Hybrid multilayer solar selective coating for high temperature solar thermal applications and a process for the preparation thereof

• US 9,726,402 B2
• Filed: 09/11/2013
• Issued: 08/08/2017
• Est. Priority Date: 02/08/2013
• Status: Active Grant

• Current Assignee: Council of Scientific & Industrial Research
• Original Assignee: Council of Scientific & Industrial Research
• Inventors: Chandra, Harish Barshilia, Basu, Jyothi Bharathibai, Vara, Lakshmi Ramachandrappa
• Primary Examiner(s): Turner, Archene
• Application Number:
  US14/764,372
• Publication Number:
  US 20160010896A1
• Time in Patent Office: 1,427 Days
• Field of Search: 204192, 20419212, 20419215, 20419226, 428216, 428336, 428469, 428472, 428697, 428698, 428699
• CPC Class Codes: C23C 14/0036 Reactive sputtering
• CPC Class Codes: C23C 14/025 Metallic sublayers
• CPC Class Codes: C23C 14/0641 Nitrides C23C14/0617 takes precedence
• CPC Class Codes: C23C 14/0676 Oxynitrides
• CPC Class Codes: C23C 14/081 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 14/083 of refractory metals or yttrium
• CPC Class Codes: C23C 14/35 by application of a magnetic field, e.g. magnetron sputtering C23C14/3457 takes precedence
• CPC Class Codes: C23C 14/352 using more than one target C23C14/56 takes precedence
• CPC Class Codes: C23C 14/505 for rotation of the substrates
• CPC Class Codes: C23C 14/584 Non-reactive treatment
• CPC Class Codes: C23C 18/122 Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
• CPC Class Codes: C23C 18/1245 Inorganic substrates other than metallic
• CPC Class Codes: C23C 18/1254 Sol or sol-gel processing
• CPC Class Codes: C23C 28/00 Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
• CPC Class Codes: C23C 28/321 with at least one metal alloy layer
• CPC Class Codes: C23C 28/34 including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
• CPC Class Codes: C23C 28/345 with at least one oxide layer
• CPC Class Codes: C23C 28/3455 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
• CPC Class Codes: C25D 5/48 After-treatment of electroplated surfaces
• CPC Class Codes: C25D 7/00 Electroplating characterised by the article coated
• CPC Class Codes: F24S 70/10 : characterised by the absorbing material absorbing coatings or surface treatment for increasing absorption F24S70/20
• CPC Class Codes: F24S 70/225 : for spectrally selective absorption
• CPC Class Codes: F24S 70/30 : Auxiliary coatings, e.g. anti-reflective coatings
• CPC Class Codes: Y02E 10/40 : Solar thermal energy, e.g. solar towers

Abstract

The present invention describes a hybrid multilayer solar selective coating having high thermal stability useful for high temperature solar thermal power generation. The hybrid multilayer solar selective coating of the present invention has been deposited using a novel combination of sputtering and sol-gel methods on metallic and non-metallic substrates, preferably on SS 304 and 321 with chrome interlayer. The hybrid multilayer solar selective coating of the present invention consists of stacks of Ti/chrome interlayer, aluminum titanium nitride (AlTiN), aluminum titanium oxynitride (AlTiON), aluminum titanium oxide (AlTiO) and organically modified silica (ormosil) layers. The chrome interlayer was deposited using an electroplating method, whereas, Ti, AlTiN, AlTiON and AlTiO layers were prepared using a four-cathode reactive unbalanced pulsed direct current magnetron sputtering technique. The ormosil layer was deposited using a sol-gel technique, which provides the enhanced absorptance and improved long term thermal stability in air and vacuum. The present invention provides a hybrid multilayer solar selective coating having absorptance >0.950, emittance <0.11 (SS substrate with chrome interlayer) and long term high thermal stability (in the order of 1000 hrs under cyclic heating conditions at 500° C. in air and 600° C. in vacuum). The hybrid multilayer solar selective coating of the present invention exhibits higher solar selectivity ratio in the order of 5-9 on metal and non-metal substrates. The hybrid multilayer solar selective absorber coating of the present invention has high oxidation resistance, stable microstructure, high adherence and graded composition particularly suitable for applications in concentrating collectors like evacuated receiver tubes and Fresnel receiver tubes useful for solar steam generation.

