CN103267379B - Full nitride weather-resisting photo-thermal coating and preparing method thereof - Google Patents
Full nitride weather-resisting photo-thermal coating and preparing method thereof Download PDFInfo
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- CN103267379B CN103267379B CN201310202827.6A CN201310202827A CN103267379B CN 103267379 B CN103267379 B CN 103267379B CN 201310202827 A CN201310202827 A CN 201310202827A CN 103267379 B CN103267379 B CN 103267379B
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Abstract
The invention relates to a full nitride weather-resisting photo-thermal coating and a preparing method thereof. Copper or aluminum or ferritic stainless steel serves as base material, and the full nitride weather-resisting photo-thermal coating sequentially comprises a first absorption sub-layer, a second absorption sub-layer and a silicon nitride anti-reflection layer. Firstly, argon gas and nitrogen gas are injected, the copper or aluminum or ferritic stainless steel serves as the base material, TiAl serves as target material, and direct current sputtering is performed; then the base material is located between the TiAl target material and Si target material, and co-sputtering is performed; finally, the base material right faces the Si target material, and sputtering is performed. According to the full nitride weather-resisting photo-thermal coating and the preparing method thereof, an absorption layer is composed of the two absorption sub-layers, and manufacturing processes are simpler and more convenient to achieve than those of multi-layer (greater than or equal to 3) gradient structures in traditional film systems. An oxygen-free coating system is achieved, weather resistance is good, and therefore the full nitride weather-resisting photo-thermal coating is suitable for being popularized for existing vacuum coating equipment in the domestic solar energy photo-thermal industry, capable of being used for manufacturing flat plate type solar heat collection panel cores, and good in application prospect.
Description
Technical field
The present invention relates to solar energy full nitride weatherability photo-thermal coating and preparation method thereof, belong to composite film material preparing technical field.
Background technology
Solar energy optical-thermal coating for selective absorption is the Core Feature part for absorbing solar energy in solar thermal collector.It is one group of thin film system with sandwich construction, and as shown in Figure 1, it comprises the infrared external reflection bottom 2, absorbed layer 3 and the anti-reflection layer 4 that are attached to base material 1 surface.
Solar energy is changed into heat energy by solar selectively absorbing coating, and the temperature of coating and base material raises thus, and with infrared thermal wave form to environmental radiation energy.In order to improve energy gain and loss ratio, require that this coating system fully can absorb the part of concentration of energy in the solar spectral that ground receives, simultaneously less to environmental radiation infrared thermal wave.This is the context request of selective absorbing.So-called " selective absorbing ", in the context of application, refer to that the light absorption of this coating system has spectrum selective, namely in solar energy spectrum wavelength 0.3--2.5 micrometer range, there is higher absorptance α value, there is low infrared emission in infrared range of spectrum than ε value simultaneously.Solar absorption is the most important light thermal property index of solar selectively absorbing coating system two than α and infrared emission than ε, wherein solar absorption depends on the selection of absorbed layer and anti-reflection layer than α, infrared emission depends primarily on the selection of infrared external reflection primer than ε, and is subject to the impact of absorbed layer.Usually, base material or its surface adopt the satisfied material for the requirement of infrared external reflection bottom and become a part for solar selectively absorbing coating system.
Up to now, for the sunshine in 0.3--2.5 micron wavelength range, the commercially available solar thermal collector adopting vacuum coating technology to prepare or solar selectively absorbing coating, its absorptance can reach about 0.93, and infrared emission ratio drops to less than 0.1.In practice, when the solar absorption of coating for selective absorption is than in the most high solar absorptance theoretical value of 0.92 to 0.96() between time, absorption efficiency has been difficult to the change with practical significance.
Utilize magnetron sputtering technology to prepare solar selectively absorbing coating, sequentially generally comprise following steps:
(1) adopt the infrared highly reflective metal base of tool, or by infrared for tool highly reflective metal deposition on base material (as stainless steel) surface, form infrared external reflection bottom;
(2) deposit absorbent layer on infrared external reflection bottom, injecting flow by continuously changing reacting gas, producing different absorption subgrades; The chemical composition of whole absorbed layer changes in gradient.
(3) on absorbed layer, deposit anti-reflection layer, be generally ceramic material (oxide or nitride).
