CN102168295B - Composite material coating having selective absorption function - Google Patents
Composite material coating having selective absorption function Download PDFInfo
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- CN102168295B CN102168295B CN2011100377767A CN201110037776A CN102168295B CN 102168295 B CN102168295 B CN 102168295B CN 2011100377767 A CN2011100377767 A CN 2011100377767A CN 201110037776 A CN201110037776 A CN 201110037776A CN 102168295 B CN102168295 B CN 102168295B
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Abstract
The invention provides a composite material coating having a selective absorption function and relates to the field of solar energy photothermal conversion technology. The composite material coating comprises, by weight, 11.8% to 38.9% of chromium element, 3.4% to 7.6% of nickel element, and 3.9% to 23.9% of oxygen element, with the balance being iron element. The composite material coating has a sunlight absorptivity-emissivity ratio greater than 9; and has good heat stability and is difficult to oxidize and corrode in a working environment with air atmosphere and at a temperature of 100 DEG C to 350 DEG C.
Description
Technical field
What the present invention relates to is the material in a kind of solar energy optical-thermal transformation technology field, specifically is a kind of composite coating with selectivity absorptive function.
Background technology
Sun power is the cleaning substitute energy that has application potential this century most.Most of concentration of energy of sunshine is in visible light and near-infrared region.Utilization to sun power (utilizes wavelength mainly to concentrate on the ultraviolet region, accounts for the 5-10% of sun power total amount) except light sensitive cell, and topmost sun power is directly changed into heat is applied to various needs exactly.At present, the solar energy thermal utilization mainly concentrates on low temperature (below 100 ℃), like solar water heater etc.The research of middle high temperature (more than 200 ℃) solar selectively absorbing coating is more potential, can be used on high-end fields such as air-conditioning, photo-thermal power generation.High working temperature is very high to the thermostability and the oxidation-resistance requirement of material, much can change in the well behaved coating of low temperature environment structure in hot environment, causes the photo-thermal conversion performance sharply to descend.
Coating for selective absorption can roughly be classified as six types: 1 bulk absorption; 2 semi-conductors-metal gradual change coating, 3 multi-layer absorber layer, 4 multiple layer metals-ceramic layer; 5 molding surfaces (surface texturing), 6 add one deck selective permeation coating on similar black matrix absorption layer.Which kind of coating no matter, its design is intended to reduce the reflectivity of coating in the solar radiation district as far as possible, improves the absorption conversion of material to luminous energy itself, also requires the thermally-stabilised height of material component under working temperature simultaneously, and oxidation-resistance is strong.Therefore, a kind of design demand of selectivity microwave absorbing coating is taken all factors into consideration above-mentioned a plurality of factor.
Molding surface is a direction of coating for selective absorption design always.Through to the material surface moulding, obtain the convex-concave surface of certain geometry, after incident photon got into coating, energy was absorbed by material itself gradually in the internal surface multiple reflection, and is converted into heat energy.H.Sai; People such as E.Rephaeli have successively reported the surface of the tetrahedron arrangement that utilizes the tungsten material construction and have simulated its optical absorption function; The result is excellent, but because the physics-chem characteristic of material itself and structural requirement property are high, does not all prepare the coating of this structure.By the composite coating that red stone, chromic oxide and spinel ferronickel oxide compound constitute, yet do not report at present with the perhaps similar tetrahedron of pyramid, vertebral body structure.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists, a kind of composite coating with selectivity absorptive function is provided, this coating sunshine specific absorption/emission ratio is greater than 9; At air atmosphere, has good thermostability in the Working environment that temperature is 100 ℃～350 ℃, difficult oxidisability and be difficult for being corroded.
The present invention realizes through following technical scheme; Component of the present invention is chromium element, nickel element, oxygen element and ferro element; Its content is: chromium element 11.8%-38.9wt%, nickel element 3.4%-7.6wt%, oxygen element 3.9%-23.9wt%, all the other are ferro element.
The sunshine specific absorption α of described matrix material is 0.905～0.936, and heat emission is 0.105～0.158 than ε 100 ℃ the time; Working environment is 100 ℃～350 ℃ of air atmosphere and temperature.
