Summary of the invention
The objective of the invention is to avoid the deficiencies in the prior art part that a kind of high-performance multilayer composite solar selective absorption coating is provided.Poor to solve present China flat-plate solar collector absorber coatings weatherability, the low problem that waits technical elements of heat absorption efficiency proposes a kind of the high temperature resistant of flat plate collector that be applicable to, humidity, the multilayer composite solar selective absorption coating that absorption efficiency is high.
For achieving the above object, the technical scheme that the present invention takes is: a kind of high-performance multilayer composite solar selective absorption coating, include and be sequentially with far-infrared reflection layer (2), compound heat absorption layer (4) and anti-oxidant and antireflection layer (5) on matrix (1), its main feature is: far-infrared reflection layer (2) is the Al layer of sputtering sedimentation on matrix (1); Compound heat absorption layer (4) is the TiNOx layer of sputtering sedimentation on far-infrared reflection layer (2), and anti-oxidant and antireflection layer (5) is the SiO of sputtering sedimentation on compound heat absorption layer (4)
2Layer.
Described high-performance multilayer composite solar selective absorption coating also includes between far-infrared reflection layer (2) and compound heat absorption layer (4) and is provided with stabilized zone (3); Stabilized zone (3) is the Ti+TiC layer of sputtering sedimentation on far-infrared reflection layer (2).
Described high-performance multilayer composite solar selective absorption coating, described matrix (1) are phosphorized copper band or oxygen-free copper stripe or aluminium strip.
Described high-performance multilayer composite solar selective absorption coating, the thickness of described far-infrared reflection layer (2) is 100~200nm.
Described high-performance multilayer composite solar selective absorption coating, the thickness of described stabilized zone (3) is 50~100nm.
Described high-performance multilayer composite solar selective absorption coating, the thickness of described compound hot coefficient layer (4) is 100~200nm.
Described high-performance multilayer composite solar selective absorption coating, described thickness anti-oxidant and antireflection layer (5) is 60~100nm.
A kind of preparation method of high-performance multilayer composite solar selective absorption coating, its main feature are that step is:
1. will carry out pretreated matrix and pack in the horizontal magnetron sputtering coater, and the vacuum of the vacuum chamber of horizontal magnetron sputtering coater will be evacuated to 2.0 * 10
-2~8.0 * 10
-3Pa;
2. feed purity and be 99.95% argon gas in vacuum chamber, making vacuum is 6.5 * 10
-2~9.0 * 10
-2Pa connects the negative DC voltage bombardment and cleans matrix 4-6min in argon gas atmosphere, remove matrix surface impurity, the activation matrix surface;
3. feed purity and be 99.95% argon gas in vacuum chamber, open the aluminium target, go up the depositing Al layer at matrix (1), wherein argon flow amount is 100~300sccm, and air pressure is 6 * 10
-2~10 * 10
-2Pa, DC voltage are 500~600V, and electric current is 70~100A, and sedimentation time is 200~300s, and the thickness of Al layer is 100~200nm;
5. in vacuum chamber, feed purity and be 99.95% argon gas, oxygen and nitrogen, open the titanium target, depositing TiN Ox layer on matrix, wherein argon flow amount is 50~100sccm, N
2Flow is 90~200sccm, O
2Flow is 100~200sccm, and air pressure is 0.1~0.2Pa, and DC voltage is 400~500V, and electric current is 35~45A, and the time is 20~30min, and the thickness of TiNOx layer is 100~200nm;
6. in vacuum chamber, feed purity and be 99.95% argon gas and oxygen, open silicon target, on matrix, deposit SiO
2Layer, wherein argon flow amount is 50~100sccm, O
2Flow is 100~200sccm, and air pressure is 0.2~0.3Pa, and DC voltage is 400~500V, and electric current is 35~40A, and the time is 10~15min, SiO
2The thickness of layer is 60~100nm.
