into base vacuum to 4.0 in advance before sputtering
×10-3, inert gas Ar is passed through as sputtering atmosphere, Ar throughputs are 1300sccm, and adjustment sputtering distance is 130mm, regulation
Sputtering pressure is 3.0 × 10-1Pa.Cu targets are opened, adjustment sputtering voltage is 400V, and sputtering current is 10A, using d.c. sputtering side
Formula prepares the thick Cu films of 140nm；
Step 2：Second layer absorbed layer is prepared on ground floor infrared-emitting layer；
Using metal W target and Zr target medium frequency magnetron sputtering methods, vacuum chamber is taken out into base vacuum to 4.0 × 10 in advance-3Pa, together
When be passed through Ar, O2Gaseous mixture, the flow of Ar is 1300sccm, O2Flow be 135sccm, regulation sputtering pressure be 2.0 ×
10-1Pa, is separately turned on W and Zr target power supplies, and adjustment W targets sputtering current is 65A, and voltage is 750V, and Zr targets sputtering current is 24A,
Voltage is 760V, and the first thick subgrade WO of 150nm are prepared on Cu filmsx+ZrOxFilm；
Adjustment O2Flow be 190sccm, regulation W targets sputtering current is 45A, continues to prepare second that thickness is 100nm
Subgrade WOx+ZrOxFilm；
Step 3：Third layer antireflection layer is prepared on the second layer；
From the Zr targets of purity 99.99%, vacuum chamber is taken out into base vacuum to 4.0 × 10 in advance before sputtering-3Pa, while being passed through
Ar、O2Gaseous mixture, adjusts Ar and O2Flow-rate ratio is 2：1, adjustment sputtering distance is 130mm, and regulation sputtering pressure is 6.0 × 10- 1Pa, during sputtering, adjustment sputtering current is 30A, and sputtering voltage is 720V, and 200nm thickness Zr is prepared using medium frequency magnetron sputtering mode
OxFilm.
Step 4：Coatings in Vacuum makes annealing treatment
The thermal-collecting tube of coating for selective absorption will be coated with carries out vacuum after annealing heat treatment, wherein, vacuum be 3.0 ×
10-3, annealing temperature is 650 DEG C, and annealing time is 3h.
The performance of solar selectively absorbing coating manufactured in the present embodiment is as follows：In air quality factors A M1.5 conditions
Under, coating absorptivity is 96.5%, and normal emittance is 0.03.Vacuum annealing treatment is carried out, 5 × 10-3Under Pa vacuums,
After 550 DEG C of vacuum annealings 2 hours, coating absorptivity is 97.1%, and normal emittance is 0.04,5 × 10-3Pa vacuums
Under, after 600 DEG C of vacuum annealings 2 hours, coating absorptivity is 97.9%, and normal emittance is 0.04.
Claims (1)
1. a kind of WOx/ZrOxThe preparation method of high temperature solar energy selective absorption coating, including following steps：
Step one：Ground floor infrared reflecting layer is prepared on matrix；
Using simple metal target direct current or medium frequency magnetron sputtering method, simple metal target is Cu targets, is prepared as sputter gas using Ar gas,
Matrix uses high-speed steel, and vacuum chamber base vacuum is evacuated into 4.0 × 10 in advance before sputtering-3~5.0 × 10-3Pa, is passed through inert gas
Used as sputtering atmosphere, Ar throughputs are 1000~1400sccm to Ar gas, and adjustment sputtering distance is 130~150mm, regulation sputtering gas
Press is 2 × 10-1~4 × 10-1Pa, opens the sputtering target power supply of simple metal target, and adjustment sputtering voltage is 380~450V, sputtering electricity
It is 45~65A to flow, and is prepared using magnetically controlled DC sputtering mode, and splash coating thickness is 140~240nm, obtains ground floor infrared
Reflecting layer；
Step 2：Second layer absorbed layer is prepared on ground floor infrared reflecting layer；
Using medium frequency magnetron sputtering method, with metal W target and Zr targets as sputtering target material, vacuum chamber is taken out into base vacuum extremely in advance first
4×10-3~5 × 10-3Pa, then passes to Ar, O2Gaseous mixture, the flow of Ar is 800~1400sccm, O2Flow be 120
