CN106500374B - A kind of biphase composite solar absorber coatings and manufacturing method - Google Patents
A kind of biphase composite solar absorber coatings and manufacturing method Download PDFInfo
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- CN106500374B CN106500374B CN201610931796.1A CN201610931796A CN106500374B CN 106500374 B CN106500374 B CN 106500374B CN 201610931796 A CN201610931796 A CN 201610931796A CN 106500374 B CN106500374 B CN 106500374B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/25—Coatings made of metallic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/30—Auxiliary coatings, e.g. anti-reflective coatings
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- 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 present invention discloses a kind of biphase composite solar absorber coatings and manufacturing method, the coating includes that infrared high reflection layer, main absorbed layer, secondary absorbed layer and anti-reflection layer are successively arranged in substrate, substrate is cleaned with chemical method and is placed in vacuum drying oven, then it vacuumizes, high flow capacity nitrogen is passed through into furnace, Ti target is opened, in the infrared high reflection layer of substrate deposition TiN；It is then shut off Ti target, AlTi alloys target is opened, is passed through the oxygen and nitrogen of low discharge, in low oxygen and low nitrogen environment, the main absorbed layer of biphase structure is deposited on infrared high reflection layer；Increase nitrogen flow, in the high nitrogen environment of hypoxemia, the secondary absorbed layer of single phase nano structure is deposited on main absorbed layer；Nitrogen is finally closed, anti-reflection layer is deposited under the conditions of high oxygen concentration, closes heater, natural cooling obtains the Ti-Al-O-N biphase composite solar absorber coatings of four-layer structure, coating absorption efficiency produced by the present invention is good, and energy conversion efficiency is high, has larger application value.
Description
Technical field
The sun light-absorbing coating and preparation method thereof that the present invention relates to a kind of for sea water desalination, and in particular to Yi Zhongshuan
Mutually nano combined solar energy absorbing coating and manufacturing method, belong to thin film materials art.
Background technique
In solar energy heat utilization technology, first have to convert solar radiation into thermal energy.In this course, it mainly adopts
With solar energy absorbing coating, which absorbs the ultraviolet most of light wave near infrared range of solar spectrum, and in infrared waves
Duan Ze is to penetrate, and coating deposition can be reflected away infrared waves using the characteristic of its high infrared reflection on the metallic substrate.This
The purpose of sample design is to avoid bringing high thermal emissivity because coating absorbs infrared waves as far as possible, causes heat-energy losses, especially
, with the raising of coating duty temperature, this Some thermal heat loss is more serious for it.Therefore the quality of the performance of coating determines solar energy
The height of hot transfer efficient.
In solar energy absorbing coating field, most commonly used is cermet absorber coatings.This coating is by nanometer ruler
The metallic particles of degree is embedded on the matrix of metal-oxide dielectric and constitutes, and has strong absorption to solar radiation；
One layer of anti-reflective coating is deposited on the coating layer, its absorptance can be made to reach 0.9 or more.Such as in household solar water system
System, what is generallyd use is Al-AlN composite absorption coating, which is deposited on the high reflective substrate such as copper or aluminium, can make to absorb
Rate is up to 0.95, and slin emissivity is down to 0.05.But since the fusing point of aluminium is low, it is easy diffusion at high temperature, and be easy by water
Vapour corrosion, causes its performance to decline, and limiting the coating can only (100 DEG C) use at low temperature.In order to be utilized in high temperature field
The metal-free ceramic-type solar energy absorbing coating material of solar energy, a series of new has been developed that, such as patent of invention
A kind of solar energy high temperature that CN102734956A is protected selects heat absorbing coating.The technical solution is first on heat collecting element substrate
Deposited metal (CrAl, NiAl, SiAl) infrared reflecting layer, then it is sequentially depositing the cermet absorbed layer, most of multilayer ingredient gradual change
Aluminum oxide anti-reflection layer is deposited afterwards.The emissivity of absorptivity and 0.04-0.08 of this coating with 0.93-0.96, photo-thermal
Conversion performance is very superior；After being heat-treated 70 hours in 400 DEG C of air, absorbent properties are but declined, and transmitting is increased
Add.
