CN115613020A - Metal blackening treatment method - Google Patents
Metal blackening treatment method Download PDFInfo
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- CN115613020A CN115613020A CN202211158278.2A CN202211158278A CN115613020A CN 115613020 A CN115613020 A CN 115613020A CN 202211158278 A CN202211158278 A CN 202211158278A CN 115613020 A CN115613020 A CN 115613020A
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 239000007769 metal material Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000004380 ashing Methods 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229940000207 selenious acid Drugs 0.000 claims abstract description 7
- 239000011669 selenium Substances 0.000 claims abstract description 7
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 14
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000008363 phosphate buffer Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 description 17
- 229910001092 metal group alloy Inorganic materials 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 239000000956 alloy Substances 0.000 description 9
- 239000006260 foam Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical group [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to a metal blackening treatment method, which comprises the following steps: firstly, coating ashing liquid on a metal material in an inert atmosphere, and heating to obtain the metal material with an ashed surface; wherein the ashing liquid is an organic mixed liquid containing nickel salt and selenium; then soaking the ashed metal material on the surface in the blackening liquid to obtain the metal material with a black film layer on the surface; wherein the blackening liquid is a mixed liquid containing selenious acid, phosphate, copper sulfate, citrate and a stabilizer. Compared with the prior art, the invention realizes a safe, simple and efficient surface blackening treatment mode, obtains a compact light-absorbing blackening coating, and has better application prospect.
Description
Technical Field
The invention belongs to the technical field of light absorption materials, and relates to a metal blackening treatment method.
Background
The metal blackening adopts chemical, electrochemical and physical methods to generate a layer of uniform and compact black film on the surface of a workpiece. Since the invention of the thermokalite phosphate blackened oxidized metal by german scientists in the last 90 s, the development of a metal surface black treatment process is relatively mature, and the process is successfully applied to industries such as light industry, machinery, daily hardware, artware, building decoration, military industry and the like. Black is the most common decorative appearance and is widely used in lighters, bicycles, display devices, lamps, architectural decorations, daily hardware, clothing accessories, electronic products and the like. The metal blackens and has good extinction ability. For example, products such as camera parts, precision optical instruments, microscopes, binoculars, and telescope tubes are blackened. The corrosion resistance and the wear resistance of parts in the upper cabin of aviation and aerospace are high, and the parts need to be subjected to extinction treatment so as to prevent dazzling reflected light from causing dizziness or disturbing sight. Automobile parts such as automobile bumpers, sun-shading equipment, extinction lampshade, brake, instrument panel and screw instrument panel of instrument panel, wiper, front lamp frame and the like are also often subjected to blackening treatment. However, the blackening film prepared by the existing blackening technology is easy to fade and scratch and is not in line with the requirements of actual life.
Disclosure of Invention
The invention aims to provide a metal blackening treatment method. The invention uses metal alloy, which can change the surface color of the metal alloy under the condition of high temperature and normal temperature, and can be made into a material with light absorption performance on the surface.
The purpose of the invention can be realized by the following technical scheme:
a metal blackening treatment method comprises the following steps:
1) Coating the ashing liquid on the metal material in an inert atmosphere, and heating to obtain the metal material with an ashed surface; wherein the ashing liquid is an organic mixed liquid containing nickel salt and selenium;
2) In the atmospheric environment, soaking the ashed metal material on the surface in blackening liquid to obtain the metal material with a black film layer on the surface; wherein the blackening liquid is a mixed liquid containing selenious acid, phosphate, copper sulfate, citrate and a stabilizer.
Further, in step 1), the metal material includes one of nickel, copper or copper-zinc alloy; particularly, one of nickel foam, nickel sheet and copper foam is preferable.
Further, in the step 1), the molar ratio of nickel to selenium in the ashing liquid is (0.5-2): 1, and the used organic solvent comprises ethylenediamine and ethanedithiol, preferably the volume ratio is (3-5): 1.
Further, in the step 1), in the heating treatment process, the heating temperature is 200-400 ℃, and the heating time is 1-5 min; the preferable heating conditions include a heating temperature of 220 to 380 ℃ and a heating time of 2 to 4min.
Further, in the step 2), the blackening liquid comprises 4-5 g/L selenious acid, 1-2 g/L phosphate, 2-5 g/L copper sulfate, 3-5 g/L citrate and 4-6 ml/L stabilizer, and the pH value is 3-6; preferably the pH is 4-5.
Further, in the step 2), the stabilizer mainly functions to maintain the pH stability of the blackening solution, and is generally selected from phosphate buffer, phosphoric acid, boric acid, ammonia water, and the like.
Further, in the step 2), in the dipping and blackening process, the dipping temperature is normal temperature, and the dipping time is 2-10 min; the dipping time is preferably 4 to 8min.