The preparation method of described high-performance multilayer composite solar selective absorption coating, the steps include: step 3. and step also include step between 5. 4. to feed purity in vacuum chamber be 99.95% argon gas, open the titanium target, depositing Ti layer on matrix, wherein argon flow amount is 100~200sccm, and air pressure is 5.0 * 10
-2~10 * 10
-2Pa, DC voltage are 500~800V, and electric current is 30~40A, and sedimentation time is 200~300s; In vacuum chamber, feed purity then again and be 99.95% argon gas and acetylene, open the titanium target, depositing Ti C layer on matrix, wherein argon flow amount is 100~200sccm, C
2H
2Flow is 100~200sccm, and air pressure is 5 * 10
-2~10 * 10
-2Pa, DC voltage are 600~700V, and electric current is 30~40A, and the time is 200~300s, and the thickness of Ti+TiC layer is 50~100nm.
The preparation method of described high-performance multilayer composite solar selective absorption coating, its step preliminary treatment described in 1. is the high-pressure ion cleaning, charges into nitrogen, pressure 2~5Pa, voltage bombardment 2000~3500V, electric current 2~4A.
The invention has the beneficial effects as follows: the sunshine absorptivity of (1) multilayer composite solar selective absorption coating of the present invention is up to 90~95%, and infrared emittance is 6%.(2) high-performance multilayer composite solar selective absorption coating of the present invention has one deck Ti+TiC stabilized zone between reflecting layer and absorbed layer, this layer can significantly improve coating's adhesion, because TiC has high temperature resistant and antioxygenic property, therefore can significantly improve the corrosion resistance and the high temperature resistant property of coating simultaneously.(3) high-performance multilayer composite solar selective absorption coating of the present invention by the accurate control of each individual layer component and thickness, can significantly improve the heat-absorption properties of coating by four-layer structure, especially can significantly reduce the infrared emittance of coating.(4) high-performance multilayer composite solar selective absorption coating of the present invention can be used on the thermal-collecting tube of trough type solar power generation, on the thermal-collecting tube of CPC formula flat-plate solar collector and on the heat-collecting plate core of ordinary flat solar thermal collector.
The specific embodiment
Below in conjunction with embodiment principle of the present invention and feature are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1: a kind of high-performance multilayer composite solar selective absorption coating, and include and on matrix 1, be sequentially with far-infrared reflection layer 2, compound heat absorption layer 4 and anti-oxidant and antireflection layer 5, far-infrared reflection layer 2 is the Al layer of sputtering sedimentation on matrix 1; Compound heat absorption layer 4 is the TiNOx layer of sputtering sedimentation on far-infrared reflection layer 2, and anti-oxidant and antireflection layer 5 is the SiO of sputtering sedimentation on compound heat absorption layer 4
2Layer.Described matrix 1 is phosphorized copper band or oxygen-free copper stripe or aluminium strip.The thickness of described far-infrared reflection layer 2 is 100~120nm.The thickness of described compound hot coefficient layer 4 is 100~120nm.Described anti-oxidant and thickness antireflection layer 5 is 60~70nm.
Embodiment 2: a kind of high-performance multilayer composite solar selective absorption coating, and include and on matrix 1, be sequentially with far-infrared reflection layer 2, compound heat absorption layer 4 and anti-oxidant and antireflection layer 5, far-infrared reflection layer 2 is the Al layer of sputtering sedimentation on matrix 1; Compound heat absorption layer 4 is the TiNOx layer of sputtering sedimentation on far-infrared reflection layer 2, and anti-oxidant and antireflection layer 5 is the SiO of sputtering sedimentation on compound heat absorption layer 4
2Layer.Described matrix 1 is phosphorized copper band or oxygen-free copper stripe or aluminium strip.The thickness of described far-infrared reflection layer 2 is 120~170nm.The thickness of described compound hot coefficient layer 4 is 120~170nm.Described anti-oxidant and thickness antireflection layer 5 is 70~90nm.
Embodiment 3: a kind of high-performance multilayer composite solar selective absorption coating, and include and on matrix 1, be sequentially with far-infrared reflection layer 2, compound heat absorption layer 4 and anti-oxidant and antireflection layer 5, far-infrared reflection layer 2 is the Al layer of sputtering sedimentation on matrix 1; Compound heat absorption layer 4 is the TiNOx layer of sputtering sedimentation on far-infrared reflection layer 2, and anti-oxidant and antireflection layer 5 is the SiO of sputtering sedimentation on compound heat absorption layer 4
2Layer.Described matrix 1 is phosphorized copper band or oxygen-free copper stripe or aluminium strip.The thickness of described far-infrared reflection layer 2 is 170~200nm.The thickness of described compound hot coefficient layer 4 is 170~200nm.Described anti-oxidant and thickness antireflection layer 5 is 90~100nm.
