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WO2012059789A1 - Fabrication de feuilles solaires sélectives par procédé de rouleau à rouleau - Google Patents

Fabrication de feuilles solaires sélectives par procédé de rouleau à rouleau Download PDF

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Publication number
WO2012059789A1
WO2012059789A1 PCT/IB2010/055006 IB2010055006W WO2012059789A1 WO 2012059789 A1 WO2012059789 A1 WO 2012059789A1 IB 2010055006 W IB2010055006 W IB 2010055006W WO 2012059789 A1 WO2012059789 A1 WO 2012059789A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
foil
layer
selective
sulphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2010/055006
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English (en)
Inventor
Figen Kadirgan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SELEKTIF TEKNOLOJI SANAYI TICARET Ltd SIRKETI
Original Assignee
SELEKTIF TEKNOLOJI SANAYI TICARET Ltd SIRKETI
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SELEKTIF TEKNOLOJI SANAYI TICARET Ltd SIRKETI filed Critical SELEKTIF TEKNOLOJI SANAYI TICARET Ltd SIRKETI
Priority to PCT/IB2010/055006 priority Critical patent/WO2012059789A1/fr
Publication of WO2012059789A1 publication Critical patent/WO2012059789A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0621—In horizontal cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0664—Isolating rolls
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0692—Regulating the thickness of the coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • 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
    • 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
    • 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
    • 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

Definitions

  • This invention relates to a method of coating metal foils, continuously using electrochemical pretreatment and deposition methods and sol-gel techniques especially for high efficient solar collectors, with selectively absorbent films and a product obtained thereof.
  • the disclosure provides an improved solar selective multilayer coating having thermal stability up to 240°C and a process therefore.
  • a tandem stack of three layers of nickel, coloured nickel and Silane is deposited on metal and non-metal substrates using a roll to roll process. While the first two layers function as the absorber layer, the third layer function as antireflection layer.
  • Methods generally involve applying a coating to an object.
  • Thermal radiation controlled objects are used in solar collector absorber panels.
  • the surface coating has to absorb radiation corresponding to the sun's solar emission spectrum that is principally from 300 to 2500 nanometers, while having a high reflectivity at longer such as above approximately 4 microns. This allows the object to absorb and retain the sun's heat because the decreased emittance at the thermal wavelengths.
  • Selective absorption light in the solar ultraviolet and near infrared regions of the wavelength can be achieved by over coating the reflective metallic surface with materials that selectively absorb solar wavelength.
  • Coated aluminum absorbers are especially valuable for heat exchange units because of the lightness of aluminum and the resultant decrease in the complexity and weight of structural elements required for support thereof. Moreover, the easy machining and fabrication of them add to their value. Coated copper absorbers are also very valuable for heat exchange units and more resistant to the corrosion, in order to overcome the weight problem, it is possible to use very thin layers of copper as substrate.
  • coated low carbon steel absorbers are interesting from the cost point of view. The most common methods for forming such surfaces are by electrochemical deposition techniques followed by chemical oxidation of the deposit or vacuum techniques.
  • Black nickel coatings are known as solar selective surfaces for the conversion of solar radiation into useful heat (J. Jurisson, et al, J. Vac. Sci. Technol. 12: 1975, 1010; H.Tabur, Low Temperature Engineering Application to Solar Energy, ed. R.C. Jordan, New York: 1969, p. 41; R.B. Pettit, R.R. Sowell, J.Vac.Sci. Technd. 13: 1976, 596, Ewa Wackelgard Solar Energy Mat. and Solar Cells, 56, 1998, 35- 44). These coatings possess good optical properties but the durability shown is often poor. They degrade completely after exposure to 200°C.
  • the invention disclosed in US patent no. 2,917,817 consists in a receiver for solar heaters, which is basically a composite body comprising a metal base and a selectively absorbent thin coating applied to the said base.
  • the nickel base is immersed into an aqueous electrolytic bath containing nickel sulphate, zinc sulphate, ammonium sulphate, ammonium tiocyanate, and citric acid.
  • the bath temperature is about 30°C.
  • the base is aluminium, it is first covered with an oxide layer; then immersed in a solution of copper nitrate, nitric acid, and potassium permanganate at 85-90°C; and finally dried and heated to 450°C so that the surface colour becomes almost black.
  • 4,177,325 discloses a panel for selectively absorbing solar energy and a method of producing thereof.
  • This panel comprises an aluminium substrate, a layer of zinc thereon, a layer of nickel over the zinc layer, and a layer of nickel oxide. Copper substrate may well be used for the same purpose.
  • the chemical oxidation of the nickel layer is performed at temperatures as high as 900-950°F.
  • US patent no. 3,920,413 discloses that an aluminium metal substrate can be cleaned, prepared to receive a brightening layer, coated with the brightening layer and further coated with a very thin solar thermal energy absorbing coating of black nickel.
  • the bath temperature is in the range from about 115° to about 140°F.
  • US patent no. 4,244,790 describe a process and aqueous composition for electrodepositing black nickel deposit directly on conductive bright copper, nickel, brass, cadmium and the like.
  • the aqueous solution is of a pH ranging from about to 8 to 12 and contains nickel ions in combination with soluble amines at 25-50°C between 1-10 minutes over a current density range of 2-25 amperes. No any explanation on spectral properties and durability of the surface is given in the invention.
  • European patent no. 0029257 explains a black, selectively absorbing layer consisting of finely comminute nickel, nickel-zinc or nickel-lead on a substrate, particularly a solar collector plate, which is protected from corrosion by a thin passivating chromic-oxide layer. Corrosion resistance in this invention is mainly achieved by the application of the chromate-layer.
  • a roll unit for use of surface treatment of copper foil defined in US patent no: 2010/0018273.
  • the electrochemical surface treatment of a copper foil is continuously performed by using a copper foil winded around a coil passing in front of opposed anodes via several upper and lower rolls arranged inside and outside of electrolytic tanks by being rewound and subject to surface treatment.
  • Current for surface treatment is flowed between anode and the copper foil as the cathode via the electrolytic solution.
  • Electrolytic solutions such as copper sulphate and chromic acid used in the surface treatment may causes a corrosive
  • a roll unit capable of inhibiting abrasion and corrosion of the roll shaft and the bearing and capable of simple replacement of bearing box, bearing and other components is provided.
  • This roll unit can be used under a corrosion environment caused by the adhesion of treatment liquid and the corrosive mist generated from the surface treatment liquids are developed.
  • the metal substrate foil winded around a coil, subject to surface treatment such as cleaning, electrochemical degreasing and brightening. Then, it is continuously coated with a layer of nickel and an outermost layer of absorbent nickel oxide-nickel zinc sulphide mixture in front of nickel anodes via several squeeze roll arranged outside of electrolytic tanks. Selective coating coated copper foil is immersed in a tank containing a dielectric material to provide the environmental protection and after the thermal treatment the foil is winded around the coil once again via a guide roll. Copper, low carbon steel or steel foils may treat according to this procedure. However aluminium foils are first coated with a layer of zinc before the nickel layer, and the nickel layer is applied thereon. The solar absorbance and emittance of the resulting selective surfaces were found to be 0.95and 0.06, respectively. The color may change from the dark blue to black according to the deposition conditions.
  • the present invention was contrived in view of the problems relating the low cost selective surface in mass production with easy machining and relates to a roll to roll unit to be used in a process that continuously perform chemical and electrochemical surface treatments and selective surface texture on a surface of rolled copper, aluminium or steel foil.
  • the electrochemical surface treatment and formation of selective layers by electro deposition is continuously performed by using an apparatus as shown in Figure 1.
  • Figure 1 shows a simple schematic diagram from the top of the continuous roll to roll process.
