WO2017116291A1 - Procédé de formation d'un revêtement couleur décoratif par anodisation - Google Patents

Procédé de formation d'un revêtement couleur décoratif par anodisation Download PDF

Info

Publication number
WO2017116291A1
WO2017116291A1 PCT/RU2016/050086 RU2016050086W WO2017116291A1 WO 2017116291 A1 WO2017116291 A1 WO 2017116291A1 RU 2016050086 W RU2016050086 W RU 2016050086W WO 2017116291 A1 WO2017116291 A1 WO 2017116291A1
Authority
WO
WIPO (PCT)
Prior art keywords
decorative coating
photonic crystal
anodizing
voltage
coating
Prior art date
Application number
PCT/RU2016/050086
Other languages
English (en)
Russian (ru)
Inventor
Кирилл Сергеевич НАПОЛЬСКИЙ
Алексей Игоревич САДЫКОВ
Филипп Сергеевич НАПОЛЬСКИЙ
Original Assignee
Кирилл Сергеевич НАПОЛЬСКИЙ
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 Кирилл Сергеевич НАПОЛЬСКИЙ filed Critical Кирилл Сергеевич НАПОЛЬСКИЙ
Publication of WO2017116291A1 publication Critical patent/WO2017116291A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/04—Producing precipitations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/14—Producing integrally coloured layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B30/00—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions
    • C30B30/02—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions using electric fields, e.g. electrolysis
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G02F1/0063—Optical properties, e.g. absorption, reflection or birefringence
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/21—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  by interference
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/23—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  for the control of the colour
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/12—Ships
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/08—Etching
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/32—Photonic crystals
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2203/00—Function characteristic
    • G02F2203/02—Function characteristic reflective

