CN209147482U - A kind of solar selectively absorbing coating - Google Patents

A kind of solar selectively absorbing coating Download PDF

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CN209147482U
CN209147482U CN201821516751.9U CN201821516751U CN209147482U CN 209147482 U CN209147482 U CN 209147482U CN 201821516751 U CN201821516751 U CN 201821516751U CN 209147482 U CN209147482 U CN 209147482U
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sub
thickness
selectively absorbing
absorbing coating
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杨中周
刘静
孙志强
余刚
汪洪
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China Building Materials Academy CBMA
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Abstract

The utility model provides a kind of solar selectively absorbing coating.The coating successively includes substrate, infrared reflecting layer, absorbed layer and anti-reflection layer from bottom to surface, and the absorbed layer includes the first sub-layer, the second sub-layer and third sub-layer, and first sub-layer is contacted with infrared reflecting layer, and the third sub-layer is contacted with anti-reflection layer；The substrate thickness is 0.3-10mm；The infrared reflecting layer, absorbed layer and anti-reflection layer overall thickness are 245-545nm；First sub-layer with a thickness of 20-40nm；Second sub-layer is with a thickness of 40-65nm；The third sub-layer is with a thickness of 15-50nm.The coating can be improved the thermal stability of solar selectively absorbing coating；The coating is through 400 DEG C of atmospheric environments annealing 2h, alternatively, in 3.0x10‑3Under pa vacuum degree, through 500 DEG C of annealing 2h, absorptivity >=0.95, emissivity Jun≤0.08 (80 DEG C).

Description

A kind of solar selectively absorbing coating
Technical field
The utility model belongs to technical field of solar utilization technique more particularly to a kind of solar selectively absorbing coating.
Background technique
Solar spectral selective absorbing coating is solar thermal collector photothermal conversion core material, at 0.3 μm -2.5 μm Sunlight wave band there is high-absorbility, there is low-E in 2.5 μm -50 μm of infrared emanation wave bands, may be implemented pair The high-selenium corn Low emissivity of solar energy radiates, and converts solar energy into thermal energy to greatest extent.Coating for selective absorption is according to work temperature The difference of degree can be divided into: low temperature coating (being lower than 100 DEG C), medium temperature coating (100-400 DEG C) and high temperature coating (being higher than 400 DEG C). Low temperature coating is mainly used for solar water heater, and medium temperature coating is mainly used in industrial process heat production, sea water desalination and solar energy Water heater, high temperature coating are mainly used for centralized solar energy thermal-power-generating.The thermal radiation loss and T of coating4Direct proportionality, because The thermal stability of this coating is also the vital performance parameter of heat collector.
Metal nitride or metal oxynitride because of its excellent inoxidizability, thermal stability and controllable optical property, It has received widespread attention and studies.Chinese invention patent CN8510042 proposes a kind of Al-N/Al coating for selective absorption, inhales For yield up to 0.93, emissivity is 0.06 (100 DEG C), and is prepared with single metal Al target that simple process and low cost is low in It is widely applied on temperature solar energy heat collection pipe.But coating thermal stability is poor, and absorbed layer is oxidizable at relatively high temperatures and phase Counterdiffusion influences coating service life.Chinese invention patent CN105222381.A proposes a kind of Cr-N-O system selective absorbing Coating, absorptivity reach 0.90, and emissivity is only 0.025, but coating is only used for middle low temperature.
Utility model content
The main purpose of the utility model is that a kind of solar selectively absorbing coating is provided, technology to be solved Problem is to improve the thermal stability for the spectral selective absorbing coating that metal nitrogen (oxygen) compound absorbs, thus more suitable for high temperature Field.
It the purpose of this utility model and solves its technical problem and adopts the following technical solutions to realize.
According to the utility model proposes a kind of solar selectively absorbing coating, the coating from bottom to surface according to Secondary includes substrate, infrared reflecting layer, absorbed layer and anti-reflection layer, and the absorbed layer includes the first sub-layer, the second sub-layer and third Sub-layer, first sub-layer are contacted with infrared reflecting layer, and the third sub-layer is contacted with anti-reflection layer；The thickness of the substrate Degree is 0.3-10mm；The overall thickness of the infrared reflecting layer, absorbed layer and anti-reflection layer is 245-545nm.