~150sccm, regulation sputtering pressure is 2 × 10-1~4 × 10-1Pa, is separately turned on W and Zr target power supplies, during sputtering, adjusts W targets
Sputtering voltage be 600~750V, sputtering current be 50~60A, Zr targets sputtering voltage be 650~800V, sputtering current be 20~
30A, prepares the first subgrade WO on ground floor infrared reflecting layerx+ZrOxFilm, thickness is 150~200nm；
Adjust sputtering pressure to 4 × 10-1~6 × 10-1Pa, increases O2Flow be 150~190sccm, adjust W target sputtering currents
It is 40~50A, other parameters are constant, in the first subgrade WOx+ZrOxContinue sputtering on film and obtain the second subgrade WOx+ZrOx
Film, thickness is 150~200nm；
Step 3：Third layer antireflection layer is prepared on second layer absorbed layer；
Using Zr targets as sputtering target material, vacuum chamber is taken out into base vacuum to 4 × 10 in advance before sputtering-3~5 × 10-3Pa, with Ar gas
As sputter gas, O2As reacting gas, O2Flow is 300~400sccm, adjusts Ar and O2Flow-rate ratio is 2.5:1~4:1,
Regulation sputtering pressure is 4 × 10-1~6 × 10-1Pa, during sputtering, adjustment sputtering voltage be 300~400V, sputtering current be 25~
30A, the ZrO that thickness is 120~200nm is obtained using medium frequency magnetron sputtering modexFilm, i.e. third layer antireflection layer；
Step 4：Coatings in Vacuum makes annealing treatment
The thermal-collecting tube of coating for selective absorption will be coated with carries out vacuum after annealing heat treatment, wherein, vacuum is 3.0 × 10-3~5
×10-3Pa, annealing temperature is 400 DEG C~650 DEG C, and annealing time is 2~5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410229712.0A CN104006560B (en) | 2014-05-28 | 2014-05-28 | A kind of WOx/ZrOxHigh temperature solar energy selective absorption coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410229712.0A CN104006560B (en) | 2014-05-28 | 2014-05-28 | A kind of WOx/ZrOxHigh temperature solar energy selective absorption coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104006560A CN104006560A (en) | 2014-08-27 |
| CN104006560B true CN104006560B (en) | 2017-06-16 |
Family
ID=51367343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410229712.0A Active CN104006560B (en) | 2014-05-28 | 2014-05-28 | A kind of WOx/ZrOxHigh temperature solar energy selective absorption coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104006560B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107270564B (en) * | 2016-04-07 | 2019-11-15 | 有研工程技术研究院有限公司 | A kind of sunlight heat absorber coatings |
| JP6540859B1 (en) * | 2018-05-09 | 2019-07-10 | 住友金属鉱山株式会社 | COMPOSITE TUNGSTEN OXIDE FILM, PROCESS FOR PRODUCING THE SAME, FILM-FORMED SUBSTRATE AND ARTICLE HAVING THE FILM |
| WO2020097811A1 (en) * | 2018-11-14 | 2020-05-22 | 香港科技大学深圳研究院 | Full-ceramic and high-temperature solar energy selective absorbing coating and manufacturing method therefor |
| CN109972110A (en) * | 2019-04-29 | 2019-07-05 | 陕西科技大学 | A kind of bilayer WOxBase photothermal conversion coating and preparation method thereof |
| CN110983280A (en) * | 2019-12-25 | 2020-04-10 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation of W-doped ZrO by ion beam assisted deposition process2Method for making thin film |
| CN110983274A (en) * | 2019-12-25 | 2020-04-10 | 中建材蚌埠玻璃工业设计研究院有限公司 | W-doped ZrO2Method for producing thin film |
| CN115058144A (en) * | 2022-06-06 | 2022-09-16 | 凌波(南通)新材料科技有限公司 | Preparation method of solar radiation absorbing coating in solar energy utilization field |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650474A (en) * | 2012-05-23 | 2012-08-29 | 北京天瑞星光热技术有限公司 | High-temperature selective solar energy-absorbing coating with Cr2O3-Al2O3 dual-ceramic structure and preparation method thereof |
| CN103388917A (en) * | 2013-07-10 | 2013-11-13 | 山东大学（威海） | Solar selective absorbing coating and preparation method thereof |
| CN103411335A (en) * | 2013-07-30 | 2013-11-27 | 中国科学院上海技术物理研究所 | Selective absorbing film set of radiation absorbing layer based on mixture |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201218622Y (en) * | 2008-04-15 | 2009-04-08 | 北京天瑞星真空技术开发有限公司 | Selective solar energy absorbing coating |