Definitions

  • the invention relates to the field of photonics, and more particularly to methods for producing colored decorative coatings.
  • the proposed method for creating a decorative coating can be used for painting metal products in various colors, changing with a change in the viewing angle.
  • the range of objects that can be decorated using the claimed invention is extremely diverse, these include electronic device housings (telephones, tablets, laptops, etc.), vehicle housings (airplanes, ships, cars, etc.), jewelry, interior items as well as metal cladding panels for buildings and various kinds of construction objects.
  • a decorative coating can be used to develop and create a wide range of high-tech optoelectronic devices that require the use of elements capable of reflecting or transmitting light with a certain adjustable wavelength (for example, Notch filters, laser generation media).
  • a certain adjustable wavelength for example, Notch filters, laser generation media.
  • Porous oxide films obtained by anodizing valve metals are widely used in science and technology.
  • a vivid example is the porous films of anodic alumina, which have been used for decorative purposes for almost 100 years [Patent specification No. 223995. No. 19839/23 from Aug. 2, 1923. London], as well as corrosion protection [Patent specification No. 223994. No. 19838/23 from Aug. 2, 1923. London].
  • Porous Anodic Aluminum Oxide Anodization and Templated Synthesis of Functional Nanostructures // Chemical Reviews, 2014, v. 114 (15), pp.
  • a known method (analogue) of coloring aluminum and its alloys by creating on their surface an oxide film having the properties of a photonic crystal [CN102181902, Method for coloring aluminum and alloy surface thereof; Zhiyuan Ling, Yisen Liu, Yi Chang, Xing Hu; September 14, 2011].
  • the invention discloses a method for painting the surface of aluminum and its alloys, which consists of the following steps: 1) cleaning and polishing the surface of aluminum or aluminum alloy; 2) conducting preliminary anodic oxidation of aluminum or aluminum alloy in a solution of sulfuric acid with a concentration of from 0.1 to 3 mol / l under constant conditions for 20 minutes to 3 hours at a voltage of 10 to 20 V using graphite as a cathode; 3) oxidation of aluminum or aluminum alloy at a temperature of from 0 to 5 ° C by applying a voltage that varies periodically in time in order to obtain a layered photonic crystal of aluminum oxide.
  • Each cycle of voltage change consists of five sections: (i) an increase in the sinusoid, (ii) a stage of constant high voltage, (in) a linear decrease in voltage, (iv, v) two sinusoidal sections of a decrease in voltage.
  • the coloring of the surface of aluminum or aluminum alloy occurs due to the presence of a photonic band gap in the photonic crystal of aluminum oxide.
  • various coating colors from the visible spectrum can be obtained by maintaining the duration of the anodizing pulses and varying only the voltage or maintaining the voltage and changing only the duration of the pulses.
  • the intense reflection of the incident light flux in narrow spectral ranges which determines the appearance of the color of the coating, is achieved due to the presence of a porous structure with a periodically changing refractive index created by anodizing the metal under cyclically changing conditions.
  • the method for forming colored coatings described in the analogue has a number of significant disadvantages:
  • anodizing is carried out under strictly periodic conditions, which does not allow to achieve the constancy of the optical period of the created structure.
  • the product of the structure period and the effective refractive index characterizing the optical period of the structure inevitably turns out to be smaller for the upper layers oxide film in comparison with the lower ones, since the upper layers are longer in an acidic electrolyte solution in which the anodic oxide is subject to chemical dissolution.
  • This feature of the structure leads to broadening of the spectral regions in which the incident light flux is reflected and, as a result, obtaining a pure color, characterized by a narrow band in the reflection spectrum, becomes impossible;
  • anodizing is carried out during stabilization (control) of the voltage, which does not allow to quickly reduce the voltage without stopping the growth of the oxide film.
  • the anodization mode proposed by the inventors [CN102181902] includes several lengthy stages of a gradual decrease in voltage, which, in turn, leads to significant time costs when obtaining a colored coating and a blurred boundary between the layers of the oxide film, characterized by low and high porosity ;
  • a mandatory stage of the process is the preliminary anodic oxidation of the metal under constant conditions for from 20 minutes to 3 hours.
  • This layer does not create and does not enhance the color of the coating, and, therefore, its exclusion is desirable to accelerate the process of forming a decorative coating.
  • This invention discloses a method for producing photonic crystals from aluminum oxide, the main stages of which are: 1) cleaning and degreasing of the surface of aluminum, electrochemical polishing; 2) anodizing aluminum in the usual way one or more times; 3) dissolution of alumina from the surface of aluminum formed during the anodizing process to obtain a clean aluminum surface; 4) anodizing the surface of aluminum obtained in stage (3) with a constant voltage of 15 to 80 V until the current density is stabilized, and then passing a high current density of 1 -20 mA / cm 2 for 10 s to 10 minutes, followed by passing a low current density of 0.1 to 10 mA / cm 2 for 10 s to 10 minutes, providing a ratio of high and low current density in the range of 2-10: 1.
  • the above procedure is repeated as many times as necessary form layers in a photonic crystal.
  • the processing time at high and low current densities is reduced by 0.5-1 second for each subsequent cycle. Due to the fact that the current density changes cyclically, an aluminum oxide film with a layered structure is formed on the aluminum surface, which has the properties of a one-dimensional photonic crystal.
  • the obtained alumina photonic crystal is placed in HgCh mercury chloride to separate the oxide film from the remaining aluminum, then the oxide film is washed and dried, thereby obtaining an alumina photonic crystal.
  • anodization is carried out with current stabilization.
  • the probability of breakdown of a dielectric film is high, which makes the formation of a photonic crystal with a homogeneous structure over a large area impossible at high current densities. This negatively affects the quality of the resulting coating and the uniformity of the color scheme.
  • the anodization mode proposed by the inventors [CN100572616] can be used only at relatively low current densities, which in turn requires a long duration of electrochemical treatment to form a coating capable of efficiently reflecting light;
  • an obligatory step in the process of obtaining a photonic crystal is the preliminary anodic oxidation of the metal under constant conditions (constant voltage).
  • the layer formed at this stage does not create and does not enhance the color of the coating, and, therefore, its exclusion is desirable to accelerate the process of forming a decorative coating;
  • Metal oxide a compound of a chemical element (metal) with oxygen in the oxidation state -2, in which oxygen is bound to the metal;
  • Porous body is the fraction of the pore volume in the total volume of the porous body
  • Pore cross section - pore cross section with a plane perpendicular to the long axis of the pore
  • “Layered product” includes at least two layers bonded together
  • Decorative coating a layer or a combination of layers located on the surface of a product and giving it the required performance characteristics
  • photonic crystal - a material with a periodic change in dielectric constant on a scale comparable to the wavelength of light
  • One-dimensional photonic crystal - a material with a periodic change in the dielectric constant in one direction at scales comparable to the wavelength of light;
  • photonic band gap a wavelength range forbidden for the propagation of radiation in a photonic crystal and characterized by intense reflection of light incident on the surface of the photonic crystal;
  • Vehicle range the range of electromagnetic radiation with wavelengths from 380 to 780 nm
  • “current stabilization mode” the mode of operation of the DC source, in which the operator sets the current, and the output voltage depends on the set current and the resistance of the external circuit.
  • the current can be either constant or vary according to the program set by the operator;
  • Voltage stabilization mode is the mode of operation of a direct current source, in which the operator sets the voltage, and the current depends on the set voltage and the resistance of the external circuit.
  • the voltage can be either constant or change according to the program set by the operator.
  • the present invention is to develop a reproducible, easy-to-implement method for producing high-quality color decorative coatings, characterized by a change in color when changing the viewing angle.
  • the quality of the decorative coating is determined by the uniformity of color, its saturation, as well as the intensity of reflection of the incident light, which determines the occurrence of color.
  • the technical result achieved by the claimed invention consists in the formation of a decorative coating characterized by pure color from a set of spectral colors, arising due to intense (at least 80%) reflection of incident light only in a narrow spectral region of visible radiation.
  • the technical result is achieved by changing the anodizing conditions that provide a porous oxide film on a metal surface that has the properties of a one-dimensional photonic crystal, reducing both the number of anodizing steps (by eliminating the stage associated with the formation of the preliminary layer) used in the formation of coatings, and reducing the time spent on one cycle during the anodizing process, as well as on the formation of the coating as a whole.
  • Another advantage of the method is its safety / environmental friendliness due to the exclusion of toxic mercury-containing substances from the technology.
  • valve metals A1, Ti, Zr, Hf, Nb, Ta, etc.
  • alloys based on them with a valve metal content of at least 50%, which are uniform in anodizing non-conductive oxide film on their surface.
  • the method of obtaining a decorative coating with a changing color when changing the viewing angle includes the formation of a one-dimensional photonic crystal with a photonic band gap in the visible range using anodic oxidation of a metal surface with cyclically changing parameters, while using current as cyclically changing parameters and voltage, and each cycle consists of two stages: at the first stage, anodization is carried out with stabilization of the current in the range from 0, 1 d 50 mA / cm 2 for a time that ensures the flow of charge from 0.05 to 5 C / cm 2; in the second stage, anodizing is carried out with voltage stabilization, increasing it from the voltage value at the end of the first stage to a value lying in the range from 10 to 200 V, with a decreasing voltage rise rate from 5 V / s to 0 V / s, and withstand the value during the time providing the flow of charge from 0.05 to 5 C / cm 2 , providing a ratio of the maximum voltage in the second stage to the minimum voltage in the first
  • valve metal or an alloy based on it with a valve metal content of at least 50% as a metal surface.
  • metal oxide-dissolving electrolytes such as aqueous or aqueous-organic acid solutions, including sulfuric, orthophosphoric, selenic, hydrofluoric, oxalic, malonic, succinic, acetic, hydroxyethylidene diphosphonic acids and mixtures thereof.
  • the acid concentration in the electrolytes is from 0.1 to 5 mol / l, and anodizing is carried out at a temperature of from -20 ° C to +40 ° C using aqueous organic electrolytes or at a temperature of from -5 ° C to +40 ° C when using aqueous solutions of electrolytes.
  • the current density value can lie in the range from 0.1 to 500 mA / cm 2
  • the voltage is in the range from 0, 1 to 200 V.
  • auxiliary functions including protective, and / or strengthening, and / or anti-glare, and / or absorbing, and / or antibacterial, and / or hydrophobic and / or oleophobic, and these layers can completely or partially penetrate into the channels of the porous structure of the photonic crystal.
  • a one-dimensional photonic crystal from an anodic metal oxide with a porous structure it is additionally formed under and / or in the lower part of the photonic crystal layer absorbing the light transmitted through the photonic crystal.
  • the resulting coating is characterized by the efficiency of reflection of incident light in the region of the photonic band gap. Due to the clear boundary between adjacent layers in the structure of the formed photonic crystals, the proposed method for producing a decorative coating allows to reduce the number of layers of a porous oxide film while maintaining the color intensity at the same level, which reduces the time of formation of a decorative coating.
  • the metal anodization during stabilization (control) of the voltage at the stage of formation of the layer with a large pore diameter increases the stability of the anodization process, minimizing the probability of breakdown of the oxide film and reducing the amount of marriage.
  • the anodization process is carried out during stabilization (control) of the current. This allows you to quickly reduce the voltage, forming a clear boundary between the layers, without stopping the growth of the oxide film, which in turn accelerates the process of formation of a photonic crystal.
  • FIG. 1 is a micrograph of a transverse cleavage of a decorative coating obtained using a scanning electron microscope and showing the porous layered structure of the oxide layer.