  • the electrolytic and chemical treatments tanks are provided with a reserve tanks and circulation pumps to assure the constant level of electrolyte in the tanks with circulation of the solutions that was flow in during the process from reserve tank to electrolytic tank. Therefore, electrolytic bath composition in the electrolytic tanks was kept as that of their initial composition.
  • each electrolytic bath a pair of rolls is supplied as guide roll.
  • Selective film coated copper foil is passed through a triple small diameter rolls to roll up and wind around the coil once again.
  • the rotating guide rolls having slight convex and concave shape is necessary to provide not only the straightening of the metal sheet but also to avoid the falling down of the metal foils because of the gravity effect.
  • the distance between two rolls is adjusted to keep away the structural deformation of the surface relatively to the foil thickness.
  • a geared motor gives the rotating movement to the rolls.
  • the invention provides an optical structure having an infrared reflective layer and a nano layer with low emissivity in the infrared region. These layers are separated by a thin film spacer of a dielectric or semiconductor material. The reflectivity and transmission of the layer are selectively controlled through the thickness of the layers such that color may be independent of the infrared properties of the absorber and reflector layer.
  • Some semiconductors are highly desirable as thin film spacer because these materials have low enough refractive indices to keep surface reflectivity at a minimum.
  • useful semiconductor materials are copper oxide, iron oxides, chromium oxides, nickel oxide, complexes of nickel-zinc sulfide, lead sulfide and so forth. One can achieve the dark colors by changing the thickness of the interference design.
  • the optical stack may be advisable to overcoat the optical stack with a dielectric layer that does not significantly alter the optical properties of the stack, but provides environmental protection to the stack.
  • a dielectric layer that does not significantly alter the optical properties of the stack, but provides environmental protection to the stack.
  • this layer can affect the color. As the dielectric thickness increases, the color may change from black dark blue.
  • the metal substrates are treated according to the following method:
  • Nickel plating with a solution containing nickel sulfamate, sulphate,
  • Electroplating is performed for 0.1-15 min., at 20-35°C, under a potential difference of 1-20 A/dm .
  • a zincating step is performed.
  • Aluminium substrates or its alloys are converted to selective absorbers for solar energy by the following steps:
  • nickel plating with a solution containing nickel sulfamate, sulphate, phosphate or chloride of following composition:
  • Electroplating is done at 1-20 A/dm 2 at 40-60°C for 10-30 minutes.
  • Electroplating is done at 20-35°C, under 1-20 A/dm .
  • the foil coated with nickel stack is immersed in 1 to 15 % Silan containing solution. Then, a heat treatment between 180 -300°C is made.
  • the resulting selective coating is deep blue-black in color and the absorptivity of the specimens is 0.93-0.97 and the emissivity is 0.05-0.12.
  • Copper substrates or its alloys are converted to selective absorbers for solar energy by
  • nickel plating with a solution containing nickel sulfamate, sulphate, phosphate or chloride of following composition:
  • Electroplating is done at 1-20 A/dm 2 at 40-60°C for 10 - 30 minutes.
  • Electroplating is done at 20-35°C, under 1-20 A/dm 2 .
  • the foil coated with nickel stack is immersed in 1 to 15 % Silan containing solution. Then, a heat treatment between 180 -300°C is made.
  • the selective coating is deep blue-black in colour and the absorptivity of the specimens is 0.93-0.97 and the emissivity is 0.05-0.12.
  • Example 3 Low carbon steel or steel substrates or its alloys are converted to selective absorbers for solar energy by the following steps:
  • nickel plating with a solution containing nickel sulfamate, sulphate, phosphate or chloride of following composition:
  • Electroplating is done at 1-20 A/dm 2 at 40-60°C for 10 - 30 minutes,
  • chloride,phosphate or nitrate of the following composition:
  • Electroplating is done at 20-35°C, under 1-20 A/dm .