Embodiment 4: a kind of high-performance multilayer composite solar selective absorption coating also includes between far-infrared reflection layer 2 and compound heat absorption layer 4 and is provided with stabilized zone 3; Stabilized zone 3 is the Ti+TiC layer of sputtering sedimentation on far-infrared reflection layer 2.The thickness of described stabilized zone 3 is 50~60nm.All the other are identical with embodiment 1.
Embodiment 5: a kind of high-performance multilayer composite solar selective absorption coating also includes between far-infrared reflection layer 2 and compound heat absorption layer 4 and is provided with stabilized zone 3; Stabilized zone 3 is the Ti+TiC layer of sputtering sedimentation on far-infrared reflection layer 2.The thickness of described stabilized zone 3 is 60~80nm.All the other are identical with embodiment 1.
Embodiment 6: a kind of high-performance multilayer composite solar selective absorption coating also includes between far-infrared reflection layer 2 and compound heat absorption layer 4 and is provided with stabilized zone 3; Stabilized zone 3 is the Ti+TiC layer of sputtering sedimentation on far-infrared reflection layer 2.The thickness of described stabilized zone 3 is 80~100nm.All the other are identical with embodiment 1.
Embodiment 7: a kind of preparation method of high-performance multilayer composite solar selective absorption coating the steps include:
1. will carry out pretreated matrix and pack in the horizontal magnetron sputtering coater, and the vacuum of the vacuum chamber of horizontal magnetron sputtering coater will be evacuated to 2.0 * 10
-2~9 * 10
-2Pa.Described preliminary treatment is the high-pressure ion cleaning, charges into nitrogen, pressure 2~5Pa, voltage bombardment 2000~2800V, electric current 2~4A.
2. feed purity and be 99.95% argon gas in vacuum chamber, making vacuum is 6.5 * 10
-2~9.0 * 10
-2Pa connects the negative DC voltage bombardment and cleans matrix 4min in argon gas atmosphere, remove matrix surface impurity, the activation matrix surface.
3. feed purity and be 99.95% argon gas in vacuum chamber, open the aluminium target, go up the depositing Al layer at matrix (1), wherein argon flow amount is 100~150sccm, and air pressure is 6 * 10
-2~10 * 10
-2Pa, DC voltage are 500~540V, and electric current is 70~80A, and sedimentation time is 200~240s, and the thickness of Al layer is 100~130nm.
5. in vacuum chamber, feed purity and be 99.95% argon gas, oxygen and nitrogen, open the titanium target, depositing TiN Ox layer on matrix, wherein argon flow amount is 50~60sccm, N
2Flow is 90~120sccm, O
2Flow is 100~120sccm, and air pressure is 0.1~0.2Pa, and DC voltage is 400~450V, and electric current is 35~38A, and the time is 20~22min, and the thickness of TiNOx layer is 100~120nm.
6. in vacuum chamber, feed purity and be 99.95% argon gas and oxygen, open silicon target, on matrix, deposit SiO
2Layer, wherein argon flow amount is 50~60sccm, O
2Flow is 100~120sccm, and air pressure is 0.2~0.3Pa, and DC voltage is 400~450V, and electric current is 35~40A, and the time is 10~12min, SiO
2The thickness of layer is 60~70nm.
Embodiment 8: a kind of preparation method of high-performance multilayer composite solar selective absorption coating the steps include:
1. will carry out pretreated matrix and pack in the horizontal magnetron sputtering coater, and the vacuum of the vacuum chamber of horizontal magnetron sputtering coater will be evacuated to 9 * 10
-2~2.0 * 10
-3Pa.Described preliminary treatment is the high-pressure ion cleaning, charges into nitrogen, pressure 2~5Pa, voltage bombardment 2800~3200V, electric current 2~4A.
2. feed purity and be 99.95% argon gas in vacuum chamber, making vacuum is 6.5 * 10
-2~9.0 * 10
-2Pa connects the negative DC voltage bombardment and cleans matrix 5min in argon gas atmosphere, remove matrix surface impurity, the activation matrix surface.