  • FIG. Figure 2 presents a graph of the dependence of the set and recorded anodizing parameters (using two cycles as an example), showing the conditions for obtaining a decorative coating.
  • the cycles are separated by a vertical dashed line.
  • Each anodizing cycle consists of two stages (on the graph are divided by vertical dotted lines). At the first stage, the current is set, and voltage is recorded, and in the second stage, voltage is set and current is recorded.
  • FIG. Figure 3 shows the specular reflection spectrum from a decorative coating, illustrating the presence of a narrow region in the visible range, within which light is reflected from the coating surface. Reflection coefficient in this area can exceed 90%.
  • FIG. Figure 4 shows the specular reflection spectra from the decorative coating, taken at various angles of incidence of light on the plane of the sample (8 °, 30 °, and 45 ° relative to the normal).
  • FIG. Figure 5 shows the specular reflection spectrum from a decorative coating obtained in a 1 M solution of sulfuric acid and consisting of 300 layers.
  • FIG. 6 is a cross-sectional diagram of a decorative coating containing two additional layers. One of them performs a protective function, and the absorbing layer enhances the color.
  • FIG. Figure 7 shows the specular reflection spectra from decorative coatings obtained in a 1 M solution of sulfuric acid and consisting of 50 layers.
  • the dotted line shows the specular reflection spectrum from the decorative coating obtained by anodizing, and the solid line from the same coating, additionally containing an absorbing layer in the lower part of the oxide film.
  • the arrows indicate a decrease in the background signal to the left and to the right of the photonic band gap in the presence of an absorbing layer, which leads to an increase in the color saturation.
  • FIG. Figure 8 shows the specular reflection spectra of the decorative coating obtained in a 0.3 M solution of sulfuric acid taken at different angles of incidence of light on the plane of the sample (8 °, 15 °, and 30 ° relative to the normal).
  • the observed shift in the reflection maximum from the region of 620 nm to the region of 580 nm leads to a change in color from red-red under normal incidence of light to yellow-green at an angle of about 30 °.
  • FIG. Figure 9 shows the specular reflection spectra from a decorative coating obtained in a 0.3 M solution of sulfuric acid to (dashed line) and after (solid line) an additional increase in the diameter of the channels in the oxide film by chemical etching in a 1 M solution of sulfuric acid for 60 minutes at a temperature of 25 ° C. Spectra were recorded at an angle of light incidence on the sample plane of 8 ° relative to the normal.
  • FIG. Figure 10 shows the specular reflection spectrum from a decorative coating obtained in a 0.3 M solution of oxalic acid. A reflection maximum is observed in the region of 650 nm, which leads to a red tint of the decorative coating when observed at a normal angle.
  • the claimed invention allows to obtain high-quality decorative coatings on a metal surface, characterized by a color change with a change in the viewing angle.
  • the technology for producing such coatings is based on the electrochemical oxidation (anodization) of a metal surface (for example, a metal foil or substrate), in which a one-dimensional photonic crystal is formed, characterized by the presence of a porous structure with many layers with alternating pore sizes (Fig. 1).
  • the surface of the metal substrate is cleaned by any methods known in the art.
  • carry out its alignment and polishing also by any methods known from the prior art, providing a surface with a roughness not exceeding 100 nm.
  • the roughness should not exceed 10 nm.
  • the cathode can be stainless steel, aluminum or any other material inert in the used electrolyte solution, for example, carbon, gold or platinum.
  • a high-quality coating is formed subject to a certain anodizing regimen, which has a cyclic nature.
  • the nature of the ongoing changes in current and voltage is significant - from low values of current density and voltage to high values within a single cycle (Fig. 2).
  • Each cycle consists of two stages: at the first stage, anodization is carried out with stabilization of the current in the range from 0.1 to 50 mA / cm 2 for a time that ensures the flow of charge from 0.05 to 5 C / cm 2 ; at the second stage, anodizing is carried out with voltage stabilization, increasing it from the voltage value at the end of the first stage to a value lying in the range from 10 to 200 V, and maintaining this value for a time that ensures the flow of charge from 0.05 to 5 C / cm 2 .
  • the number of cycles can lie in the range from 20 to 300 - depending on the color saturation that needs to be obtained.
  • An increase in q leads to a shift of the photonic band gap toward longer wavelengths, and as a result, the color of the coating changes from violet to red.
  • the specular reflection spectrum at an angle of incidence of light close to normal for the yellow-green decorative coating formed by the above method is shown in FIG. 3. It is important to note that the reflection coefficient in the region of the photonic band gap exceeds 90%, which indicates the extremely high quality of the formed one-dimensional photonic crystal. A high reflection coefficient in the photonic band gap leads to a bright color of the decorative coating.
  • the color saturation of the coating increases with increasing number of layers forming a porous structure. So the coating, consisting of 300 layers (example 1, sample 10, the specular reflection spectrum is shown in Fig. 5), has a saturated blue when observed at a normal angle passing through violet to black when the viewing angle changes from the normal to the direction along the plane of the sample.
  • an effective way to increase the color saturation is to create an absorbing layer (see example 3, Fig. 6 and 7).
  • aqueous or aqueous-organic solutions of acids can be used, including sulfuric, orthophosphoric, selenic, hydrofluoric, oxalic, malonic, succinic, acetic, hydroxyethylidene diphosphonic acids and mixtures thereof.
  • acids including sulfuric, orthophosphoric, selenic, hydrofluoric, oxalic, malonic, succinic, acetic, hydroxyethylidene diphosphonic acids and mixtures thereof.
  • an electrolyte with an acid concentration of 0.1 to 5 mol / l is used in the anodizing process, at a temperature of from -20 ° C to +40 ° C for aqueous-organic electrolytes, or at a temperature of from -5 ° C to + 40 ° C for aqueous solutions of electrolytes.
  • the optimum temperature range for anodizing depends on the composition of the electrolyte: the stronger the acid and its concentration, the lower the recommended temperature of the electrolyte.
  • strong acids such as sulfuric or selenium
  • the temperature of low concentration solutions of weak acid electrolytes such as oxalic, malonic and hydroxyethylidene diphosphonic, can be increased to several tens of degrees Celsius.
  • an acid mixture as an electrolyte with a concentration ratio of up to 1: 1. It is preferable to use an electrolyte based on one acid rather than an acid mixture, since a simpler composition facilitates the process of adjusting the concentration of electrolyte components during its long-term use.
  • an increase in pore diameter is carried out by chemical etching in solutions of acids or mixtures thereof at room or elevated temperature.
  • An increase in the diameter of the channels can lead to a substantial increase in the light reflection coefficient in the region of the photonic band gap (Fig. 9) and, as a result, to an increase in the color intensity.
  • an excessive increase in the diameter of the channels can degrade the mechanical characteristics of the resulting coating.
  • the degree of increase in the diameter of the channels can reach up to 2 times, compared with the initial diameter.
  • the final value of the increase in the diameter of the channels is determined by the optimal ratio of mechanical and optical characteristics.
  • the etching time can be up to 5 hours.
  • solutions of various acids and / or mixtures thereof, for example, sulfuric, phosphoric, oxalic, acetic and other acids with a concentration of from 0.1 to 2 mol / L can be used.
  • the preferred temperature of the solution during chemical etching is in the range from 20 to 60 ° C.
  • the formed coating may contain additional layers formed on the surface of the porous layer of the photonic crystal, for example, performing auxiliary functions, including protective, and / or strengthening, and / or anti-reflective, and / or absorbing, and / or antibacterial, and / or hydrophobic and / or oleophobic.
  • the most important of the above layers are the absorbing layer, with which you can achieve enhanced color (see example 3 and Fig. 7), and protective - prevents the penetration of liquids into the channels of the oxide film (see example 2).
  • the formation of a protective layer is important for the following reasons.
  • the pores in its structure are oriented mainly perpendicular to the surface of the decorative coating and are open from the upper side.
  • the position of the photonic band gap which determines the color of the decorative coating, can be estimated using the Bragg-Snell law:
  • w e ff is the effective refractive index
  • d is the periodicity of the structure
  • ⁇ is the angle of incidence of light on the sample (counted from the normal to the film)
  • ⁇ is the wavelength corresponding to the maximum of the reflection band
  • t is the reflection order.
  • a continuous protective layer is formed on the surface of the decorative coating from a material transparent in the visible spectrum, which can be either organic polymeric (polyvinyl chloride, polypropylene, polyester, polyethylene, fluoroplast, etc.) or inorganic materials (ABO3 , Si0 2 , etc.).
  • the protective layer is formed by lamination.
  • the lamination technology is well established in the industry, in particular to protect printed products from various external influences.
  • various materials can be used, for example, polypropylene, polyvinyl chloride, polyester, etc.
  • the outer surface of the decorative coating with a protective layer the latter can partially penetrate the channels of the oxide film (see Fig. 6).
  • the protective layer can be formed in other ways, including, but not limited to:
  • the formation of the absorbing layer can significantly enhance the color of the decorative coating by increasing the ratio of the useful signal / background. Coatings obtained during even 25 cycles with an absorbing layer have an intense color, while without it they are almost transparent.
  • the absorbent layer can also be formed in other ways. For example, by staining with dark paint. The best effect is achieved when using black paint. Various types of paints are suitable for coloring, for example, those used in the automotive industry. To achieve the best effect, the thickness of the paint layer should exceed 3 microns.
  • an absorbent coating in the form of a black film with a thickness of more than 10 microns on one side of the photonic crystal.
  • glue for attaching the absorbing layer, it is necessary that it does not lose its properties under the conditions of further operation of the decorative coating.
  • FIG. Figure 6 shows an example of a decorative coating structure that simultaneously contains a protective layer to prevent liquids from entering the channels of the porous oxide film (Example 2) and an absorbing layer to increase the color intensity (Example 3).
  • micro- and nanostructured polymer layers and nanocomposites based on them can be applied, which provide strengthening, antibacterial, anti-reflective, hydrophobic or oleophobic functions or combinations thereof.
  • Decorative coatings of various colors on the surface of aluminum were obtained as follows. At the preliminary stage, aluminum plates (thickness 0.1 mm, aluminum content no less than 99.99%) were subjected to electrochemical polishing in a mixture containing 185 g / l CrO3 and 878 ml / l H3PO4, at a temperature of 80 ° C and vigorous stirring. The anode plate A1 was polished, and the cathode was a similar aluminum plate, which exceeded the size of the anode by 2–10 times in area. The process was carried out in a pulsed galvanostatic mode at a current density of 400 mA / cm 2 . The pulse length was 3 seconds, the interval between pulses was 40 seconds.
  • the duration of electrochemical polishing was limited to 30 cycles. After polishing A1, the plates were washed with water to remove an electrolyte solution from their surface. Polishing ensured the production of A1 plates with an average roughness R a of not more than 10 nm.
  • the prepared aluminum plate was placed in an electrochemical bath. Solutions of sulfuric and oxalic acids served as the electrolyte (see table. 1). During anodization, the electrolyte was intensively mixed, and its temperature was maintained at a constant value (see table. 1). To form an oxide film with variable porosity, which subsequently acts as a photonic crystal that reflects light of certain wavelengths, the anodization method was used, cyclically changing the current density and voltage. Moreover, each cycle consisted of two stages: at the first stage, anodizing was performed in the mode of current stabilization, and at the second stage, voltage stabilization. First (stage 1, Fig. 2), anodization was carried out in the galvanostatic mode at a current density (see table. 1).
  • stage 2 Fig. 2
  • the anodizing voltage was increased to U2 at a speed of v 2 and held at this value until the charge qi flowed (see Table 1).
  • the charges and qi were counted from the beginning of the corresponding stage and found by numerical integration of the current versus time
  • the decorative coating has a structure with variable porosity, changing quasiperiodically in the direction normal to the surface of the coating, while the pores are oriented mainly perpendicular to the surface of the decorative coating.
  • the layered structure is formed due to different anodizing voltages at successive stages of the electrochemical oxidation process. The ratio of the average voltage in the second stage and the corresponding value in the first stage for all examples exceeded 1.5. Note that when anodizing aluminum at high current densities (more than 15 mA / cm 2 ), intensive cooling of the electrolyte is required to maintain its temperature at a constant value to prevent breakdown of the oxide film.
  • Table 1 Parameters for producing decorative coatings on the surface of aluminum.
  • the color of the resulting decorative coatings at a normal angle is shown in table 1. At the same time, it changed (see table 2) when the sample was rotated, which is associated with the diffractive nature of the appearance of the color. Table 2. The color change of decorative coatings with varying viewing angles.
  • a colored decorative coating with a protective layer on its surface was formed as follows.
  • a one-dimensional photonic crystal was formed on the metal surface using anodization method from the anodic oxide of the metal to be treated (see Example 1).
  • the pores formed during the anodic oxidation of the metal in metal oxide-dissolving electrolytes are oriented mainly perpendicular to the surface of the decorative coating and are open from the upper side.
  • a decorative coating on the surface of aluminum with enhanced color was obtained as follows.
  • a one-dimensional photonic crystal was formed from the anodic oxide of the metal to be treated on the metal surface by anodization (see Example 1). Then, to reduce the reflectivity of aluminum, the metal was deposited using cathodic reduction in the lower part of the channels of the oxide film (closer to the metal) (scheme see in FIG. 6).
  • a solution containing 18 g / l SnS0 4 and 20 g / l H2SO4 was used as an electrolyte for metal deposition. The deposition was carried out in a two-electrode configuration by increasing the voltage at a speed of 0.25 V / s from 0 to 6 V and then maintaining it at a constant voltage for 300 s.
  • the channels in the lower part of the oxide film were filled with nanostructured tin, which is black due to the small particle size.
  • the presence of an absorbing layer of nanostructures in the channels of the oxide film is manifested in a significant decrease in the background intensity (see Fig. 7). This, in turn, leads to an increase in the signal / background ratio, and, as a result, to an increase in color.
  • the sample of the decorative coating after anodizing had only a slightly noticeable greenish tint, while after electrodeposition of tin a saturated green color was observed at a normal angle.
  • a decorative coating on the surface of the valve metal alloy was prepared as follows.
  • the surface of the D16T alloy (A1 content 90.9-94.7%) was anodized in a 0.3 M sulfuric acid solution.
  • Stainless steel was used as the cathode.
  • the electrolyte was intensively mixed, and its temperature was maintained in the range from 0 to 3 ° C.
  • the current density and voltage were cyclically changed during the anodization process.
  • each cycle consisted of two stages: at the first stage, anodizing was performed in the mode of current stabilization, and at the second stage, voltage stabilization.
  • the ratio of the average voltage in the second stage and the corresponding value in the first stage was 1.8.
  • Charges and qi were counted from the beginning of the corresponding stage and the numerical integration of the time dependence of the current was found. To form coatings of different colors, the parameters q ⁇ and qi were changed. The charges of the corresponding stages for each subsequent anodizing cycle were reduced by 0.1%. The number of anodizing cycles was 80.
  • the alloy with a porous oxide film on its surface was removed from the electrochemical bath, washed with water, and dried in air.
  • the specular reflection spectra at various angles of incidence of light on the surface of the decorative coating are shown in FIG. 8. It is easy to see that with an increase in the angle of incidence of light, the reflection maximum shifts toward shorter wavelengths, which is accompanied by a change in color from orange to green.
  • a decorative orange-red coating on the surface of aluminum was prepared as follows.
  • the aluminum surface was anodized in a 0.3 M solution of oxalic acid ( ⁇ 2 ⁇ 2 ⁇ 4).
  • a platinum wire was used as a cathode.
  • the electrolyte was intensively mixed, and its temperature was maintained in the range from 5 to 10 ° C.
  • the current density and voltage were cyclically changed during the anodization process.
  • each cycle consisted of two stages: at the first stage, anodizing was performed in the mode of current stabilization, and at the second stage, voltage stabilization.
  • the ratio of the average voltage in the second stage and the corresponding value in the first stage was 1,5.
  • the charges and qi were counted from the beginning of the corresponding stage and found by numerical integration of the time dependence of the current.
  • the charges of the corresponding stages for each subsequent anodizing cycle were reduced by 0.1%.
  • the number of anodizing cycles was 80.
  • the alloy with a porous oxide film on its surface was removed from the electrochemical bath, washed with water, and dried in air.
  • the spectrum of specular reflection when light is incident on the surface of the decorative coating at an angle close to normal is shown in FIG. 10.
  • the pronounced reflection maximum at 660 nm determines the orange-red color of the coating at a normal angle.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Nonlinear Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne la technologie de formation d'un revêtement décoratif qui, observé à un angle droit, peut prendre n'importe quelle couleur de l'arc-en-ciel qui varie en fonction de l'angle d'observation. Le revêtement qui réfléchit le flux lumineux qui tombe sur lui dans des bandes spectrales étroites est constitué d'un oxyde de métal valve obtenu par l'anodisation et possède une structure à porosité variable qui change périodiquement dans la direction de la normale par rapport au revêtement de surface, les pores étant orientés principalement de façon perpendiculaire par rapport à la surface de revêtement décoratif. Lors de la formation du revêtement décoratif, la porosité provisoire est créée dans la couche d'oxyde par la modification périodique des conditions d'anodisation du métal dont la tension et la densité de courant en alternant les modes de stabilisation de courant et de stabilisation de tension. Ce procédé permet d'obtenir une frontière bien tracée entre les couches à faible porosité et grande porosité, ce qui augmente l'effet de réflexion de lumière et, partant, renforce la saturation de lumière et l'intensité de coloration du revêtement décoratif.
PCT/RU2016/050086 2015-12-28 2016-12-28 Procédé de formation d'un revêtement couleur décoratif par anodisation WO2017116291A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2015156041A RU2620801C1 (ru) 2015-12-28 2015-12-28 Способ формирования цветного декоративного покрытия с помощью анодирования
RU2015156041 2015-12-28