| CN101737982B (en) * | 2009-11-25 | 2012-05-30 | 北京航空航天大学 | Solar selectively absorbing coating and preparation method thereof |
-
2014
- 2014-05-28 CN CN201410229712.0A patent/CN104006560B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650474A (en) * | 2012-05-23 | 2012-08-29 | 北京天瑞星光热技术有限公司 | High-temperature selective solar energy-absorbing coating with Cr2O3-Al2O3 dual-ceramic structure and preparation method thereof |
| CN103388917A (en) * | 2013-07-10 | 2013-11-13 | 山东大学（威海） | Solar selective absorbing coating and preparation method thereof |
| CN103411335A (en) * | 2013-07-30 | 2013-11-27 | 中国科学院上海技术物理研究所 | Selective absorbing film set of radiation absorbing layer based on mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104006560A (en) | 2014-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104006560B (en) | A kind of WOx/ZrOxHigh temperature solar energy selective absorption coating and preparation method thereof | |
| CN201218622Y (en) | Selective solar energy absorbing coating | |
| CN101922816B (en) | Solar selective absorbing coating and preparation method thereof | |
| CN102102918B (en) | Cr series high-temperature solar selective absorbing coating and preparation method thereof | |
| CN102620456B (en) | Medium-and-low-temperature solar selective absorption thin film and preparation method thereof | |
| CN104005003B (en) | High temperature and salt spray resistance solar energy selective absorbing coating in atmosphere and preparation method of coating | |
| CN101806508B (en) | High temperature solar energy selective absorption coating and preparation method thereof | |
| CN100543499C (en) | A kind of solar energy selective absorption coating | |
| CN101666557B (en) | Non-vacuum solar spectrum selective absorption film and preparation method thereof | |
| CN107314559B (en) | Photothermal conversion coating and preparation method thereof | |
| CN106884145B (en) | A kind of coating for selective absorption of sunlight spectrum and preparation method thereof | |
| CN105091377B (en) | A kind of solar selectively absorbing coating and preparation method thereof | |
| CN102277555A (en) | TiN and AlN combined high-temperature solar selectively absorbing coating with double-ceramic structure and preparation method thereof | |
| CN101737982A (en) | Solar selectively absorbing coating and preparation method thereof | |
| CN102286720B (en) | High-temperature solar selective absorbing coating with SiO2 and Cr2O3 double-ceramic structure and preparation method thereof | |
| CN102328476B (en) | High-temperature solar energy selective absorption coating comprising TiO2 and Al2O3 double ceramic structures and preparation method thereof | |
| CN103302917B (en) | A kind of double absorption layer TiON weatherability photo-thermal coating and preparation method thereof | |
| CN109338297B (en) | Hafnium diboride-zirconium diboride-based high-temperature solar energy absorption coating and preparation method thereof | |
| CN103317788A (en) | Spectrum selective absorbing coating and preparation method thereof | |
| CN102328475B (en) | High-temperature solar selective absorption coating with SiO2 and TiO2 bi-ceramic structure and preparation method thereof | |
| CN105274474B (en) | A kind of high temperature resistance multilayer solar selectively absorbing coating and preparation method thereof | |
| CN106568207B (en) | High temperature coating for selective absorption of sunlight spectrum and preparation method thereof | |
| CN102954611B (en) | Medium-high temperature spectrum selective absorbing coating | |
| CN102650474A (en) | High-temperature selective solar energy-absorbing coating with Cr2O3-Al2O3 dual-ceramic structure and preparation method thereof | |
| CN106322799A (en) | Solar spectral selective absorbing coating used in medium and low vacuum environment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |