CN110128873B - Black diamond mirror silver pigment and manufacturing method thereof - Google Patents
Black diamond mirror silver pigment and manufacturing method thereof Download PDFInfo
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- CN110128873B CN110128873B CN201811062271.4A CN201811062271A CN110128873B CN 110128873 B CN110128873 B CN 110128873B CN 201811062271 A CN201811062271 A CN 201811062271A CN 110128873 B CN110128873 B CN 110128873B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a black diamond mirror silver pigment and a manufacturing method thereof. The black diamond mirror silver pigment consists of 10-15% of flaky composite metal particles, 84-90% of a dispersing agent and 0-1.5% of an auxiliary agent; the manufacturing method comprises the following steps: coating a resin layer with the thickness of 1-2 microns on a plastic film substrate, and depositing aluminum and nickel on the surface of the resin layer in sequence by using a PVD (physical vapor deposition) method to form a composite metal film with the thickness of nanometer; dissolving the resin by using a solvent, and separating the composite metal film from the base material to obtain a mixed solution consisting of the solvent, the resin and the composite metal sheet; and thirdly, crushing and filtering the mixture, adding an auxiliary agent, and adjusting the solid content by using a solvent to obtain the black diamond mirror silver pigment consisting of the solvent, the auxiliary agent and the composite metal sheet with the nanometer thickness.
Description
Technical Field
The invention relates to the technical field of printing ink, in particular to a black diamond mirror silver pigment and a manufacturing method thereof.
Background
The mirror silver is a pasty high-grade metal pigment prepared by taking aluminum as a material, and dispersing aluminum sheet particles with the thickness of 20-40 nm in an organic solvent by utilizing a PVD (physical vapor deposition) method, and after mirror ink prepared by the paste is printed on a printing surface, nano aluminum sheets are arranged in parallel, so that a light reflection effect like a silver mirror is formed, and the mirror silver is named as 'mirror silver'.
The mirror silver is silvery white and has single color, and the market needs the mirror silver with other colors all the time. In order to obtain the black diamond mirror silver effect, the ink industry adopts a method of adding black organic dye into mirror silver, although the black diamond color can be obtained, the mirror effect and the metal luster specific to the mirror silver are greatly weakened, and at present, the market lacks a mirror pigment which can not only keep the mirror effect and the metal luster of the mirror silver, but also has the black diamond color.
Disclosure of Invention
The invention provides a black diamond mirror silver pigment which takes aluminum and nickel as composite materials, not only keeps the mirror effect and the metal luster not weakened as the existing mirror silver, but also has the black diamond color, and can ensure that the black diamond mirror silver pigment has controllable color depth by adjusting the proportion of the aluminum and the nickel. The invention also aims to provide a method for manufacturing the black diamond mirror silver pigment through vacuum sputtering coating, vacuum ion coating or vacuum evaporation coating.
The technical scheme of the invention is that the black diamond mirror-like silver pigment is characterized by comprising flaky composite metal particles, a dispersant and an auxiliary agent; the black diamond mirror silver pigment is prepared from the following ingredients in percentage by weight:
10-15% of composite metal sheet particles, 84-90% of dispersing agent and 0-1.5% of auxiliary agent.
Preferably, the method comprises the following steps: the flaky composite metal particles refer to a multilayer nano-film formed by compounding aluminum and nickel, the multilayer structure of the flaky composite metal particles can be aluminum-nickel-aluminum or aluminum-nickel or nickel-aluminum-nickel, the total thickness of the multilayer film is 8-20 nm, the particle size (d50) is 5-20 μm, and the flaky composite metal particles comprise the following components in percentage by mass: 60-100% of aluminum and 0-40% of nickel; the dispersing agent is propylene glycol methyl ether, propylene glycol methyl ether acetate and ethylene glycol monobutyl ether with the purity of more than 99.5 percent; the auxiliary agent is an anti-settling agent.