It the purpose of this utility model and solves its technical problem also following technical measures can be used to further realize.
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer with a thickness of 120- 300nm；The absorbed layer with a thickness of 75-155nm；The anti-reflection layer with a thickness of 50-90nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein first sub-layer with a thickness of 20-40nm； Second sub-layer is with a thickness of 40-65nm；The third sub-layer is with a thickness of 15-50nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein second sub-layer with a thickness of 50-60nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein the third sub-layer with a thickness of 35-50nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer with a thickness of 120- 220nm；First sub-layer with a thickness of 30nm；Second sub-layer is with a thickness of 40-50nm；The third sub-layer is thick Degree is 35-50nm；The anti-reflection layer with a thickness of 50-75nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein the substrate is Cu, Al, stainless steel or glass A combination of one or more；The infrared reflecting layer is the combination of one or more of Cu, W and Mo；Institute The anti-reflection layer stated is SiO2。
Preferably, solar selectively absorbing coating above-mentioned, wherein first sub-layer is CrSiN, wherein CrSi Content be greater than N content；Second sub-layer is CrSiN, wherein the content of CrSi is less than or equal to the content of N；Described Third sub-layer is CrSiNO, wherein the content of CrSi is less than or equal to the sum of N and O content.
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer is Cu piece.
By above-mentioned technical proposal, utility model has the advantages that
1, solar energy type selecting absorber coatings provided by the utility model have the nitridation of infrared reflecting layer, silicon containing transition metal Object and nox adsorption layer, antireflection layer composition, the refractive index from absorbed layer to surface antireflection layer material are gradually successively decreased, shape At gradient, make the utility model absorber coatings in 0.3 μm of -2.5 μm of absorptivity with higher of solar energy spectral limit, 2.5 μm -48 μm of heat radiation infrared region have low radiance.Since the nitride and nitrogen oxides of silicon containing transition metal have There is excellent high-temperature stability, so that absorber coatings are still kept good after 400 DEG C of atmospheric environments and 500 DEG C of vacuum environment annealing Good thermal stability.
2, compared with using monometallic Cr-N-O, Al-N-O system absorber coatings, the utility model absorber coatings have higher Thermal stability, be more suitable for high temperature absorber coatings field.
The above description is merely an outline of the technical solution of the present invention, in order to better understand the skill of the utility model Art means, and can be implemented in accordance with the contents of the specification, below on the preferred embodiment of the present invention and the accompanying drawings in detail It describes in detail bright as after.
Detailed description of the invention
The structural schematic diagram of Fig. 1 solar selectively absorbing coating described in the utility model.
Specific embodiment
Further to illustrate that the utility model is the technical means and efficacy reaching predetermined goal of the invention and being taken, below In conjunction with attached drawing and preferred embodiment, to according to the utility model proposes a kind of solar selectively absorbing coating, it is specific real Mode, structure, feature are applied, detailed description is as follows.In the following description, different " embodiment " or " embodiment " refers to different It surely is the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be by any suitable form groups It closes.
The utility model provides a kind of solar selectively absorbing coating, and the coating successively includes from bottom to surface Substrate 1, infrared reflecting layer 2, absorbed layer 3 and anti-reflection layer 4, the absorbed layer 3 include the first sub-layer 31, the second sub-layer 32 and the Three sub-layers 33, first sub-layer 31 are contacted with infrared reflecting layer 2, and the third sub-layer 33 contacts 4 with anti-reflection layer；It is described Substrate 1 with a thickness of 0.3-10mm；The overall thickness of the infrared reflecting layer 2, absorbed layer 3 and anti-reflection layer 4 is 245- 545nm。
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer 2 with a thickness of 120- 300nm；The absorbed layer 3 with a thickness of 75-155nm；The anti-reflection layer 4 with a thickness of 50-90nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein first sub-layer 31 with a thickness of 20- 40nm；Second sub-layer 32 is with a thickness of 40-65nm；The third sub-layer 33 is with a thickness of 15-50nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein second sub-layer 32 with a thickness of 50- 60nm。
Preferably, solar selectively absorbing coating above-mentioned, wherein the third sub-layer 33 with a thickness of 35- 50nm。
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer 2 with a thickness of 120- 220nm；First sub-layer 31 with a thickness of 30nm；Second sub-layer 32 is with a thickness of 40-50nm；The third is sub- Layer 33 is with a thickness of 35-50nm；The anti-reflection layer 4 with a thickness of 50-75nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein the substrate 1 is Cu, Al, stainless steel or glass A combination of one or more；The infrared reflecting layer 2 is the combination of one or more of Cu, W and Mo；Institute The anti-reflection layer stated is SiO2。
Preferably, solar selectively absorbing coating above-mentioned, wherein first sub-layer 31 is CrSiN, wherein The content of CrSi is greater than the content of N；Second sub-layer 32 is CrSiN, wherein the content of CrSi is less than or equal to the content of N； The third sub-layer 33 is CrSiNO, wherein the content of CrSi is less than or equal to the sum of N and O content.