Metal-free ceramic-type absorber coatings mostly use magnetron sputtering technique to prepare, and the coating layer thickness of technology preparation can be controlled
System can carry out the preparation of coating with binding isotherm calculated result.Using effective media theory and computer modeling technique, pass through number
Value optimization can calculate optical parameter and thickness that specific coating material obtains optimal selection absorbability, then utilize the skill
The controllable advantage of art thickness prepares coating.The absorptance of the coating of this method preparation is higher than 0.9, and emissivity is lower than 0.1, true
There is preferable thermal stability in the air；Low-temperature solar energy utilizes field realization commercialization in solar water heating system and other
Using.However this method is mostly in atomic state since the ionization level of sputter metal atoms is low, the energy itself carried is low,
Causing the coating deposited by this method, there are two apparent defects.First is that the binding force with substrate is low, the target sputtered out
Atom neutral itself, loose in conjunction with substrate, mostly physical adherence, therefore binding force is low.Second is that due to the energy of atom
Low, the cavity easy to form during coatings growth, these cavities can become the diffusion admittance of oxygen, under the high temperature conditions will
Metal component oxidation, makes coating lose absorbent properties.
Especially in some novel solar seawater desalination systems.It is right due to the temperature cycles for running-resting round the clock
Absorber coatings and the higher requirement of the adhesive force of substrate.In addition, system work is in the steam ambient of high temperature, absorber coatings are not only
High temperature oxidation resisting is wanted, long-term seawater corrosion resistance is also needed.Arc ion plating (aip) is a kind of physical gas phase deposition technology, due to having
Pollution-free, the features such as ionization level is high, deposition rate is fast, ion energy is big, at low cost, be the main preparation skill of current hard coat
Art.The ionization level of the metallic atom of arc evaporation can prepare fine and close coating material up to 90% or more；Coating is realized simultaneously
With the chemical bonding of base material, adhesive force is improved, meets seawater desalination system to the performance requirement of solar energy absorbing coating.
Summary of the invention
The present invention is intended to provide a kind of efficient sunlight absorber coatings and preparation method thereof for sea water desalination.Using big
The characteristics of power cathodic arc ion plating technology plasma high ionization level, the biphase composite absorption for preparing compact structure apply
Layer.And make the coating that there is good inoxidizability and sea water corrosion resistant, while can be well combined with base material, it is full
Sufficient solar seawater desalination application conditions.And provide the preparation method of the coating material.
Absorber coatings technical solution provided by the present invention is:
A kind of biphase composite solar absorber coatings, it is characterised in that: infrared high reflection is successively arranged in substrate
Layer, main absorbed layer, secondary absorbed layer and anti-reflection layer, wherein substrate is made of the porous material of hydrophily and seawater corrosion resistance, red
Outer high reflection layer is the transition metal nitride material of seawater corrosion resistance, and main absorbed layer is two kinds of gold with different optical properties
Category receives nano-particle material and inlays and form in the dielectric, and secondary absorbed layer inlays electricity by single-phase transition metal nitride nano material
It being formed in medium, anti-reflection layer is low refractive index material layer, the overall reflectivity of coating is advantageously reduced by coating grading structure,
Improve absorptivity.
As an improvement, the porosity of porous material that substrate is made, between 20-80%, pore size is that 0.1-10 is micro-
Between rice, substrate thickness is being greater than or equal to 1 millimeter；Infrared high reflection layer is TiN or ZrN layers with a thickness of 0.1-1 microns；It is main
Absorbed layer is embedded in electric Jie by the transition metal nanoparticles and transition metal nitride nano material of two kinds of different optical properties
Formed in matter, wherein transition metal nanoparticles to the absorption peak of solar radiation between 200-400 nanometers, transitional metal nitride
For the absorption peak of object nano material between 500-700 nanometers, the ratio of two kinds of material nano crystalline substances is adjustable between 0-1, two kinds of materials
3-15 nanometers of nano particle size of material, the coating layer thickness of main absorbed layer is at 30-100 nanometers；The single-phase transition metal of secondary absorbed layer
3-10 nanometers of nitride nano-material granular size, 30-100 nanometers of coating layer thickness；The Refractive Index of Material of anti-reflection layer is 1.8-2,
50-100 nanometers of its thickness.