Another technical solution of the present invention is a method for producing the black diamond mirror-like silver pigment, comprising the steps of:
coating a resin layer with the thickness of 1-2 microns on a plastic film substrate, and depositing aluminum and nickel on the surface of the resin layer in sequence by using a PVD (physical vapor deposition) method to form a composite metal film with the thickness of nanometer;
dissolving the resin by using a solvent, and separating the composite metal film from the base material to obtain a mixed solution consisting of the solvent, the resin and the composite metal sheet;
and thirdly, crushing and filtering the mixture, adding an auxiliary agent, and adjusting the solid content by using a solvent to obtain the black diamond mirror silver pigment consisting of the solvent, the auxiliary agent and the composite metal sheet with the nanometer thickness.
Preferably, the method comprises the following steps: the PVD method of the first step is a continuous winding type vacuum sputtering coating, a continuous winding type vacuum ion coating, or a continuous winding type vacuum evaporation coating.
Preferably, the method comprises the following steps: the process includes: the PET film coated with the resin layer is placed in a continuous winding magnetron sputtering coating machine, a high-purity nickel target and two high-purity aluminum targets are combined and arranged according to the sequence of aluminum-nickel-aluminum, and the sputtering operation is mainly carried out under the following conditions: the winding speed is 10m/min, the vacuum degree of the cryogenic pump is 2.5 multiplied by 10-1Pa, molecular pump vacuum degree 10-1Pa, degree of vacuum in winding zone 5.8X 10-1Pa, vacuum degree of film coating area 1.2X 10-1Pa, direct current 10A, and argon as discharge working gas, and forming a smooth and compact aluminum-nickel-aluminum composite metal layer with the thickness of 8-9 nm by sputtering coating.
Preferably, the method comprises the following steps: the process includes: placing the PET film coated with the resin layer in a continuous winding magnetron sputtering coating machine, adopting the combination of two high-purity nickel targets and four high-purity aluminum targets, arranging according to the sequence of nickel-aluminum-nickel, and carrying out sputtering operation under the main conditions: the winding speed is 15m/min, the vacuum degree of the cryogenic pump is 2.5 multiplied by 10-1Pa, molecular pump vacuum degree 10- 1Pa, degree of vacuum in winding zone 5.8X 10-1Pa, vacuum degree of film coating area 1.2X 10-1Pa, direct current 10A, and discharge working gas argon; and sputtering and coating to form a smooth and compact nickel-aluminum-nickel composite metal layer with the thickness of 10-12 nm.
Preferably, the method comprises the following steps: the process step three further includes: and (3) stirring the liquid-solid mixture at a high speed for crushing, filtering to separate resin, adding propylene glycol methyl ether acetate into the obtained slurry to adjust the solid content, and adding 1% of an anti-settling agent to obtain the black diamond mirror-like silver pigment of the dark green slurry fluid, wherein the content of the composite metal is 15%, the content of propylene glycol methyl ether acetate serving as a solvent is 84%, the anti-settling agent is 1%, the thickness of the particle sheet is 8-9 nm, and the particle size (d50) is 5-6 mu m.
Preferably, the method comprises the following steps: the process step three further includes: and (2) stirring the liquid-solid mixture at a high speed, crushing, filtering to separate resin, and mixing the flaky alloy slurry, the stearic acid and the propylene glycol monomethyl ether according to a mass ratio of 10: 1: 89 mixing, reacting at the rotating speed of 50 revolutions per minute and the temperature of 60 ℃ for 5 hours to ensure that hard fatty acid is adsorbed on the surface of the laser sheet-shaped composite metal, and adding 1 percent of anti-settling agent to prepare black diamond mirror surface silver paste of dark green slurry-like fluid; the thickness of the particle piece of the black diamond mirror silver paste is 10-12 nm, the particle size (d50) is 9-10 microns, the content of composite metal of the paste is 10%, the solvent propylene glycol methyl ether is 89%, and the anti-settling agent is 1%.
Preferably, the method comprises the following steps: the plastic film in the process is polyethylene terephthalate (PET) or polypropylene (PP).