  • the foil coated with nickel stack is immersed in 1 to 15 % Silan containing solution. Then, a heat treatment between 180 -300°C is made.
  • the selective coating is deep blue-black in color and the absorptivity of the specimens is 0.93-0.97 and the emissivity is 0.05-0.12.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Cette invention concerne un procédé continu de traitement de surface et de revêtement de feuilles (faites de métaux tels que le cuivre, l'aluminium, l'acier ou autres métaux ou de matériaux non métalliques) pour leur conférer des propriétés sélectives vis-à-vis du spectre solaire et pour améliorer le rendement de la fabrication de surfaces sélectives. Ledit procédé de traitement de surface continu permettant l'obtention d'une surface solaire sélective présentant un haut coefficient d'absorption et un faible coefficient d'émission, comprend les étapes consistant à : traiter les feuilles métalliques par traitement chimique et électrochimique afin de nettoyer la surface de la feuille, et procéder au dépôt électrochimique de films minces et/ou nanofilms en faisant passer la feuille métallique en tant que cathode face à des anodes par l'intermédiaire de rouleaux et en empêchant un liquide fixé à la surface d'être entraîné vers la cuve suivante. L'appareil de l'invention comprend deux rouleaux en acier inoxydable (d'enroulage et de ré-enroulage) de diamètre supérieur, et des rouleaux de guidage de diamètres inférieurs disposés entre des cuves de traitement de surface, de dépôt et de revêtement diélectrique. Un traitement thermique au four est effectué sur la surface de la feuille avant son ré-enroulage. Le procédé de l'invention permet d'obtenir un dépôt sélectif uniforme et adhérant sur un substrat conducteur en forme de feuille.
PCT/IB2010/055006 2010-11-04 2010-11-04 Fabrication de feuilles solaires sélectives par procédé de rouleau à rouleau Ceased WO2012059789A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014019702A (ja) * 2012-07-19 2014-02-03 Universal Display Corp ジアリールアミノ置換金属錯体
CN106931662A (zh) * 2017-03-24 2017-07-07 广西南宁市丽农太阳能有限公司 多孔导流隔板的双水箱太阳能热水器
CN106931664A (zh) * 2017-03-24 2017-07-07 广西南宁市丽农太阳能有限公司 竖管导流隔板的双水箱太阳能热水器
CN106949645A (zh) * 2017-03-24 2017-07-14 广西南宁市丽农太阳能有限公司 一种内设导流隔板的双水箱太阳能热水器
CN107014095A (zh) * 2017-03-24 2017-08-04 广西南宁市丽农太阳能有限公司 一种设有多孔导流隔板的双水箱太阳能热水器
CN107024011A (zh) * 2017-03-24 2017-08-08 广西南宁市丽农太阳能有限公司 一种设有导流隔板的双水箱太阳能热水器
CN107059084A (zh) * 2017-01-03 2017-08-18 本溪市通宝冶金设备制造有限公司 防止轧辊镀铬污染环境的方法
CN113818064A (zh) * 2021-07-08 2021-12-21 长春工业大学 一种可以实现高效光热转换的针叶状镍黑膜

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US2377550A (en) * 1940-12-02 1945-06-05 Hanson Van Winkle Munning Co Apparatus for electrogalvanizing
US2522071A (en) * 1943-04-06 1950-09-12 Tait William Henry Valve structure for passage of strip material through the wall of liquid treatment baths
US2917817A (en) 1955-03-25 1959-12-22 Res Council Of Israel Receiver for solar energy collectors
US3328992A (en) * 1963-06-04 1967-07-04 United Eng Foundry Co Method of and apparatus for obtaining flat metallic strip
US3920413A (en) 1974-04-05 1975-11-18 Nasa Panel for selectively absorbing solar thermal energy and the method of producing said panel