A kind of above-mentioned biphase composite solar absorber coatings method of manufacture, which comprises the following steps:
Step 1: getting out the equipment for manufacturing the biphase composite solar absorber coatings, which includes having furnace
The vacuum drying oven of door is equipped with rotatable work rest in vacuum drying oven, set around work rest in vacuum drying oven there are two symmetrical plus
Hot device, vacuum drying oven are respectively arranged on the left side and the right side AlTi alloys target and Ti target；
Step 2: the cleaning of base material, the porous material of substrate will be made successively in acetone, alcohol and deionized water
Each ultrasonic cleaning 8-30min, which is placed in drier, dries, and is then loaded into vacuum drying oven on work rest, closes fire door；
Step 3: the acquisition of vacuum environment, by vaccum-pumping equipment by the environment that is evacuated in vacuum drying oven；
Step 4: starting device, allows work rest to rotate with matrix, Ti target is then opened, is discharged using large power electric arc
Technology is evaporated Ti ion from Ti target with electric current, in vacuum drying oven in be passed through high flow capacity nitrogen, TiN is formed on the substrate
Infrared high reflection layer；
Step 5: closing Ti target, opening AlTi alloys target and adjusting electric current, low discharge oxygen is passed through into vacuum drying oven, and
Nitrogen is adjusted to low discharge, under low oxygen and low nitrogen environment, the main absorbed layer of biphase structure is deposited on infrared high reflection layer；
Step 6: increasing the flow for being passed through nitrogen in vacuum drying oven, under the high nitrogen environment of hypoxemia, deposited on main absorbed layer single-phase
The secondary absorbed layer of nanostructure；
Step 7: closing nitrogen stream meter, the oxygen flow being passed through in vacuum drying oven is increased, is sunk in high oxygen concentration condition
Product anti-reflection layer；
Step 8: preparation terminate, close AlTi alloys target and vacuum drying oven heater, then naturally cool to 100 DEG C with
Under, obtain the Ti-Al-O-N biphase composite solar absorber coatings of four-layer structure.
Preferably, the vaccum-pumping equipment of the vacuum drying oven includes mechanical pump and molecular pump, when being vacuumized in step 3,
Mechanical pump pumping is first passed through, after vacuum furnace pressure reaches 2pa or less, opening molecular pump will be evacuated, and will be pumped into vacuum drying oven
High vacuum system, until 8 × 10-4Pa or less.
Preferably, in the step 4, the arc discharge power of Ti target is 0.2-0.5 kilowatts, in vacuum drying oven in lead to
The flow for entering nitrogen is 200-500SCCM, and the revolving speed of work rest is set as 3-5rpm.Primarily to improving plasma intermediate ion
Energy, form coating and substrate and be chemically combined, improve binding force.
Preferably, the power of AlTi alloys target is 0.1-0.3 kilowatts in the step 5, it is passed through oxygen in vacuum drying oven
Flow be 10-30SCCM, the flow of low discharge nitrogen is 20-50SCCM, biphase structure main absorbed layer deposition after adjusting
Time is 1-3min.
Preferably, the power of AlTi alloys target is 0.1-0.3 kilowatts, nitrogen flow model after increase in the step 6
Enclosing is 60-100SCCM, and secondary absorbed layer sedimentation time is 1-3min.
Preferably, the power of AlTi alloys target is 0.1-0.3 kilowatts, the oxygen flow after increase in the step 7
For 200-500SCCM, anti-reflection layer sedimentation time is 1-3min.
The present invention is beneficial to being:
1) absorber coatings comprising biphase particle are used, coating is effectively widened to the absorption spectrum width of solar radiation, mentions
The absorptivity of high coating, and then improve photothermal conversion efficiency.
2) use cathodic arc ion plating technology, the plasma ionization level of the technology is high, and ion energy is high, make coating with
Base material is combined closely, not easily to fall off；High energy ion has effect of impact to coating simultaneously, during can eliminating coatings growth
Cavity, obtain the coating of compact structure, effectively improve the inoxidizability and sea water corrosion resistant of coating.
3) the technology coating deposition rate wants fast an order of magnitude with respect to magnetron sputtering technique, saves the time, reduces cost,
And meet the requirement of micro-nano hole substrate not plug-hole during the deposition process.