Compared with the prior art, the invention has the beneficial effects that:
the black diamond mirror surface silver pigment disclosed by the invention has the advantages that the nano composite metal sheet made of the aluminum and nickel composite metal material has different absorption and reflectivity for different wavelengths of light from pure aluminum, so that the change of the color depth of the black diamond can be realized by adjusting the ratio of aluminum to nickel.
The black diamond mirror surface silver pigment can accurately control the thickness of the composite metal membrane, so that the light absorption and reflectivity are controlled, and the color of the black diamond can be adjusted to a certain degree.
The black diamond mirror silver pigment is compounded by aluminum and nickel, so that the water resistance of the black diamond mirror silver pigment is enhanced compared with that of the existing mirror silver.
The black diamond mirror-surface silver pigment prepared by the invention has uniform thickness of composite metal flaky particles, smooth surface, thickness of 8-20 nm and particle size (d50) of 5-20 microns; the scattering and diffuse reflection of the surface and edge light is not serious, thereby ensuring the brightness, metallic feeling and mirror effect of the prior mirror silver.
The black diamond mirror silver pigment prepared by the method is a blackish green pasty fluid in appearance, and is stable in storage and free of settlement.
Detailed Description
The invention will be further described in detail with reference to the following examples:
[ example 1]
The black diamond mirror silver pigment is a blackish green slurry fluid in appearance and consists of flaky composite metal particles, a dispersing agent and an auxiliary agent; the black diamond mirror silver pigment is prepared from the following ingredients in percentage by weight:
15% of composite metal sheet particles, 84% of dispersing agent and 1% of auxiliary agent.
In the embodiment, the multilayer structure of the composite metal sheet particle is an aluminum-nickel-aluminum type, the total thickness is 8-9 nm, and the particle size (d50) is 5-6 μm; the dispersant is propylene glycol methyl ether acetate; the auxiliary agent is an anti-settling agent.
The preparation method of the black diamond mirror silver pigment comprises the following steps:
coating a transparent resin layer with the thickness of 1-2 microns on a PET (polyethylene terephthalate) film with the thickness of 16 microns on a coating machine;
arranging the PET film coated with the resin layer in a continuous winding magnetron sputtering coating machine, combining a high-purity nickel target and two high-purity aluminum targets, arranging the targets in an aluminum-nickel-aluminum sequence, and performing sputtering operation under the main conditions: the winding speed is 10m/min, the vacuum degree of the cryogenic pump is 2.5 multiplied by 10-1Pa, molecular pump vacuum degree 10-1Pa, degree of vacuum in winding zone 5.8X 10-1Pa, vacuum degree of film coating area 1.2X 10-1Pa, direct current 10A, and discharge working gas argon. Sputtering and coating to form a smooth and compact aluminum-nickel-aluminum composite metal layer with the thickness of 8-9 nm;
thirdly, the PET composite metal film is placed in propylene glycol methyl ether acetate to be soaked, so that the resin layer is dissolved, the metal layer is separated from the film, and a liquid-solid mixture containing the composite metal sheet, the resin and the propylene glycol methyl ether acetate is obtained;
fourthly, the liquid-solid mixture is stirred at a high speed to be crushed, the resin is separated by filtering, propylene glycol methyl ether acetate is added into the obtained slurry to adjust the solid content, and 1% of anti-settling agent is added to prepare the black diamond mirror-like silver pigment of the embodiment 1.
[ example 2]
The black diamond mirror silver pigment is a blackish green slurry fluid in appearance and consists of flaky composite metal particles, a dispersing agent and an auxiliary agent; the black diamond mirror silver pigment is prepared from the following ingredients in percentage by weight:
10% of composite metal sheet particles, 89% of dispersing agent and 1% of auxiliary agent.
In the embodiment, the multilayer structure of the composite metal sheet particle is a nickel-aluminum-nickel type, the total thickness is 10-12 nm, and the particle size (d50) is 9-10 μm; the dispersant is propylene glycol methyl ether; the auxiliary agent is an anti-settling agent.