Described oxygen element, ferro element and chromium element form Fe with the form of O-Fe, O-Cr chemical bond respectively
2O
3, Cr
2O
3And be present in the matrix material, nickel element, ferro element and oxygen element then form the NiFe with spinel structure with the Fe-Ni-O chemical bond
2O
4
The surface tissue of described matrix material is arranged by cone and is constituted, and the height of cone is 50～150 nanometers, and adjacent facies basialis pyramidis between centers is 50～200 nanometers.This structure helps repeatedly reflecting at material surface after light wave gets into coating, and the matrix material that is progressively had bulk absorption property absorbs.
Matrix material according to the invention is 100～350 ℃ of following Stability Analysis of Structures, and difficult oxidation is corrosion-resistant, even also do not have considerable change in medium-term and long-term its optical property of using of air atmosphere.
The present invention adopts self-assembling technique to construct said composite coating structure.Through control corrosion speed and corrosion position, guide the Cr in the alloy system at alloy surface, Ni, Fe metallic element carry out redox reaction and re-assembly at alloy surface, have formed the Fe with vertebral body structure
2O
3, Cr
2O
3, NiFe
2O
4Matrix material.
Description of drawings
Fig. 1 is the surface three dimension structure iron of embodiment 1 composite coating.
Fig. 2 has the spectral reflectance figure of composite coating in the 0.2-2.5 micrometer range of selectivity absorptive function for embodiment 1; Wherein: solid line is the reflectivity curve of the coating just prepared, dotted line be coating in air through the reflectivity curve behind 300 ℃ of high-temperature calcination 100h.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
The component of present embodiment and weight percent are: Cr (38.9%), and Ni (7.6%), O (23.9%), surplus is Fe.Coating is that the following stated scheme realizes: (composition is: Cr:12%～18% with alloy slice; Ni:6%～10%; Surplus is Fe, contains stainless steel but is not limited to stainless steel) be working electrode, graphite cake is a counter electrode, the corrosive fluid of chromic acid (2.2mol/L) and sulfuric acid (5.5mol/L) composition, temperature is 60 ± 1 ℃.This system is applied a pulsed voltage, and the generating positive and negative voltage peak pulse duration is 1: 3, and current density is controlled at 20mA/cm
2～30mA/cm
2, etching time is 30min.Finish deionized water rinsing, 60 ℃ of oven for drying.
The surface topography of coating is observed under AFM and is obtained (as shown in Figure 1); Coatingsurface is made up of regular relatively cone array; Vertebral height 50～150 nanometers; Bottom center's spacing 150～200 nanometers, coarse surface helps being absorbed in of sunshine, and the matrix material in multiple internal reflection in coated gradually absorbs.
The metal composite of forming coating is by Cr
2O
3, Fe
2O
3And NiFe
2O
4Three kinds of materials are formed.
The reflectivity curve of coating is reference with AM1.5 solar radiation spectral line shown in Fig. 2 (solid line), and the specific absorption that calculates coating is 0.934, and emission is 0.132 than (20 ℃).
The heat stability test of sample is in 300 ℃ air ambient, to carry out, and behind the calcining 12h, sample naturally cools to room temperature.Record reflectivity curve such as Fig. 2 (dotted line) of coating, the specific absorption of calculating coating is 0.936, and emission is than (20 ℃) 0.132; Continue calcining 100h, the specific absorption of coating and emission are than equal no change.
The component of present embodiment and weight percent are: Cr (11.8%), and Ni (3.4%), O (3.9%), surplus is Fe.The preparation method of coating is referring to embodiment 1, and the corrosive fluid temperature is 30 ± 1 ℃, and current density is controlled at 15mA/cm
2～20mA/cm
2, etching time is 25min, all the other steps are with embodiment 1.
Coating surface structure is arranged by similar pyramidal centrum and is constituted, the high 50～100nm of centrum, and bottom center is apart from 100～150nm.
The metal composite mixture of forming coating is by Cr
2O
3, Fe
2O
3And NiFe
2O
4Three kinds of materials are formed.
With AM1.5 solar radiation spectral line is reference, and the specific absorption of measuring coating is 0.905, and emission is 0.079 than (20 ℃).In the air 300 ℃ of annealing after 24 hours surface color do not have considerable change, also no change is compared in the absorption of coating/emission.