Publications (1)

Publication Number Publication Date
WO2017116291A1 true WO2017116291A1 (fr) 2017-07-06

Family

ID=59032013

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2016/050086 WO2017116291A1 (fr) 2015-12-28 2016-12-28 Procédé de formation d'un revêtement couleur décoratif par anodisation

Country Status (2)

Country Link
RU (1) RU2620801C1 (fr)
WO (1) WO2017116291A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109989086A (zh) * 2019-04-19 2019-07-09 河北工业大学 一种具有高饱和度结构色的多孔氧化铝光子晶体薄膜的制备方法
CN113818062A (zh) * 2021-09-10 2021-12-21 西北有色金属研究院 一种利用低酸度溶液阳极氧化铌或铌合金的方法
CN113981501A (zh) * 2021-12-09 2022-01-28 陕西宝成航空仪表有限责任公司 高发射率阳极氧化黑色热控涂层工艺
WO2022063230A1 (fr) * 2020-09-25 2022-03-31 北京华宇创新钽铌科技有限公司 Procédé de fabrication d'article coloré et coque de téléphone mobile

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2724308C1 (ru) * 2019-03-20 2020-06-22 Сергей Евгеньевич Кушнир Оптический фильтр с многослойной структурой из анодного оксида алюминия и способ его формирования с помощью анодирования