Detailed description of the invention
Fig. 1 is biphase composite solar absorber coatings structural schematic diagram；
Fig. 2 is the schematic diagram for manufacturing biphase composite solar absorber coatings equipment；
Fig. 3 is biphase composite solar absorber coatings reflectance spectrum figure；
In figure, 1- vacuum pumping opening, 2- work rest, 3-Ti target, 4- heater, 5- fire door, 6-AlTi alloys target, 7- vacuum
Room, 8- substrate, the infrared high reflection layer of 9-, the main absorbed layer of 10-, 11- absorbed layer, 12- anti-reflection layer.
Specific embodiment
Implement the device of the method for the present invention as shown in Fig. 2, device is the vacuum drying oven with fire door 5, vacuum drying oven furnace wall surrounds
Vacuum chamber 7,7 height of vacuum chamber are 0.5-1.5 meters, and volume is 50 × 50 × 50 centimetres.Fire door 5 is equipped with before vacuum chamber 7, with side
Just the handling of base material.Vacuum chamber 7 is equipped with vacuum pumping opening 1, and the vacuum suction device of vacuum drying oven is right by vacuum pumping opening 1
Vacuum chamber 7 is vacuumized, and vacuum suction device is made of mechanical pump and molecular pump, and ultimate vacuum can achieve 8 × 10-4Pa。
7 left and right sides furnace wall of vacuum chamber is respectively provided with the Ti target 3 of AlTi alloys target 6 and high-purity, the AlTi atomic ratio of AlTi alloys target 6
The target current of the Ti target 3 of 67:33, AlTi alloys target 6 and high-purity is adjustable in 20-170A.Vacuum drying oven is built-in, and there are two right
Claim the heater 4 of distribution, is used for hot donut 7.Work rest 2 can rotate counterclockwise, and revolving speed is adjustable in 1-5rpm, and
It is connected in back bias voltage.The furnace wall of vacuum drying oven is also provided with the multiple flues that can be passed through the working gas such as oxygen, nitrogen and argon gas
Road is equipped with mass flowmenter control by each gas pipeline and is passed through working gas uninterrupted.
As shown in Figure 1, being biphase composite solar absorber coatings structural schematic diagram of the present invention, including in substrate 8
It is successively arranged infrared high reflection layer 9, main absorbed layer 10, secondary absorbed layer 11 and anti-reflection layer 12, wherein substrate 8 is using hydrophily and resistance to
The porous material of seawater corrosion is made, transition metal nitride material of the infrared high reflection layer 9 using seawater corrosion resistance, main absorption
Layer 10 receives nano-particle material for two kinds of metals with different optical properties and inlays and form in the dielectric, secondary absorbed layer 11 by
Single-phase transition metal nitride nano material, which is inlayed in dielectric, to be formed, and anti-reflection layer 12 is low refractive index material layer, passes through coating
Grading structure advantageously reduces the overall reflectivity of coating, improves absorptivity.
The porosity of porous material that substrate 8 is made is between 20-80%, between 0.1-10 microns of pore size, base
8 thickness of bottom is being greater than or equal to 1 millimeter；
Infrared high reflection layer 9 is TiN or ZrN layers with a thickness of 0.1-1 microns, material of the infrared high reflection layer 9 than substrate 8
Pore size is slightly smaller, guarantees during the deposition process not plug-hole；
Main absorbed layer 10 by two kinds of different optical properties transition metal nanoparticles and transition metal nitride nanometer material
Material is inlayed to be formed in the dielectric, i.e., the absorption peak position of two kinds nano particles is different, and is in solar radiation 300-2500
In nanometer range, to widen the absorption spectra of coating；Wherein transition metal nanoparticles are to the absorption peak of solar radiation in visible light
Between inclined 200-400 nanometers of ultraviolet band, inclined infrared band 500-700 nanometers in visible light of transition metal nitride nano material
Between, the ratio of two kinds of material nano crystalline substances is adjustable between 0-1, and two kinds of material nanoparticle sizes are 3-15 nanometers equal, main absorption
The coating layer thickness of layer 10 is at 30-100 nanometers；
3-10 nanometers of single-phase transition metal nitride nano-grain size of secondary absorbed layer 11, coating layer thickness 30-100
Nanometer, nano particle mainly select transition metal nitride nano particle, cooperate main absorbed layer 10, form grading structure；
Anti-reflection layer 12 is low-index material, the material choosing according to used by main absorbed layer 10 and time absorbed layer 11
It takes, on the one hand thickness control plays antireflective, on the one hand protect primary and secondary absorbed layer not oxidized and extra large at 50-100 nanometers
Aqueous corrosion, the Refractive Index of Material of anti-reflection layer 12 are 1.8-2.