Magnetron sputtering technique such as carries out in the vacuum chamber shown in Fig. 2, and wherein magnetic field is crossing with E-field normal, makes electronics cycloid motion of spinning in space move to anode (i.e. base material).In classical theory, electronics clashes into ar atmo on the way and causes ar atmo to split into argon ion and another free electron.Argon cation is bombarding cathode (i.e. target) under the effect of electromagnetic field.The cathodic metal particle deposition sputtered is on anode base material; The secondary electron sputtered adds electron motion and defines self-holding radiance electric discharge.The power supply of magnetron sputtering can use dc source, the pulse power, midfrequent AC power supply, radio-frequency power supply or combinationally use above-mentioned several power supply.
Can obtain diversified metallic film material by magnetically controlled DC sputtering technology, this technology uses inert gas (being generally argon gas) for sputtering medium.Can obtain diversified thin dielectric film or metal-non-metal composite film material by reaction magnetocontrol sputtering technology, these dielectric substances are that metal targets and active gases react and generate.Inert gas and active gases can inject vacuum chamber by air inlet pipe separately or after mixing.While sputter coating, maintain vacuum with vavuum pump.Gas inject flow is in units of sccm, and gas inject amount namely per minute gas volume in units of cubic centimetre at standard conditions calculates.In the existing vacuum coating equipment of domestic solar energy optical-thermal industry, generally obtain equipment vacuum by diffusion pump, diffusion pump machine oil is very easily oxidized, and then affects equipment vacuum situation.
In vacuum coating practice, must according to factor testing and measuring technology parameters such as the volume of vacuum chamber and shape, the vavuum pump pumping efficiency that can reach and vacuum coating power, to prepare satisfactory thin-film material.The main technologic parameters of adjustable comprises injection flow, the vacuum coating power and sputtering time etc. of various gas.Vacuum coating power is larger, and metal ion deposition is faster; Sputtering time is substantially only relevant to deposit thickness.When plated metal-nonmetallic composite, improve vacuum coating power, then need the injection flow correspondingly improving reacting gas to obtain specific metal and nonmetal ratio.But when power is excessive, reaction is unstable, can not obtain uniform thin-film material.
Summary of the invention
The object of this invention is to provide a kind of full nitride weatherability photo-thermal coating and preparation method thereof, this coating adopts double absorption layer structure, in preparation technology, is easy to regulation and control, good weatherability, be suitable for hot operation in vacuum or air, its solar absorption ratio is greater than 0.92, and infrared emission ratio is less than 0.1.
The technical scheme that the present invention takes is:
A kind of full nitride weatherability photo-thermal coating, using copper, aluminium or ferritic stainless steel as base material, comprise the first absorption subgrade, second successively and absorb subgrade, silicon nitride anti-reflection layer, first absorbs subgrade deposition 30-150nm, second absorbs subgrade deposition 30-150nm, second tenor absorbed in subgrade absorbs subgrade lower than first, and silicon nitride anti-reflection layer deposit thickness is 20-60nm.
Preferred ferritic stainless steel is as base material.
The preparation method of above-mentioned full nitride weatherability photo-thermal coating, comprises step as follows:
(1) using copper, aluminium or ferritic stainless steel as base material, take TiAl as target, the argon gas of flow 35-45sccm is injected in chamber, regulate chamber pressure at 0.3-0.6Pa, the flow that reinjects is the nitrogen of 2-5sccm, d.c. sputtering power 100-120w, base material is for target as sputter 8-12 minute, and target and substrate frame central shaft distance are 10cm;
(2) change substrate location, make base material between TiAl target and Si target two target, keep base material rotational velocity 10-20 rev/min simultaneously, changing logical nitrogen flow is 18-24sccm, TiAl target power is 100-120w, Si target power is 85-100w, cosputtering 12-18 minute;
(3) change substrate location, make base material just to Si target, target and substrate frame central shaft distance are 10cm, keep base material rotational velocity 10-20 rev/min, logical nitrogen flow is 18-24sccm, Si target power is 85-100w simultaneously, sputtering 13-18 minute, prepares anti-reflection layer.