Embodiment 3
The component of present embodiment and weight percent are: Cr (22.6%), and Ni (6.4%), O (18.6%), all the other are Fe.The preparation method of coating is referring to embodiment 1, and the corrosive fluid temperature is 50 ± 1 ℃, and current density is controlled at 20mA/cm
2～25mA/cm
2, etching time is 20min, all the other steps are with embodiment 1.
Coating surface structure is arranged by similar pyramidal centrum and is constituted, the high 50～100nm of centrum, and bottom center is apart from 150～200nm.
The metal composite of forming coating is by Cr
2O
3, Fe
2O
3And NiFe
2O
4Three kinds of materials are formed.
With AM1.5 solar radiation spectral line is reference, and the specific absorption of measuring coating is 0.921, and emission is 0.132 than (20 ℃).Absorption/the emission of 300 ℃ of annealing coating after 100 hours is 0.923/0.105 than (20 ℃) in the air.
Claims (5)
1. the composite coating with selectivity absorptive function is characterized in that, its component is chromium element, nickel element, oxygen element and ferro element.
2. the composite coating with selectivity absorptive function according to claim 1 is characterized in that, its content is: chromium element 11.8%-38.9wt%, nickel element 3.4%-7.6wt%, oxygen element 3.9%-23.9wt%, all the other are ferro element.
3. the composite coating with selectivity absorptive function according to claim 1 and 2 is characterized in that, the sunshine specific absorption α of described matrix material is 0.905～0.936, and heat emission is 0.105～0.158 than ε 100 ℃ the time; Working environment is 100 ℃～350 ℃ of air atmosphere and temperature.
4. the composite coating with selectivity absorptive function according to claim 1 and 2 is characterized in that, described oxygen element, ferro element and chromium element form Fe with the form of O-Fe, O-Cr and Fe-Ni-O chemical bond respectively
2O
3, Cr
2O
3And NiFe
2O
4And be present in the matrix material.
5. the composite coating with selectivity absorptive function according to claim 1 and 2; It is characterized in that; The surface tissue of described matrix material is arranged by cone and is constituted, and the height of cone is 50～150 nanometers, and adjacent facies basialis pyramidis between centers is 50～200 nanometers.
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|---|---|---|---|
| CN2011100377767A CN102168295B (en) | 2011-02-15 | 2011-02-15 | Composite material coating having selective absorption function |
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|---|---|---|---|
| CN2011100377767A CN102168295B (en) | 2011-02-15 | 2011-02-15 | Composite material coating having selective absorption function |
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| CN102168295B true CN102168295B (en) | 2012-05-30 |
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ID=44489603
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3107494B2 (en) * | 1994-06-24 | 2000-11-06 | 文化シヤッター株式会社 | Lighting window of steel plate door |
| CN1367849A (en) * | 1999-08-17 | 2002-09-04 | 岛屿涂层有限公司 | Light alloy-based composite protective multifunction coating |
| CN101748465A (en) * | 2009-12-31 | 2010-06-23 | 哈尔滨工业大学 | Method for preparing coating with thermostability and high emissivity on titanium alloy substrate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0762276B2 (en) * | 1989-09-22 | 1995-07-05 | 新日本製鐵株式会社 | Zinc-chromium alloy plated steel sheet excellent in weldability and workability and method for producing the same |
| WO2007058603A1 (en) * | 2005-11-18 | 2007-05-24 | Replisaurus Technologies Ab | Method of forming a multilayer structure |
-
2011
- 2011-02-15 CN CN2011100377767A patent/CN102168295B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3107494B2 (en) * | 1994-06-24 | 2000-11-06 | 文化シヤッター株式会社 | Lighting window of steel plate door |
| CN1367849A (en) * | 1999-08-17 | 2002-09-04 | 岛屿涂层有限公司 | Light alloy-based composite protective multifunction coating |
| CN101748465A (en) * | 2009-12-31 | 2010-06-23 | 哈尔滨工业大学 | Method for preparing coating with thermostability and high emissivity on titanium alloy substrate |
Non-Patent Citations (2)
| Title |
|---|
| 李鹏.选择性吸收黑铬涂层及其应用.《太阳能》.2005,(第03期),35-37. * |
| 陈延禧等.电化学表面技术在太阳能热转换中的应用.《材料保护》.1995,第28卷(第11期),11. * |
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