A kind of above-mentioned biphase composite solar absorber coatings method of manufacture, comprising the following steps:
Step 1: getting out the equipment for manufacturing the biphase composite solar absorber coatings, which includes having furnace
The vacuum drying oven of door is equipped with rotatable work rest 2 in vacuum drying oven, sets that there are two symmetrical in vacuum drying oven around work rest 2
Heater 4, vacuum drying oven are respectively arranged on the left side and the right side AlTi alloys target 6 and Ti target 3；
Step 2: the cleaning of base material, will make the porous material of substrate 8 successively in acetone, alcohol and deionized water
In be respectively cleaned by ultrasonic 8-30min and be placed in drier and dry, be then loaded into vacuum drying oven on work rest 2, close fire door 5；
Step 3: the acquisition of vacuum environment, by vaccum-pumping equipment by the environment that is evacuated in vacuum drying oven, the vacuum drying oven
Vaccum-pumping equipment include mechanical pump and molecular pump, when vacuumizing, first pass through mechanical pump pumping, when vacuum furnace pressure reach
After 2pa or less, opening molecular pump will be evacuated, and high vacuum system will be pumped into vacuum drying oven, until 8 × 10-4Pa or less；
Step 4: starting device, allows work rest 2 to rotate with matrix 8, the revolving speed of work rest 2 is set as 3-5rpm, then
Ti target 3 is opened, Ti ion is evaporated from Ti target with electric current using large power electric arc discharge technology, the electric arc of Ti target 3 is put
Electrical power is 0.2-0.5 kilowatts；It is 200-500SCCM (for mass flow unit, standard state that flow is passed through in vacuum drying oven
Ml/min) nitrogen, substrate formed TiN infrared high reflection layer 9；Sedimentation time is 3-8 minutes；
Step 5: closing Ti target, opening AlTi alloys target 6 and adjusting electric current, the power for adjusting AlTi alloys target 6 is 0.1-
0.3 kilowatt, it is passed through flow into vacuum drying oven and is the oxygen of 10-30SCCM, and nitrogen is adjusted to low discharge, low discharge after adjusting
The flow of nitrogen is 20-50SCCM, and under low oxygen and low nitrogen environment, the main suction of biphase structure is deposited on infrared high reflection layer 9
Receive layer 10, sedimentation time 1-3min；
The flow of nitrogen is passed through in vacuum drying oven to 60-100SCCM, under the high nitrogen environment of hypoxemia, in main absorption Step 6: increasing
The secondary absorbed layer 11 of single phase nano structure, sedimentation time 1-3min are deposited on layer 10；
Step 7: nitrogen stream meter is closed, by the oxygen flow being passed through in vacuum drying oven to 200-500SCCM, in high oxygen concentration
Anti-reflection layer 12 is deposited under the conditions of degree, 12 sedimentation time of anti-reflection layer is 1-3min；
Step 8: preparation terminates, the heater 4 of AlTi alloys target 6 and vacuum drying oven is closed, then naturally cools to 100 DEG C
Hereinafter, obtaining the Ti-Al-O-N biphase composite solar absorber coatings of four-layer structure.
In the preparation process of main absorbed layer 10 and time absorbed layer 11, the flow of oxygen is remained unchanged, and is passed through by control
The ratio of the nitrogen flow control two-phase particle of vacuum chamber 7.During deposition, the oxygen being passed through in vacuum chamber 7 is adjusted
Throughput to a certain value, due to Al ion ratio Ti ion be easier with O ions binding so that the Al ion that target is evaporated is big
Subparticipation is reacted with O ion, forms amorphous Al2O3.Amorphous Al2O3For dielectric.In the insufficient situation of nitrogen, Ti from
Sub- a part forms TiN nano particle with N ions binding, and a part forms Ti nano particle, and is embedded in amorphous nickel/phosphorus/aluminium oxide,
Biphase nanocrystalline composite coating is eventually formed as main absorbed layer 10.Under conditions of nitrogen abundance, Ti ion and N ions binding
It forms TiN nano particle to be embedded in amorphous nickel/phosphorus/aluminium oxide, forms single phase nano composite coating as time absorbed layer 11.In oxygen stream
Under conditions of amount is sufficient, all fully oxidized formation amorphous titanium aluminum oxide of Ti and Al ion, as anti-reflection layer 12.