US4088547A (en) 1976-09-01 1978-05-09 Borg-Warner Corporation Method for producing a coated metal nodular solar heat collector
US4177325A (en) 1977-08-31 1979-12-04 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Aluminium or copper substrate panel for selective absorption of solar energy
US4244790A (en) 1979-08-31 1981-01-13 Oxy Metal Industries Corporation Composition and method for electrodeposition of black nickel
EP0029257A1 (fr) 1979-06-25 1981-05-27 Koninklijke Philips Electronics N.V. Substrat recouvert d'une couche noire résistant à la corrosion et procédé d'obtention d'un tel substrat
WO2005042805A1 (fr) * 2003-10-31 2005-05-12 Figen Kadirgan Procede de depot selectif d'un film absorbant sur un substrat metallique
US20100018273A1 (en) 2006-12-28 2010-01-28 Nippon Mining & Metals Co., Ltd. Roll Unit for use in Surface Treatment of Copper Foil

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US2522071A (en) * 1943-04-06 1950-09-12 Tait William Henry Valve structure for passage of strip material through the wall of liquid treatment baths
US2917817A (en) 1955-03-25 1959-12-22 Res Council Of Israel Receiver for solar energy collectors
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US3920413A (en) 1974-04-05 1975-11-18 Nasa Panel for selectively absorbing solar thermal energy and the method of producing said panel
US4088547A (en) 1976-09-01 1978-05-09 Borg-Warner Corporation Method for producing a coated metal nodular solar heat collector
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EP0029257A1 (fr) 1979-06-25 1981-05-27 Koninklijke Philips Electronics N.V. Substrat recouvert d'une couche noire résistant à la corrosion et procédé d'obtention d'un tel substrat
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WO2005042805A1 (fr) * 2003-10-31 2005-05-12 Figen Kadirgan Procede de depot selectif d'un film absorbant sur un substrat metallique
TR200602074T1 (tr) 2003-10-31 2007-02-21 Kadirgan F�Gen Metal bir yüzey üzerine seçici absorplayıcı film kaplama yöntemi.
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Title
"Metal Finishing Handbook", 1974, pages: 350
EWA WACKELGARD SOLAR ENERGY MAT. AND SOLAR CELLS, vol. 56, 1998, pages 35 - 44
H.TABUR: "Low Temperature Engineering Application to Solar Energy", 1969, pages: 41
J. JURISSON ET AL., J. VAC. SCI. TECHNOL., vol. 12, 1975, pages 1010
R.B. PETTITR.R. SOWELL, J.VAC.SCI. TECHND., vol. 13, 1976, pages 596

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014019702A (ja) * 2012-07-19 2014-02-03 Universal Display Corp ジアリールアミノ置換金属錯体
CN107059084A (zh) * 2017-01-03 2017-08-18 本溪市通宝冶金设备制造有限公司 防止轧辊镀铬污染环境的方法
CN106931662A (zh) * 2017-03-24 2017-07-07 广西南宁市丽农太阳能有限公司 多孔导流隔板的双水箱太阳能热水器
CN106931664A (zh) * 2017-03-24 2017-07-07 广西南宁市丽农太阳能有限公司 竖管导流隔板的双水箱太阳能热水器
CN106949645A (zh) * 2017-03-24 2017-07-14 广西南宁市丽农太阳能有限公司 一种内设导流隔板的双水箱太阳能热水器
CN107014095A (zh) * 2017-03-24 2017-08-04 广西南宁市丽农太阳能有限公司 一种设有多孔导流隔板的双水箱太阳能热水器
CN107024011A (zh) * 2017-03-24 2017-08-08 广西南宁市丽农太阳能有限公司 一种设有导流隔板的双水箱太阳能热水器
CN113818064A (zh) * 2021-07-08 2021-12-21 长春工业大学 一种可以实现高效光热转换的针叶状镍黑膜
CN113818064B (zh) * 2021-07-08 2023-10-31 长春工业大学 一种可以实现高效光热转换的针叶状镍黑膜

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