The preparation method of the black diamond mirror silver pigment comprises the following steps:
coating a transparent resin layer with the thickness of 1-2 microns on a PET (polyethylene terephthalate) film with the thickness of 12 microns on a coating machine;
placing the PET film coated with the resin layer in a continuous winding magnetron sputtering coating machine, combining two high-purity nickel targets and four high-purity aluminum targets, arranging the high-purity nickel targets and the high-purity aluminum targets in the order of nickel-aluminum-nickel, and performing sputtering operation under the main conditions: the winding speed is 15m/min, the vacuum degree of the cryogenic pump is 2.5 multiplied by 10-1Pa, molecular pump vacuum degree 10-1Pa, degree of vacuum in winding zone 5.8X 10-1Pa, vacuum degree of film coating area 1.2X 10-1Pa, direct current 10A, and argon as discharge working gas, and forming a smooth and compact nickel-aluminum-nickel composite metal layer with the thickness of 10-12 nm by sputtering coating;
thirdly, the PET composite metal film is placed in propylene glycol methyl ether for soaking, so that the resin layer is dissolved, the metal layer is separated from the film, and a liquid-solid mixture containing the composite metal sheet, the resin and the propylene glycol methyl ether is obtained;
fourthly, the liquid-solid mixture is stirred at a high speed to be crushed, then the liquid-solid mixture is filtered to separate the resin, and the flaky alloy slurry, the stearic acid and the propylene glycol monomethyl ether are mixed according to the mass ratio of 10: 1: 89 and reacting at 60 ℃ for 5 hours at the rotating speed of 50 rpm to adsorb hard fatty acid on the surface of the laser sheet-shaped composite metal, and adding 1 percent of anti-settling agent to prepare the black diamond mirror surface silver paste of the embodiment 2.
[ application example ]
Taking 45 g of the black diamond mirror-surface silver paste prepared in the example 1 and 45 g of special mirror-surface resin (prepared by using a solvent), uniformly mixing the two, adding propylene glycol methyl ether of which the amount is not more than 5 g according to the requirement to prepare the ink into proper viscosity, printing the prepared ink on a glass mobile phone back plate by using a 420-mesh screen, drying the ink, baking the ink at 120 ℃ for 30min, and taking out the ink to obtain a performance detection result as follows:
mirror surface effect: the black diamond mirror surface with metal luster is observed in a standard lamp source box by visual observation, eyebrows and fine parts can be clearly identified by the mirror, and the mirror surface effect is good.
Shielding property: and the ink printing layer is uniform in thickness and good in light shielding property when observed in a standard light source box.
Boiling test: and (3) putting the glass plate into water, boiling for 30min, taking out, drying, observing, and slightly reducing the definition of the mirror surface to be qualified.
And (3) carrying out a hundred-grid test: and 3M adhesive tape method, qualified.
The above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.
Claims (4)
1. The black diamond mirror-surface silver pigment is characterized by consisting of flaky composite metal particles, a dispersing agent and an auxiliary agent; the black diamond mirror silver pigment is prepared from the following ingredients in percentage by weight:
10-15% of composite metal sheet particles, 84-90% of dispersing agent and 0-1.5% of auxiliary agent; the flaky composite metal particles refer to a multi-layer nano membrane formed by compounding aluminum and nickel, the multi-layer structure of the flaky composite metal particles can be aluminum-nickel-aluminum or aluminum-nickel or nickel-aluminum-nickel, the thickness of the flaky composite metal particles is 8-20 nm, the particle size (d50) is 5-20 mu m, and the auxiliary agent is an anti-settling agent.