In the infrared high reflection layer 9 of depositing TiN, use is high-power, primarily to improving the energy of plasma intermediate ion
Amount forms coating and substrate 8 and is chemically combined, improves binding force.By controlling the ratio of the oxygen and nitrogen that are passed through reaction chamber,
The nanocrystalline ratio of Ti and TiN is adjusted, biphase crystal composite material is obtained, makes coating that there are wide spectrum absorbent properties.It obtains
The single-phase nano combined absorbing material of TiN makes it form grading structure with main absorbed layer, reduces reflection, improves absorbent properties.It is passed through
Excessive oxygen, obtains fully oxidized amorphous titanium aluminum oxide, and coating interface is effectively reduced in 1.8-2 or so in refractive index
Reflection；The oxide coating compact structure simultaneously, there is no cavities, cover main absorbed layer 10 and time absorbed layer 11, prevent from receiving
Rice grain and high temperature air and contact with sea water improve coating performance stability.The infrared high reflection layer of TiN is below in conjunction with specific
Further description of the technical solution of the present invention for embodiment:
10-3Under the vacuum degree of Pa, control 2 revolving speed of work rest is 5rpm, and the nitrogen of 300SCCM is passed through into vacuum drying oven
Gas, the energetic ion being evaporated using Ti target 3 through over cleaning stainless steel and capillary porous material substrate 8 on depositing TiN
Infrared high reflection layer 9, the power of sedimentary origin is 0.3 kilowatt, and the bias on workpiece is -150V, and sedimentation time 5min, this is red
Outer high reflection layer 9 with a thickness of 200 nanometers；After deposition, Ti target 3 is closed, it is 20SCCM's that flow is passed through into vacuum drying oven
Oxygen, and adjusting stream of nitrogen gas amount is 20SCCM, opens AlTi alloys target 6, adjusting sets 6 electric current of AlTi alloys target as 65A, right
The power answered is 0.2 kilowatt, deposits main absorbed layer 10, sedimentation time 1.5min, main absorbed layer 10 is with a thickness of 60 nanometers；Increase
Nitrogen flow is 80 SCCM, deposits time absorbed layer 11, sedimentation time 1min, secondary absorbed layer 11 is with a thickness of 40 nanometers；Close nitrogen
Air-flow meter continues growing the flow of oxygen to 300SCCM, deposits anti-reflection layer 12 under oxygen environment, sedimentation time 2min is thick
Degree is 60 nanometers；Deposition terminates natural cooling, and overall thickness is 260 nanometers, obtains the sun light-absorbing coating of four-layer structure.Its
Reflectance spectrum in 0.3-25 micron range is as shown in Fig. 3, calculate stainless steel base coating absorptivity be 0.936,
Emissivity is 0.175；It is 0.958 in the absorptivity of porous NiO substrate, emissivity 0.471.
Claims (7)
1. a kind of biphase composite solar absorber coatings, it is characterised in that: be successively arranged in substrate infrared high reflection layer,
Main absorbed layer, secondary absorbed layer and anti-reflection layer, wherein substrate is made of the porous material of hydrophily and seawater corrosion resistance, infrared height
Reflecting layer is the transition metal nitride material of seawater corrosion resistance, and main absorbed layer is two kinds of nanometers with different optical properties
Grain material is inlayed to be formed in the dielectric, and secondary absorbed layer inlays group in dielectric by single-phase transition metal nitride nano material
At anti-reflection layer is low refractive index material layer, and the overall reflectivity of coating is advantageously reduced by coating grading structure, improves and absorbs
Rate；The porosity of porous material that substrate is made is between 20-80%, and pore size is 0.1-10 microns, and substrate thickness exists
More than or equal to 1 millimeter；Infrared high reflection layer is TiN or ZrN layers with a thickness of 0.1-1 microns；Main absorbed layer is by two kinds of differences
The transition metal nanoparticles and transition metal nitride nano material of optical property are inlayed and are formed in the dielectric, wherein transition
Metal nanoparticle to the absorption peak of solar radiation between 200-400 nanometers, the absorption of transition metal nitride nano material
Between 500-700 nanometers, the ratio of two kinds of material nano crystalline substances is adjustable between 0-1 at peak, two kinds of material nanoparticle size 3-
15 nanometers, the coating layer thickness of main absorbed layer is at 30-100 nanometers；The single-phase transition metal nitride nano material of secondary absorbed layer
3-10 nanometers of size, 30-100 nanometers of coating layer thickness of grain；The Refractive Index of Material of anti-reflection layer be 1.8-2,50-100 nanometers of thickness.