The preparation method comprises the steps of taking a metal alloy material as a raw material, firstly performing graying treatment on a heating plate by using a precursor solution, burying the grayed metal alloy material after the treatment in a solution containing blackening liquid, blackening at normal temperature for 4-10min, separating the metal alloy material and the surface blackening liquid after the reaction is finished, and cleaning and drying a treated product to obtain the required light absorption blackening coating. The method realizes a safe, simple and efficient surface blackening treatment mode, and obtains the compact light absorption blackening coating.
Wherein, nickel nitrate and selenium powder in the precursor solution react at the temperature of 200-400 ℃ to generate a compact gray film, the component of the film is nickel selenide, and the film coating has good optical performance. The nickel element exists on the surface of the metal alloy material treated by the precursor solution, so that the light absorption performance of the surface of the metal alloy is improved.
Compared with the prior art, the invention has the following characteristics:
1) The method for preparing the light-absorbing blackening coating is simple, safe and efficient;
2) By adopting the raw materials and the preparation method, the light-absorbing and blackening coating material prepared by the method is safe and pollution-free in preparation process, and can be improved in conductivity and other characteristics to a certain extent.
Drawings
FIG. 1 is a surface of a copper-zinc alloy sheet of example 1 before treatment;
FIG. 2 is a surface of the copper-zinc alloy sheet of example 1 after treatment;
FIG. 3 is the surface of example 2 before nickel foam treatment.
FIG. 4 is the surface of example 2 after the nickel foam treatment.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A metal blackening treatment method comprises the following steps:
1) Cleaning oil stains or dust on the surface of a metal material with distilled water, wherein some metals are possibly oxidized in the air after being placed in the air for a long time, and in order to eliminate some oxides on the surface of the metals, strong acid and strong alkali or an organic reagent is usually adopted for surface cleaning, and then drying treatment is carried out in an environment of 60-120 ℃ to dry water for 0.5-24 hours;
wherein the metal material comprises one of transition metals such as nickel, copper or copper-zinc alloy; particularly, the material is one of foamed nickel, nickel sheet or foamed copper; the strong acid and strong alkali solution is common non-toxic and non-volatile reagents such as hydrochloric acid, sodium hydroxide and the like;
preferred drying conditions include: the drying temperature is 100-110 ℃, and the drying time is 2-8h; the aim is to completely volatilize the moisture on the surface of the metal material and prevent the preparation of the blackening film from being influenced by the reaction of the moisture in the material and the precursor solution or the blackening liquid;
2) The preparation process of the precursor solution is carried out in a glove box filled with inert gas, nickel nitrate and selenium powder are respectively weighed according to the molar ratio of Ni/Se (0.5-2) to 1, added into the mixed solution of ethylenediamine and ethanedithiol according to the volume ratio of (3-5) to 1, and then stirred until all solids are dissolved;
wherein the inert gas is a gas which does not react with alkali metal at normal temperature and comprises one or a mixture of nitrogen, argon, helium or hydrogen;
3) Drop coating of precursor solution to a surface area of 4cm 2 Placing the metal material on a heating plate, wherein 0.1-0.4 mL of precursor solution is dripped on the metal material, the heating temperature is 200-400 ℃, and the reaction time is 1-5 min, so as to obtain the metal material with the ashed surface; then naturally cooling the metal material to room temperature, washing the metal material with deionized water and absolute ethyl alcohol for a plurality of times, and then drying the metal material for 4 to 8 hours in vacuum at the temperature of between 60 and 100 ℃;
wherein the preferable heating temperature is 220-380 ℃, and the heating time is 2-4 min;
4) Preparing metal blackening liquid at normal temperature, wherein the metal blackening liquid comprises 4-5 g/L selenious acid, 1-2 g/L phosphate, 2-5 g/L copper sulfate, 3-5 g/L citrate, 5ml/L stabilizer, water as a solvent, and the pH value of the solution is controlled to be 3-6 (preferably 4-5);
5) Immersing the metal material with the ashed surface in blackening liquid, and blackening for 2-10 min (preferably 4-8 min) at normal temperature; at the moment, a thin and compact black film layer with firm combination and better corrosion resistance is quickly formed on the surface of the ashing metal material.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
a metal blackening treatment method comprises the following steps:
1) Cleaning oil stain or dust of an H60 copper-zinc alloy material of Tianjin and benefit metal material sales Limited company with distilled water, cleaning with hydrochloric acid, and drying at 80 ℃ for 12H;
2) The preparation process of the precursor solution is carried out in a glove box filled with argon, nickel nitrate and selenium powder are respectively weighed according to the molar ratio of Ni/Se of 1;
3) Drop-coating the precursor solution to a surface area of 4cm 2 Placing the metal material dropwise coated with 0.4mL of precursor solution on a heating plate at the heating temperature of 300 ℃ for 3min to obtain the metal material with ashed surface; then naturally cooling the metal material to room temperature, washing the metal material with deionized water and absolute ethyl alcohol for a plurality of times, and then drying the metal material for 6 hours in vacuum at the temperature of 80 ℃;
4) Preparing metal blackening liquid at normal temperature, wherein the metal blackening liquid comprises 4.5g/L selenious acid, 1.5g/L phosphate, 3.5g/L copper sulfate and 4g/L citrate, a stabilizer is 5ml/L phosphate buffer, a solvent is water, and the pH value of the solution is controlled to be 4-5
5) Immersing the metal material with the ashed surface in blackening liquid, and blackening for 6min at normal temperature; at the moment, a thin and compact black film layer with firm combination and better corrosion resistance is quickly formed on the surface of the incinerated metal material, then the copper-zinc alloy with the blackened surface and the solution are separated, the surface of the copper-zinc alloy material is washed for a plurality of times by deionized water and absolute ethyl alcohol, and then the copper-zinc alloy with the blackened layer is obtained by vacuum drying.