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181902A (zh) * 2011-04-21 2011-09-14 华南理工大学 一种对铝及其合金表面进行着色的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2077612C1 (ru) * 1993-09-14 1997-04-20 Мамаев Анатолий Иванович Способ нанесения покрытия на вентильные металлы и их сплавы
JP4536866B2 (ja) * 1999-04-27 2010-09-01 キヤノン株式会社 ナノ構造体及びその製造方法
CN100572616C (zh) * 2007-09-26 2009-12-23 武汉大学 一种高质量氧化铝光子晶体的制备方法
RU2555366C2 (ru) * 2010-08-16 2015-07-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет имени М.В.Ломоносова" (МГУ) Способ получения анодного оксида алюминия с высокоупорядоченной пористой структурой и способ формирования массивов анизотропных наноструктур на его основе

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181902A (zh) * 2011-04-21 2011-09-14 华南理工大学 一种对铝及其合金表面进行着色的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIKUCHI TATSUYA ET AL.: "Fabrication of self -ordered porous alumina via etidronic acid anodizing and structural color generation from submicrometer-scale dimple array", ELECTROCHIMICA ACTA, vol. 156, 2015, pages 235 - 243, XP029200670 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109989086A (zh) * 2019-04-19 2019-07-09 河北工业大学 一种具有高饱和度结构色的多孔氧化铝光子晶体薄膜的制备方法
CN109989086B (zh) * 2019-04-19 2020-11-03 河北工业大学 一种具有高饱和度结构色的多孔氧化铝光子晶体薄膜的制备方法
WO2022063230A1 (fr) * 2020-09-25 2022-03-31 北京华宇创新钽铌科技有限公司 Procédé de fabrication d'article coloré et coque de téléphone mobile
CN113818062A (zh) * 2021-09-10 2021-12-21 西北有色金属研究院 一种利用低酸度溶液阳极氧化铌或铌合金的方法
CN113981501A (zh) * 2021-12-09 2022-01-28 陕西宝成航空仪表有限责任公司 高发射率阳极氧化黑色热控涂层工艺
CN113981501B (zh) * 2021-12-09 2022-10-04 陕西宝成航空仪表有限责任公司 高发射率阳极氧化黑色热控涂层工艺

Also Published As

Publication number Publication date
RU2620801C1 (ru) 2017-05-29

Similar Documents

Publication Publication Date Title
WO2017116291A1 (fr) Procédé de formation d'un revêtement couleur décoratif par anodisation
US11131036B2 (en) Cosmetic anodic oxide coatings
US9487879B2 (en) Anodized films with branched pore structures
KR101832059B1 (ko) 내지문 특성을 가지고 있는 장식용 타이타늄 산화막 제조 방법
Karambakhsh et al. Pure commercial titanium color anodizing and corrosion resistance
Kushnir et al. Anodizing with voltage versus optical path length modulation: a new tool for the preparation of photonic structures
JP3279958B2 (ja) 反射率向上複合層を有するリフレクタ及びその製造方法
Xu et al. Optical properties and color generation mechanism of porous anodic alumina films
CN100572616C (zh) 一种高质量氧化铝光子晶体的制备方法
KR102156628B1 (ko) 알루미늄 부재 및 그 제조 방법
CN102597331A (zh) 阳极化和抛光表面处理
US20140209467A1 (en) Method For Producing White Anodized Aluminum Oxide
Li et al. Crack-free 2D-inverse opal anatase TiO 2 films on rigid and flexible transparent conducting substrates: low temperature large area fabrication and electrochromic properties
EP0714039B1 (fr) Surface d'aluminium pour application dans le technique d'éclairage
Wei et al. Easy preparation of anodic aluminum oxide photonic crystal films with tunable structural colors
EP3652363A1 (fr) Produit laminé en alliage d'aluminium à couleurs iridescentes intenses
EP3088565B1 (fr) Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier
US9435050B2 (en) Method of making a porous TiO2 photonic film
KR102136920B1 (ko) 표면 플라즈몬 구조 층의 신속한 형성 방법
CN109989086B (zh) 一种具有高饱和度结构色的多孔氧化铝光子晶体薄膜的制备方法
Shelkovnikov et al. Enhanced reflective interference spectra of nanoporous anodic alumina films by double electrochemical deposition of chemical metal nanoparticles
RU2724308C1 (ru) Оптический фильтр с многослойной структурой из анодного оксида алюминия и способ его формирования с помощью анодирования
JP3816754B2 (ja) グレー系色複合皮膜を有するアルミニウム材及びアルミニウム合金材並びにその製造方法
WO2021215939A1 (fr) Procédé d'application de revêtements de couleur sur des alliages
Mohammadpour et al. Comparison of various anodization and annealing conditions of titanium dioxide nanotubular film on MB degradation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16882192

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1)EPC

122 Ep: pct application non-entry in european phase

Ref document number: 16882192

Country of ref document: EP

Kind code of ref document: A1