2. a kind of biphase composite solar absorber coatings method described in manufacturing claims 1, which is characterized in that including following
Step:
Step 1: getting out the equipment for manufacturing the biphase composite solar absorber coatings, which includes with fire door
Vacuum drying oven, vacuum drying oven is interior to be equipped with rotatable work rest, sets around work rest there are two symmetrical heater in vacuum drying oven,
Vacuum drying oven is respectively arranged on the left side and the right side AlTi alloys target and Ti target；
Step 2: the cleaning of base material, it is successively each super in acetone, alcohol and deionized water that the porous material of substrate will be made
Sound cleaning 8-30min, which is placed in drier, dries, and is then loaded into vacuum drying oven on work rest, closes fire door；
Step 3: the acquisition of vacuum environment, by vaccum-pumping equipment by the environment that is evacuated in vacuum drying oven；
Step 4: starting device, allows work rest to rotate with matrix, Ti target is then opened, large power electric arc discharge technology is utilized
Ti ion is evaporated from Ti target with electric current, in vacuum drying oven in be passed through high flow capacity nitrogen, the red of TiN is formed on the substrate
Outer high reflection layer；
Step 5: closing Ti target, open AlTi alloys target and simultaneously adjust electric current, be passed through low discharge oxygen into vacuum drying oven, and by nitrogen
Gas is adjusted to low discharge, and under low oxygen and low nitrogen environment, the main absorbed layer of biphase structure is deposited on infrared high reflection layer；
Step 6: increasing the flow for being passed through nitrogen in vacuum drying oven, under the high nitrogen environment of hypoxemia, single phase nano is deposited on main absorbed layer
The secondary absorbed layer of structure；
Step 7: closing nitrogen stream meter, the oxygen flow being passed through in vacuum drying oven is increased, deposits and subtracts under the conditions of high oxygen concentration
Anti- layer；
Step 8: preparation terminates, the heater of AlTi alloys target and vacuum drying oven is closed, then naturally cools to 100 DEG C hereinafter, obtaining
To the Ti-Al-O-N biphase composite solar absorber coatings of four-layer structure.
3. a kind of manufacture biphase composite solar absorber coatings method as claimed in claim 2, it is characterised in that: described true
The vaccum-pumping equipment of empty furnace includes mechanical pump and molecular pump, when vacuumizing in step 3, first passes through mechanical pump pumping, works as vacuum
After furnace pressure reaches 2pa or less, opening molecular pump will be evacuated, and high vacuum system will be pumped into vacuum drying oven, until 8 × 10-4pa
Below.
4. a kind of manufacture biphase composite solar absorber coatings method as claimed in claim 2, it is characterised in that: the step
In rapid four, the arc discharge power of Ti target is 0.2-0.5 kilowatts, in vacuum drying oven in be passed through the flow of nitrogen be 200-
The revolving speed of 500SCCM, work rest are set as 3-5rpm.
5. a kind of manufacture biphase composite solar absorber coatings method as claimed in claim 2, it is characterised in that: the step
In rapid five, the power of AlTi alloys target is 0.1-0.3 kilowatts, and the flow for being passed through oxygen in vacuum drying oven is 10-30SCCM, after adjusting
The flow of low discharge nitrogen is 20-50SCCM, and the main absorbed layer sedimentation time of biphase structure is 1-3min.
6. a kind of manufacture biphase composite solar absorber coatings method as claimed in claim 2, it is characterised in that: the step
In rapid six, the power of AlTi alloys target is 0.1-0.3 kilowatts, and nitrogen flow range is 60-100SCCM after increase, secondary absorbed layer
Sedimentation time is 1-3min.
7. a kind of manufacture biphase composite solar absorber coatings method as claimed in claim 2, it is characterised in that: the step
In rapid seven, the power of AlTi alloys target is 0.1-0.3 kilowatts, and the oxygen flow after increase is 200-500SCCM, anti-reflection layer deposition
Time is 1-3min.
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