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer 2 is Cu piece.
The material of first sub-layer 31, the second sub-layer 31 is CrSiN；The material of the third sub-layer 33 is CrSiNO。
Preferably, solar selectively absorbing coating above-mentioned, wherein in first sub-layer 31, with atom number Meter, the content of CrSi are greater than the content of N；In second sub-layer 32, in terms of atom number, the content of CrSi is less than etc. In the content of N；In the third sub-layer 33, in terms of atom number, the content of CrSi is less than or equal to the sum of N and O content.
Preferably, solar selectively absorbing coating above-mentioned, wherein the substrate 1 is Cu, Al, stainless steel or glass A combination of one or more；The infrared reflecting layer 2 is the combination of one or more of Cu, W or Mo；Institute The anti-reflection layer stated is SiO2。
Preferably, solar selectively absorbing coating above-mentioned, wherein the substrate with a thickness of 0.3-10mm；It is described Infrared reflecting layer, absorbed layer and anti-reflection layer overall thickness be 245-545nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer 2 with a thickness of 120- 300nm；The absorbed layer 3 with a thickness of 75-155nm；The anti-reflection layer 4 with a thickness of 50-90nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein first sub-layer 31 with a thickness of 20- 40nm；Second sub-layer 32 is with a thickness of 40-65nm；The third sub-layer 33 is with a thickness of 15-50nm.
Preferably, solar selectively absorbing coating above-mentioned, wherein the infrared reflecting layer 2 with a thickness of 120- 220nm；First sub-layer 31 with a thickness of 30nm；Second sub-layer 32 is with a thickness of 40-50nm；The third is sub- Layer 33 is with a thickness of 35-50nm；The anti-reflection layer 4 with a thickness of 50-75nm；The infrared reflecting layer is Cu piece.
Solar selectively absorbing coating provided by the utility model: the absorptivity of the coating is greater than 0.95, emissivity Less than 0.07 (80 DEG C).After 400 DEG C of atmospheric environments anneal 2h, absorptivity is greater than 0.94, and emissivity is less than or equal to 0.08 (80 DEG C), in 3.0x10‐3Under pa vacuum degree, after 500 DEG C of annealing times are 2h, absorptivity is greater than 0.95, and emissivity is less than or equal to 0.07(80℃)。
The utility model proposes a kind of solar selectively absorbing coating pass through following steps obtain:
(1) pretreatment of substrate:
First the substrate 1 is tentatively cleaned using neutral detergent solution and deionized water, later in filming equipment into piece Room bombards 1 surface of substrate by radio-frequency ion source and carries out secondary cleaning, obtains pretreated substrate；Technological parameter setting As follows: radio-frequency power supply sputtering power is 200w, and working gas is the Ar that purity is 99.99%, flow 45sccm, operating air pressure It is 9.8 × 10‐2MTorr, sputtering time 360s.
(2) infrared reflecting layer 2 is deposited on the substrate 1:
The Ni metal target or W target or Mo target that purity is 99.95% are chosen, being passed through purity is 99.99% working gas Ar, is adopted With pulsed dc magnetron sputtering method, realize on the substrate 1 deposited cu layer or W layer or Mo layers as infrared reflecting layer 2.Technique Parameter setting is as follows: pulse dc power sputtering power is 1200w, and the flow of Ar working gas is 50sccm, and operating air pressure is 5mTorr, for substrate 1 in generated beneath back and forth movement (the referred to as first movement), the temperature of substrate 1 is room temperature.