Absorbed layer prepared by the present invention, absorbs subgrade by two and forms, more easy relative to multilayer (>=3) the gradient-structure production technology in conventional film system.This coating for selective absorption is the composite film material formed by titanium-aluminium alloy and nonmetal gas reaction sputtering sedimentation and titanium-aluminium alloy and nonmetal silicon cosputtering reactive deposition, and silicon and nonmetal gas reaction sputtering sedimentation form solar heat-collection plate core.Described nonmetal gas is nitrogen.Full nitride weatherability photo-thermal coating prepared by the present invention is anaerobic coating system, good weatherability, and be adapted at the existing vacuum coating equipment of domestic solar energy optical-thermal industry is promoted, can be used for preparing flat panel solar heat collecting plate core, application prospect is good.
Advantage of the present invention is:
(1) do not use acetylene gas preparing in coating procedure, but add silicide in the coating with silicon target, eliminate the potential safety hazard in preparation process, be suitable for large-scale production.
(2) coating prepared can tolerate the high-temperature baking up to 500 ° of C in an atmosphere, toasts after 2 hours, and coating morphology, composition and light thermal property thereof still keep well (absorb >=90%, launch <10%).Concrete outcome is shown in Fig. 5,6 and table 1; 250cm in Fig. 6
-1place peak by Ti and Al ion at 250-350cm
-1acoustic vibration in (LA and TA) region causes, 635cm
-1place peak by N ion at 400-650cm
-1vibration of optical in (LO and TO) region causes.From Raman spectrum, coating is after 600 DEG C of heat treatment, and its composition does not have change substantially, and coating heat resistance is good.
Table 1: the change of coating absorptivity, emissivity before and after heatproof
Accompanying drawing explanation
Fig. 1 is existing full nitride weatherability photo-thermal coating structure;
Fig. 2 is magnetron sputtering apparatus;
Fig. 3 is the present invention's full nitride weatherability photo-thermal coating structure;
Fig. 4 sputters schematic diagram;
Fig. 5 TiAlN-TiAlSiN-Si
3n
4the SEM photo of coating; A (), without heat treatment and (b) 500 ° of C, toasts rear TiAlN-TiAlSiN-Si for 2 hours
3n
4the SEM photo of coating;
TiAlN-TiAlSiN-Si after Fig. 6 heat treatments at different
3n
4the Raman spectrum of coating; In figure, a-f spectral line is respectively the test of the Raman after without heat treatment, 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C heat treatments spectral line.
Wherein, 1 is base material, and 2 is infrared external reflection bottom, and 3 is that absorbed layer, 4 is for anti-reflection layer, 5 is air inlet, and 6 is circular magnetic control target, and 7 is substrate frame, and 8 is chip bench, 9 is copper, aluminium or ferrite stainless steel substrate, and 10, first absorbs subgrade, and 11, second absorbs subgrade, and 12 is silicon nitride anti-reflection layer.
Detailed description of the invention
Coating structure of the present invention as shown in Figure 3.Copper, aluminium or ferrite stainless steel substrate 9, first absorbs subgrade 10, second and absorbs subgrade 11 and silicon nitride anti-reflection layer 12.Major experimental equipment of the present invention is TSU-600 magnetic control film coating machines.This apparatus cavity structure as shown in Figure 2, air inlet 5, two circular magnetic control targets 6, substrate frame 7 and chip bench 8.Equipment adopts mechanical pump to take out low vacuum in magnetron sputtering chamber, then takes out Gao Zhenzhi by molecular pump and be greater than 10
-4pa.
Embodiment 1
The preparation method of full nitride weatherability photo-thermal coating, comprises step as follows:
(1) in chamber, the argon gas of flow 35sccm is injected by air inlet 5, conditioning equipment flow-limiting valve makes chamber pressure at 0.3Pa, the flow that reinjects is the nitrogen of 2sccm, d.c. sputtering power 100w, stainless steel is selected to be substrate, take TiAl as target, base material was for target as sputter about 10 minutes, and preparation Ti-Al-N film absorbs subgrade as first.
(2) regulate revoluting motor to change substrate location, make base material between two targets.Open spinning motor, base material rotational velocity is 10 revs/min simultaneously.Under above-mentioned aeration condition, change nitrogen flow be 18sccm, TiAl target power be 100w, Si target power is 85w, and cosputtering about 15 minutes, preparation Ti-Al-Si-N film absorbs subgrade as second.
(3) again regulate revoluting motor, make base material just to Si target, keep base material rotational velocity 20 revs/min simultaneously.Maintenance walks aeration status, and Si target power is 100w, sputters about 15 minutes, preparation Si
xn
yas anti-reflection layer.