3. feed purity and be 99.95% argon gas in vacuum chamber, open the aluminium target, go up the depositing Al layer at matrix (1), wherein argon flow amount is 150~220sccm, and air pressure is 6 * 10
-2~10 * 10
-2Pa, DC voltage are 540~560V, and electric current is 80~90A, and sedimentation time is 240~280s, and the thickness of Al layer is 130~160nm.
5. in vacuum chamber, feed purity and be 99.95% argon gas, oxygen and nitrogen, open the titanium target, depositing TiN Ox layer on matrix, wherein argon flow amount is 60~80sccm, N
2Flow is 120~150sccm, O
2Flow is 120~150sccm, and air pressure is 0.1~0.2Pa, and DC voltage is 450~480V, and electric current is 38~42A, and the time is 22~26min, and the thickness of TiNOx layer is 120~160nm.
6. in vacuum chamber, feed purity and be 99.95% argon gas and oxygen, open silicon target, on matrix, deposit SiO
2Layer, wherein argon flow amount is 60~80sccm, O
2Flow is 120~160sccm, and air pressure is 0.2~0.3Pa, and DC voltage is 450~480V, and electric current is 35~40A, and the time is 12~14min, SiO
2The thickness of layer is 70~90nm.
Embodiment 9: a kind of preparation method of high-performance multilayer composite solar selective absorption coating the steps include:
1. will carry out pretreated matrix and pack in the horizontal magnetron sputtering coater, and the vacuum of the vacuum chamber of horizontal magnetron sputtering coater will be evacuated to 2.0 * 10
-3~8.0 * 10
-3Pa.Described preliminary treatment is the high-pressure ion cleaning, charges into nitrogen, pressure 2~5Pa, voltage bombardment 3200~3500V, electric current 2~4A.
2. feed purity and be 99.95% argon gas in vacuum chamber, making vacuum is 6.5 * 10
-2~9.0 * 10
-2Pa connects the negative DC voltage bombardment and cleans matrix 6min in argon gas atmosphere, remove matrix surface impurity, the activation matrix surface.
3. feed purity and be 99.95% argon gas in vacuum chamber, open the aluminium target, go up the depositing Al layer at matrix (1), wherein argon flow amount is 220~300sccm, and air pressure is 6 * 10
-2~10 * 10
-2Pa, DC voltage are 560~600V, and electric current is 90~100A, and sedimentation time is 280~300s, and the thickness of Al layer is 160~200nm.
5. in vacuum chamber, feed purity and be 99.95% argon gas, oxygen and nitrogen, open the titanium target, depositing TiN Ox layer on matrix, wherein argon flow amount is 80~100sccm, N
2Flow is 150~200sccm, O
2Flow is 150~200sccm, and air pressure is 0.1~0.2Pa, and DC voltage is 480~500V, and electric current is 42~45A, and the time is 26~30min, and the thickness of TiNOx layer is 160~200nm.
6. in vacuum chamber, feed purity and be 99.95% argon gas and oxygen, open silicon target, on matrix, deposit SiO
2Layer, wherein argon flow amount is 80~100sccm, O
2Flow is 160~200sccm, and air pressure is 0.2~0.3Pa, and DC voltage is 480~500V, and electric current is 35~40A, and the time is 14~15min, SiO
2The thickness of layer is 90~100nm.
Embodiment 10: a kind of preparation method of high-performance multilayer composite solar selective absorption coating, the steps include: step 3. and step also include step between 5. 4. to feed purity in vacuum chamber be 99.95% argon gas, open the titanium target, depositing Ti layer on matrix, wherein argon flow amount is 100~120sccm, and air pressure is 5.0 * 10
-2~10 * 10
-2Pa, DC voltage are 500~580V, and electric current is 30~35A, and sedimentation time is 200~240s; In vacuum chamber, feed purity then again and be 99.95% argon gas and acetylene, open the titanium target, depositing Ti C layer on matrix, wherein argon flow amount is 100~120sccm, C
2H
2Flow is 100~120sccm, and air pressure is 5 * 10
-2~10 * 10
-2Pa, DC voltage are 600~620V, and electric current is 30~35A, and the time is 200~220s, and the thickness of Ti+TiC layer is 50~60nm.All the other steps are with embodiment 7.