(3) the first sub-layer 31 is deposited on infrared reflecting layer 2:
CrSi (7:3, at%) target that purity is 99.7% is chosen, being successively passed through purity is the work of 99.99% inertia Gas Ar, the first reaction gas N2, passed through using pulse dc power magnetron sputtering method and bombard CrSi target, on infrared reflecting layer 2 The material for depositing the first sub-layer 31 described in first sub-layer 31 is CrSiN, wherein the content of CrSi is big in terms of atom number In the content of N, it is labeled as CrSiN (H).
The technological parameter setting that first sub-layer 31 deposits are as follows: pulse dc power sputtering power is 1500w, work gas Pressure is 5mTorr, and the flow of working gas Ar is 50sccm, the first reaction gas N2Flow be 15sccm, infrared reflecting layer 2/ For substrate 1 in CrSi generated beneath back and forth movement (the referred to as second movement), temperature is room temperature.
(4) the second sub-layer 32 is deposited in the first sub-layer 31:
CrSi (7:3, at%) target that purity is 99.7% is chosen, being successively passed through purity is the work of 99.99% inertia Gas Ar, the first reaction gas N2, using pulse dc power magnetron sputtering method by bombardment CrSi target, in the first sub-layer 31 Deposit the second sub-layer 32；The material of second sub-layer 32 is CrSiN, wherein the content of CrSi is less than in terms of atom number Content equal to N is labeled as CrSiN (L).
The technological parameter setting that second sub-layer 32 deposits are as follows: pulse dc power sputtering power is 1500w, work gas Pressure is 5mTorr, and the flow of working gas Ar is 50sccm, the first reaction gas N2Flow be 50sccm, the first sub-layer 31/ For 2/ substrate 1 of infrared reflecting layer in CrSi generated beneath back and forth movement (referred to as third movement), temperature is room temperature.
(5) third sub-layer 33 is deposited in the second sub-layer 32:
CrSi (7:3, at%) target that purity is 99.7% is chosen, being successively passed through purity is the work of 99.99% inertia Gas Ar, the first reaction gas N2, the second reaction gas O2, using pulse dc power magnetron sputtering method by bombarding CrSi target, Third sub-layer 33 is deposited in the second sub-layer 32；The material of the third sub-layer 33 is CrSiNO.
The technological parameter setting that the third sub-layer 33 deposits are as follows: pulse dc power sputtering power is 1500w, work gas Pressure is 5mTorr, and the flow of working gas Ar is 50sccm, the first reaction gas N2Flow be 50sccm, the second reaction gas O2Flow be 10sccm, 2/ substrate 1 of the second 32/ first sub-layer of sub-layer, 31/ infrared reflecting layer transports back and forth in CrSi generated beneath Dynamic (the referred to as the 4th movement), temperature is room temperature.
(6) anti-reflection layer 4 is deposited in third sub-layer 33:
The SiAl target (7:3, wt%) that purity is 99.7% is chosen, being passed through purity is 99.99% inert working gas Ar With the second reaction gas O2, using pulse dc power magnetron sputtering method by bombardment SiAl target, in third sub-layer 33/ second 32/ first sub-layer of sub-layer, 31/ infrared reflecting layer, 2/ substrate 1 deposits SiO2As the anti-reflection layer 4.
The technological parameter that the anti-reflection layer 4 deposits is provided that pulse dc power sputtering power is 2000w, work gas Pressure is 5mTorr, and the flow of the working gas is 30sccm, the second reaction gas O2Flow be 14sccm, third is sub- Layer 33/ second 32/ first sub-layer of sub-layer, 31/ infrared reflecting layer, 2/ substrate 1 is in SiAl generated beneath back and forth movement (the referred to as the 5th fortune It is dynamic), temperature is room temperature.
Coating performance test:
By the cooling 20min of the sample of solar selectively absorbing coating obtained according to the method described above, slice is shut down； Then, the sample is made annealing treatment according to following two annealing process respectively, then measures the absorptivity of the coating And emissivity, absorption of the observation by the absorptivity and emissivity and the coating without annealing of the coating after high-temperature process The variation of rate and emissivity.
Annealing process 1: sample after cooling is annealed 2h under conditions of atmospheric environment, 400 DEG C of temperature.