Claims

1. A hybrid multilayer solar selective coating comprising a tandem stack of layers containing an interlayer of chromium, a first absorber layer of aluminum-titanium nitride (AlTiN), a second absorber layer of aluminum-titanium oxynitride (AlTiON), an antireflection layer of aluminum-titanium oxide (AlTiO) and a barrier layer of organically modified silica (ormosil), wherein said coating exhibits a thermal resistance up to 500°

C. in air and up to 600°

C. in vacuum with a solar selectivity ratio in the order of 5 to 9.

2. The hybrid multilayer solar selective coating as claimed in claim 1, wherein said coating is stable under UV irradiation, external environment and thermal shock.

3. The hybrid multilayer solar selective coating as claimed in claim 1, wherein thicknesses of first absorber layer, second absorber layer, antireflection layer and barrier layer are in the range of 30-70 nm, 20-40 nm, 30-55 nm and 50-200 nm, respectively.

4. The hybrid multilayer solar selective coating as claimed in claim 1, wherein thickness of chrome interlayer is in the range of 3-7 μ

m.

5. The hybrid multilayer solar selective coating as claimed in claim 1, wherein the composition of the first absorber layer is:

Al=25-55 at. %, Ti=10-25 at. % and N=30-50 at. %, second absorber layer is;

Al=15-30 at. %, Ti=10-15 at. %, N=10-20 at. %, anti-reflection layer is Al=15-30 at. %, Ti=5-15 at. % and O=40-80 at. % organically modified sol-gel silica layer (ormosil) is Si=16-30 at. %, C=3-15 at. %, O=25-59 at. % and H=8-44 at. %.

6. The hybrid multilayer solar selective coating as claimed in claim 1, wherein said coating is useful for solar thermal power generation.

7. A process for the preparation of a hybrid multilayer solar selective coating as claimed in claim 1, comprising the steps of:

a. metallographically polishing and chemically cleaning of substrate in an ultrasonic agitator in acetone, absolute alcohol and trichloroethylene;

b. depositing a interlayer either by sputtering or electroplating;

c. depositing solar absorber layers consisting of aluminum titanium nitride (AlTiN), aluminum titanium oxynitride (AlTiON) and aluminum titanium oxide (AlTiO) using four-cathode reactive pulsed direct current unbalanced magnetron sputtering system;

d. depositing ormosil layer by dip-coating to obtain hybrid multilayer solar selective coating.

8. The process as claimed in claim 7, wherein said substrate is selected from metallic and non-metallic group.

9. The process as claimed in claim 8, wherein said substrate comprises stainless steel having a chrome interlayer configured for reducing emittance.

10. The process as claimed in claim 7, wherein said ormosil layer is prepared by sol gel method using a sol prepared by two precursor silanes consisting of (a) a silane of formula SiR′

₄, wherein R′

is a hydrolysable alkoxy group and (b) silane of the formula SiR′

_nR″

_(4-n), where R′

is a hydrolysable alkoxy group and R″

is non-hydrolysable group comprising of any one of the groups such as alkyl, vinyl, alkenyl or aryl group, or alkyl group with a functional group such as epoxy, amino, isocyanate or acrylate group containing at least one such non-hydrolysable group.

11. The process as claimed in claim 10, wherein the silane of formula SiR′

₄ and the silane of the formula SiR′

_nR″

_(4-n) are present in a molar ratio of 1;

10 to 10;

1.

12. The process as claimed in claim 10, wherein the silane of formula SiR′

₄ comprises tetraethoxysilane and the silane of the formula SiR′

_nR″

_(4-n) comprises methyl triethoxysilane.

13. The hybrid multilayer solar selective coating as claimed in claim 1, wherein said coating has an absorptance of 0.950 or more and an emittance of 0.11 or less.