Fig. 1 shows the surface of the copper-zinc alloy thin plate before treatment in example 1, and it can be seen from fig. 1 that the surface of the copper-zinc alloy material before treatment is smooth and golden yellow, and the blackness of the surface of the material before treatment is 0.052. Fig. 2 shows the surface of the copper-zinc alloy sheet of example 1 in example 1, and it can be seen from fig. 2 that the surface of the copper-zinc alloy material treated by the method has a dense black film, and the blackness of the black film on the surface of the material is measured to be 0.96. As can be seen from the comparison between fig. 1 and fig. 2, the surface of the copper-zinc alloy material is significantly changed by the treatment of the method, and this also demonstrates that the method can indeed form a dense black film on the surface of the metal alloy, so that the surface of the metal alloy has light absorptivity.
Example 2:
a metal blackening treatment method, which is different from the embodiment 1 only in that: the metal material is foamed nickel; the rest is the same as example 1.
FIG. 3 is a surface image of the foam nickel of example 2 before treatment, and it can be seen from FIG. 3 that the foam nickel before treatment has a non-smooth surface and no significant light absorption. FIG. 4 is a surface view of the nickel foam treated in example 2, and it can be seen from FIG. 4 that the black film is formed on the surface of the nickel foam treated by the method. As can be seen from the comparison between FIG. 3 and FIG. 4, the treatment of the method produces a significant change on the surface of the nickel foam, and the method can effectively produce a blackened film with light absorption on the surface of the metal alloy.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A metal blackening treatment method is characterized by comprising the following steps:
1) Coating the ashing liquid on the metal material in an inert atmosphere, and heating to obtain a metal material with an ashed surface; wherein the ashing liquid is an organic mixed liquid containing nickel salt and selenium;
2) Soaking the ashed metal material on the surface in blackening liquid to obtain a metal material with a black film layer on the surface; wherein the blackening liquid is a mixed liquid containing selenious acid, phosphate, copper sulfate, citrate and a stabilizer.
2. A metal blackening method according to claim 1, wherein in step 1), the metal material comprises one of nickel, copper or copper-zinc alloy.
3. The metal blackening method according to claim 1, wherein in the step 1), the molar ratio of nickel to selenium in the ashing solution is (0.5-2): 1.
4. The metal blackening method according to claim 1, wherein in the step 1), the organic solvent used in the ashing solution comprises ethylenediamine and ethanedithiol in a volume ratio of (3-5) to 1.
5. A metal blackening method according to claim 1, wherein in the step 1), the heating temperature is 200-400 ℃ and the heating time is 1-5 min in the heating process.
6. A metal blackening treatment method according to claim 5, wherein the heating temperature is 220 to 380 ℃ and the heating time is 2 to 4min in the heating treatment process.
7. The metal blackening method of claim 1, wherein in the step 2), the blackening liquid comprises 4-5 g/L selenious acid, 1-2 g/L phosphate, 2-5 g/L copper sulfate, 3-5 g/L citrate and 4-6 ml/L stabilizer, and the pH value is 3-6;
wherein the stabilizer is one of phosphate buffer, phosphoric acid, boric acid or ammonia water.
8. The metal blackening treatment method of claim 1, wherein the pH of the blackening liquid in step 2) is 4-5.
9. A metal blackening treatment method according to claim 1, wherein in the step 2), the dipping temperature is normal temperature and the dipping time is 2-10 min in the dipping and blackening process.
10. A metal blackening treatment method according to claim 9, wherein the immersion time is 4 to 8min during the immersion blackening process.
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