Annealing process 2: by sample after cooling in vacuum degree 3.0x10‐3The environment of pa is annealed under conditions of 500 DEG C of temperature 2h。
Same part sample, only selects a kind of annealing process to be made annealing treatment；Same batch of sample, need to take more than one piece sample, no Annealing process with sample need to cover above two annealing process.
The coating is made annealing treatment；After the coating is measured respectively without annealing and annealing Coating absorptivity and emissivity, the variation and emissivity of absorptivity when calculating after its annealing with without annealing Variation；Smaller, emissivity the variation of variation of the absorptivity is smaller, indicates that the thermal stability of the coating is better.
Embodiment 1-5
According to above-mentioned solar selectively absorbing coating preparation method the step of (1)-(6) preparation solar energy Coating for selective absorption.
Its thermal stability is evaluated according to the evaluation method of the thermal stability of above-mentioned solar selectively absorbing coating.
Material, technological parameter and the performance of the embodiment 1-5 is shown in Table one.
Material, technological parameter and the performance table of one embodiment 1-5 of table
According to the thermal stability of the material of target listed by table one, the technological parameter of deposition and obtained absorber coatings Data it is visible:
Solar selectively absorbing coating prepared by embodiment 1-5 is in 400 DEG C of atmospheric environment, temperature annealing 2h Afterwards, performance change very little: 1) its coating absorptivity only has the decaying of very little, and decaying is less than or equal to 0.4%；2) its coating is sent out The rate of penetrating only has the raising of very little, and variation is less than or equal to 1%；Show good thermal stability.
Vacuum environment, temperature of the solar selectively absorbing coating prepared by embodiment 1-5 in vacuum degree 3.0x10-3pa After spending 500 DEG C of annealing 2h, performance change very little: 1) its coating absorptivity only has the decaying of very little, and decaying is less than etc. In 0.3%；2) its coatings emissivity only has the raising of very little, and variation is less than or equal to 1%；Show good thermostabilization Property.
The above descriptions are merely preferred embodiments of the present invention, not makees in any form to the utility model Limitation, any simple modification, equivalent change and modification made by the above technical examples according to the technical essence of the present invention, It is still within the scope of the technical solutions of the present invention.

Claims (7)

1. a kind of solar selectively absorbing coating, the coating successively include from bottom to surface substrate, infrared reflecting layer, Absorbed layer and anti-reflection layer, the absorbed layer include the first sub-layer, the second sub-layer and third sub-layer, first sub-layer with it is red Outer reflective layer contact, the third sub-layer are contacted with anti-reflection layer, it is characterised in that:
The substrate with a thickness of 0.3-10mm；
The overall thickness of the infrared reflecting layer, absorbed layer and anti-reflection layer is 245-545nm；
The third sub-layer with a thickness of 15-25nm；
First sub-layer is CrSiN, wherein the content of CrSi is greater than the content of N；
Second sub-layer is CrSiN, wherein the content of CrSi is less than or equal to the content of N；
The third sub-layer is CrSiNO, wherein the content of CrSi is less than or equal to the sum of N and O content.
2. solar selectively absorbing coating according to claim 1, it is characterised in that:
The infrared reflecting layer with a thickness of 120-300nm；
The absorbed layer with a thickness of 75-155nm；
The anti-reflection layer with a thickness of 50-90nm.
3. solar selectively absorbing coating according to claim 1, it is characterised in that:
First sub-layer with a thickness of 20-40nm；
Second sub-layer is with a thickness of 40-65nm.
4. solar selectively absorbing coating according to claim 1, it is characterised in that:
Second sub-layer with a thickness of 50-60nm.
5. solar selectively absorbing coating according to claim 1, it is characterised in that:
The infrared reflecting layer with a thickness of 120-220nm；
First sub-layer with a thickness of 30nm；
Second sub-layer is with a thickness of 40-50nm；
The anti-reflection layer with a thickness of 50-75nm.
6. solar selectively absorbing coating according to claim 1, it is characterised in that:
The substrate is one kind of Cu, Al, stainless steel or glass；
The infrared reflecting layer is one of Cu, W and Mo；
The anti-reflection layer is SiO2。
7. solar selectively absorbing coating according to claim 1, it is characterised in that:
The infrared reflecting layer is Cu piece.
CN201821516751.9U 2018-09-17 2018-09-17 A kind of solar selectively absorbing coating Active CN209147482U (en)

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