2. A method for producing a black diamond mirror-like silver pigment, comprising the steps of:
coating a resin layer with the thickness of 1-2 microns on a plastic film substrate, and depositing aluminum and nickel on the surface of the resin layer in sequence by using a PVD (physical vapor deposition) method to form a composite metal film with the thickness of nanometer; the PVD method is continuous winding type vacuum sputtering coating or continuous winding type vacuum ion coating or continuous winding type vacuum evaporation coating; the plastic film is polyethylene terephthalate (PET) or polypropylene (PP);
the process includes: placing the PET film coated with the resin layer in a continuous winding magnetron sputtering coating machine, and adopting high-purity nickelThe target is combined with two high-purity aluminum targets, the targets are arranged according to the sequence of aluminum-nickel-aluminum, and the main conditions of the sputtering operation are as follows: the winding speed is 10m/min, the vacuum degree of the cryogenic pump is 2.5 multiplied by 10-1Pa, molecular pump vacuum degree 10-1Pa, degree of vacuum in winding zone 5.8X 10-1Pa, vacuum degree of film coating area 1.2X 10-1Pa, direct current 10A, and argon as discharge working gas, and forming a smooth and compact aluminum-nickel-aluminum composite metal layer with the thickness of 8-9 nm by sputtering coating;
dissolving the resin by using a solvent, and separating the composite metal film from the base material to obtain a mixed solution consisting of the solvent, the resin and the composite metal sheet;
thirdly, crushing and filtering the mixture, adding an auxiliary agent, and adjusting the solid content by using a solvent to obtain the black diamond mirror silver pigment consisting of the solvent, the auxiliary agent and the composite metal sheet with the nanometer thickness;
the process step three further includes: and (3) stirring the liquid-solid mixture at a high speed for crushing, filtering to separate resin, adding propylene glycol methyl ether acetate into the obtained slurry to adjust the solid content, and adding 1% of an anti-settling agent to obtain the black diamond mirror-like silver pigment of the dark green slurry fluid, wherein the content of the composite metal is 15%, the content of propylene glycol methyl ether acetate serving as a solvent is 84%, the anti-settling agent is 1%, the thickness of the particle sheet is 8-9 nm, and the particle size (d50) is 5-6 mu m.
3. The method for manufacturing a black diamond mirror surface silver pigment according to claim 2, wherein the step further includes: placing the PET film coated with the resin layer in a continuous winding magnetron sputtering coating machine, adopting the combination of two high-purity nickel targets and four high-purity aluminum targets, arranging according to the sequence of nickel-aluminum-nickel, and carrying out sputtering operation under the main conditions: the winding speed is 15m/min, the vacuum degree of the cryogenic pump is 2.5 multiplied by 10-1Pa, molecular pump vacuum degree 10-1Pa, degree of vacuum in winding zone 5.8X 10-1Pa, vacuum degree of film coating area 1.2X 10-1Pa, direct current 10A, and discharge working gas argon; and sputtering and coating to form a smooth and compact nickel-aluminum-nickel composite metal layer with the thickness of 10-12 nm.
4. The method for producing a black diamond mirror-like silver pigment according to claim 2, wherein the step iii further comprises: and (2) stirring the liquid-solid mixture at a high speed, crushing, filtering to separate resin, and mixing the flaky alloy slurry, the stearic acid and the propylene glycol monomethyl ether according to a mass ratio of 10: 1: 89 mixing, reacting for 5 hours at the rotating speed of 50 revolutions per minute and the temperature of 60 ℃ to ensure that the hard fatty acid is adsorbed on the surface of the sheet-shaped composite metal, and adding 1 percent of anti-settling agent to prepare black diamond mirror surface silver paste of dark green slurry-like fluid; the thickness of the particle piece of the black diamond mirror silver paste is 10-12 nm, the particle size (d50) is 9-10 microns, the content of composite metal of the paste is 10%, the solvent propylene glycol methyl ether is 89%, and the anti-settling agent is 1%.
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"Commercial white paint as back surface reflector for thin-film solar cells";Berger,Olaf等;《SOLAR ENERGY MATERIALS AND SOLAR CELLS》;20070430;第91卷(第13期);第1215-1221页 * |
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