Embodiment 11: a kind of preparation method of high-performance multilayer composite solar selective absorption coating, the steps include: step 3. and step also include step between 5. 4. to feed purity in vacuum chamber be 99.95% argon gas, open the titanium target, depositing Ti layer on matrix, wherein argon flow amount is 120~160sccm, and air pressure is 5.0 * 10
-2~10 * 10
-2Pa, DC voltage are 580~680V, and electric current is 35~38A, and sedimentation time is 240~280s; In vacuum chamber, feed purity then again and be 99.95% argon gas and acetylene, open the titanium target, depositing Ti C layer on matrix, wherein argon flow amount is 120~160sccm, C
2H
2Flow is 120~160sccm, and air pressure is 5 * 10
-2~10 * 10
-2Pa, DC voltage are 620~660V, and electric current is 35~38A, and the time is 220~260s, and the thickness of Ti+TiC layer is 60~80nm.All the other steps are with embodiment 8.
Embodiment 12: a kind of preparation method of high-performance multilayer composite solar selective absorption coating, the steps include: step 3. and step also include step between 5. 4. to feed purity in vacuum chamber be 99.95% argon gas, open the titanium target, depositing Ti layer on matrix, wherein argon flow amount is 160~200sccm, and air pressure is 5.0 * 10
-2~10 * 10
-2Pa, DC voltage are 680~800V, and electric current is 38~40A, and sedimentation time is 280~300s; In vacuum chamber, feed purity then again and be 99.95% argon gas and acetylene, open the titanium target, depositing Ti C layer on matrix, wherein argon flow amount is 160~200sccm, C
2H
2Flow is 160~200sccm, and air pressure is 5 * 10
-2~10 * 10
-2Pa, DC voltage are 660~700V, and electric current is 38~40A, and the time is 260~300s, and the thickness of Ti+TiC layer is 80~100nm.All the other steps are with embodiment 9.
Embodiment 13: a kind of preparation method of high-performance multilayer composite solar selective absorption coating is characterized in that step is:
1. will carry out pretreated matrix and pack in the magnetron sputtering coater of bedroom, and the vacuum of the vacuum chamber of bedroom magnetron sputtering coater will be evacuated to 2.0 * 10
-2~8.0 * 10
-3Described preliminary treatment is the high-pressure ion cleaning, charges into nitrogen, pressure 2~5Pa, voltage bombardment 3200~3500V, electric current 2~4A.
2. feed purity and be 99.95% argon gas in vacuum chamber, making vacuum is 6.5 * 10
-2~9.0 * 10
-2Pa connects the negative DC voltage bombardment and cleans matrix 5min in argon gas atmosphere, remove matrix surface impurity, the activation matrix surface;
3. in vacuum chamber, feed purity and be 99.95% argon gas, play the aluminium target, depositing Al layer on matrix, wherein the Ar flow is 260sccm, air pressure is 6.5 * 10
-2Pa, DC voltage are 580V, and electric current is 100A, and sedimentation time is 300s, and the thickness of Al layer is 100~200nm;
4. in vacuum chamber, feed purity and be 99.95% argon gas, play the titanium target, depositing Ti layer on matrix, wherein the Ar flow is 170sccm, air pressure is 7.5 * 10
-2Pa, DC voltage are 640V, and electric current is 35A, and sedimentation time is 300s; In vacuum chamber, feed purity then and be 99.95% argon gas and acetylene, play the titanium target, depositing Ti C layer on matrix, wherein the Ar flow is 170sccm, C
2H
2Flow is 120sccm, and air pressure is 5.7 * 10
-2Pa, DC voltage are 660V, and electric current is 29A, and the time is 300s, and the thickness of Ti+TiC layer is 50~100nm;
5. in vacuum chamber, feed purity and be 99.95% argon gas, oxygen and nitrogen, play the titanium target, depositing TiN Ox layer on matrix, wherein the Ar flow is 60sccm, N
2Flow is 90sccm, O
2Flow is 100sccm, and air pressure is 0.11Pa, and DC voltage is 440~490V, and electric current is 37A, and the time is 30min, and the thickness of TiNOx layer is 100~200nm;
6. in vacuum chamber, feed purity and be 99.95% argon gas and oxygen, play silicon target, on matrix, deposit SiO
2Layer, wherein the Ar flow is 60sccm, O
2Flow is 120sccm, and air pressure is 0.2Pa, and DC voltage is 400~450V, and electric current is 39A, and the time is 10min, SiO
2The thickness of layer is 60~100nm.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.