Embodiment 2
The preparation method of full nitride weatherability photo-thermal coating, comprises step as follows:
(1) in chamber, the argon gas of flow 45sccm is injected by air inlet 5, conditioning equipment flow-limiting valve makes chamber pressure at 0.6Pa, the flow that reinjects is the nitrogen of 5sccm, d.c. sputtering power 120w, stainless steel is selected to be substrate, take TiAl as target, base material was for target as sputter about 10 minutes, and preparation Ti-Al-N film absorbs subgrade as first.
(2) regulate revoluting motor to change substrate location, make base material between two targets.Open spinning motor, base material rotational velocity is 20 revs/min simultaneously.Under above-mentioned aeration condition, change nitrogen flow be 24sccm, TiAl target power be 120w, Si target power is 100w, and cosputtering about 15 minutes, preparation Ti-Al-Si-N film absorbs subgrade as second.
(3) again regulate revoluting motor, make base material just to Si target, keep base material rotational velocity 10 revs/min simultaneously.Maintenance walks aeration status, and Si target power is 85w, sputters about 15 minutes, preparation Si
xn
yas anti-reflection layer.
Claims (1)
1. the preparation method of a full nitride weatherability photo-thermal coating, this full nitride weatherability photo-thermal coating is using ferritic stainless steel as base material, comprise the first absorption subgrade, second successively and absorb subgrade, silicon nitride anti-reflection layer, first absorption subgrade is Ti-Al-N film, deposit thickness is 30-150nm, second absorption subgrade is Ti-Al-Si-N film, deposit thickness is 30-150nm, second tenor absorbed in subgrade absorbs subgrade lower than first, and silicon nitride anti-reflection layer deposit thickness is 20-60nm; Preparation method comprises the steps:
(1) using ferritic stainless steel as base material, take TiAl as target, in chamber, inject the argon gas of flow 35-45sccm, regulate chamber pressure at 0.3-0.6Pa, the flow that reinjects is the nitrogen of 2-5sccm, d.c. sputtering power 100-120w, and base material is for target as sputter 8-12 minute; Target and substrate frame central shaft distance are 10cm; Preparation Ti-Al-N film absorbs subgrade as first;
(2) change substrate location, make base material between TiAl target and Si target two target, keep base material rotational velocity 10-20 rev/min simultaneously, changing logical nitrogen flow is 18-24sccm, TiAl target power is 100-120w, Si target power is 85-100w, cosputtering 12-18 minute; Preparation Ti-Al-Si-N film absorbs subgrade as second;
(3) change substrate location, make base material just to Si target, target and substrate frame central shaft distance are 10cm, keep base material rotational velocity 10-20 rev/min, logical nitrogen flow is 18-24sccm, Si target power is 85-100w simultaneously, sputtering 13-18 minute, preparation Si
xn
yas anti-reflection layer.
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| DE102008010199A1 (en) * | 2008-02-20 | 2009-08-27 | Schott Ag | Radiation-selective absorber coating, absorber tube and method for its production |
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Effective date of registration: 20201225 Address after: 246001 e-commerce Industrial Park, NO.48 Renmin Road, Yingjiang District, Anqing City, Anhui Province Patentee after: Wang Zhao Address before: 250061 Qianfo campus, Shandong University, 17923 Jingshi Road, Lixia District, Jinan City, Shandong Province Patentee before: OuYang Jun |
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Effective date of registration: 20211009 Address after: 271000 high end talent entrepreneurship base in the middle of Nantianmen street, high tech Zone, Tai'an City, Shandong Province Patentee after: Taian Zhongquan Information Technology Co.,Ltd. Address before: 246001 e-commerce Industrial Park, No. 48, Renmin Road, Yingjiang District, Anqing City, Anhui Province Patentee before: Wang Zhao Effective date of registration: 20211009 Address after: 271000 China Taishan high-end talent entrepreneurship base in the middle of Nantianmen street, development zone, Tai'an City, Shandong Province Patentee after: Taian Taishan Technology Co.,Ltd. Address before: 271000 high end talent entrepreneurship base in the middle of Nantianmen street, high tech Zone, Tai'an City, Shandong Province Patentee before: Taian Zhongquan Information Technology Co.,Ltd. |