CN111005049A - Method for in-situ growth of black ceramic film on titanium alloy surface - Google Patents
Method for in-situ growth of black ceramic film on titanium alloy surface Download PDFInfo
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- CN111005049A CN111005049A CN201911376260.8A CN201911376260A CN111005049A CN 111005049 A CN111005049 A CN 111005049A CN 201911376260 A CN201911376260 A CN 201911376260A CN 111005049 A CN111005049 A CN 111005049A
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- 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
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- 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
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- 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
- C25D11/026—Anodisation with spark discharge
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Abstract
The invention discloses a method for in-situ growth of a black ceramic film on the surface of a titanium alloy, which comprises the following steps: polishing the surface of a titanium alloy workpiece to be treated, cleaning and drying to obtain a pretreated titanium alloy workpiece; placing the pretreated titanium alloy workpiece in electrolyte, and adding a coloring agent and a stabilizing agent into the electrolyte to perform micro-arc oxidation treatment, so as to obtain a black ceramic film layer growing in situ on the surface of the titanium alloy; wherein the colorant comprises 6-12 g/L of Na2WO48 to 12g/L of Na3VO44-8 g/L of FeSO44-8 g/L of Ni (CH)3COO)2And 1-3 g/L of Cu (CH)3COO)2(ii) a The stabilizer is 3-8 g/L sodium citrate. The film formed by the invention is more compact, and has high hardness, good color retention, strong film/base binding force and ideal film performance.
Description
Technical Field
The invention relates to the technical field of metal coloring, in particular to a method for growing a black ceramic film layer on the surface of a titanium alloy in situ.
Background
At present, in titanium and titanium alloy products treated by a surface engineering technology, a black ceramic layer has unique optical function and decorative performance, excellent corrosion resistance and good mechanical performance, so the black ceramic layer has wide application prospect in the fields of aerospace, optical instruments, electronic devices and the like.
In the prior art, the titanium alloy coloring technology mainly comprises anodic oxidation, sol-gel, electrochemical plating, vacuum coating and the like, but black film layers formed by the technologies in respective working environments are loose, have poor bonding force and are not ideal in coloring effect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for growing the black ceramic film on the surface of the titanium alloy in situ, and the formed film is more compact, high in hardness, good in color retention, strong in film/base binding force and very ideal in film performance.
The purpose of the invention is realized by the following technical scheme:
a method for in-situ growth of a black ceramic film on the surface of a titanium alloy comprises the following steps:
wherein the electrolyte comprises 8-12 g/L of Na2SiO32-6 g/L KOH and 2-8 g/L (NaPO)3)6(ii) a The colorant comprises 6-12 g/L of Na2WO48 to 12g/L of Na3VO44-8 g/L of FeSO44-8 g/L of Ni (CH)3COO)2And 1-3 g/L of Cu (CH)3COO)2(ii) a The stabilizing agent is 3-8 g/L sodium citrate.
Preferably, the micro-arc oxidation treatment adopts the following process parameters: under the constant current mode, the forward current density is 8-14A/dm2The negative current density is 2-6A/dm2The frequency is 500 Hz-1000 Hz, the positive duty ratio is 30% -70%, the negative duty ratio is 10% -30%, and the time is 10-20 min.
Preferably, the titanium alloy workpieces to be treated are a Ti6Al4V alloy and a Ti6Al7Nb alloy.
According to the technical scheme provided by the invention, the method for in-situ growth of the black ceramic film on the surface of the titanium alloy adopts the electrolyte, the coloring agent and the stabilizing agent with specific components to carry out micro-arc oxidation treatment, and the black ceramic film is directly grown in situ on the surface of the titanium alloy under the action of instantaneous high-temperature sintering of a microcell by controlling various process parameters of the micro-arc oxidation treatment; the black ceramic film prepared by the method is not only more compact, but also has high hardness, strong film/base binding force, good color stability and excellent wear resistance and corrosion resistance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for in-situ growth of a black ceramic film on a titanium alloy surface according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The method for growing the black ceramic film on the surface of the titanium alloy in situ provided by the invention is described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
As shown in fig. 1, a method for in-situ growing a black ceramic film on a titanium alloy surface may include the following steps:
And 2, placing the pretreated titanium alloy workpiece in electrolyte, and adding a coloring agent and a stabilizing agent into the electrolyte to perform micro-arc oxidation treatment, so as to obtain an in-situ grown black ceramic film layer on the surface of the titanium alloy.
Specifically, the method for in-situ growth of the black ceramic film layer on the surface of the titanium alloy can comprise the following embodiments:
(1) the titanium alloy workpiece to be treated is Ti6Al4V alloy and Ti6Al7Nb alloy. In practical applications, the titanium alloy workpiece to be treated may be: a disc with a diameter of 52mm and a thickness of 4 mm.
(2) The electrolyte comprises 8-12 g/L of Na2SiO32-6 g/L KOH and 2-8 g/L (NaPO)3)6(ii) a The colorant comprises 6-12 g/L of Na2WO48 to 12g/L of Na3VO44-8 g/L of FeSO44-8 g/L of Ni (CH)3COO)2And 1-3 g/L of Cu (CH)3COO)2(ii) a The stabilizing agent is 3-8 g/L sodium citrate.
(3) The micro-arc oxidation treatment adopts the following process parameters: under the constant current mode, the forward current density is 8-14A/dm2The negative current density is 2-6A/dm2The frequency is 500 Hz-1000 Hz, the forward duty ratio is 30 percent70 percent, 10 to 30 percent of negative duty ratio and 10 to 20 min.
Further, the method for in-situ growth of the black ceramic film layer on the surface of the titanium alloy provided by the invention adopts specific process parameters to carry out micro-arc oxidation treatment, the film layer is repeatedly punctured to form a porous discharge channel under the action of local high temperature and high pressure, and a black compound containing W, V, Fe and Ni is formed at the interface of the film layer and the electrolyte and has certain color and luster. The black ceramic layer generated by micro-arc oxidation treatment is generated in situ on the surface of the titanium alloy substrate, so the black ceramic layer has good film/substrate binding force.
In conclusion, the film formed by the embodiment of the invention is more compact, and has high hardness, good color retention, strong film/substrate bonding force and ideal film performance.
In order to more clearly show the technical solutions and the technical effects provided by the present invention, the method for in-situ growing a black ceramic film on a titanium alloy surface provided by the present invention is described in detail below with specific embodiments.
Example 1
A method for in-situ growth of a black ceramic film layer on the surface of a titanium alloy can comprise the following steps:
and step A, sequentially grinding the surface of the titanium alloy workpiece to be treated on 180#, 400#, 800# and 1200# silicon carbide abrasive paper, polishing with polishing cloth to achieve a mirror surface effect, and then respectively carrying out ultrasonic cleaning with deionized water and absolute ethyl alcohol and drying to obtain the pretreated titanium alloy workpiece.
Step B, placing the pretreated titanium alloy workpiece in Na containing 10g/L2SiO35g/L KOH and 4g/L (NaPO)3)6And Na with a concentration of 8g/L is added to the electrolyte2WO48g/L of Na3VO45g/L of FeSO45g/L of Ni (CH)3COO)2And 2g/L of Cu (CH)3COO)2The colorant and 6g/L sodium citrate (as a stabilizer) are subjected to micro-arc oxidation treatment, so that an in-situ layer is obtained on the surface of the titanium alloyAnd growing a black ceramic film layer.
Specifically, the micro-arc oxidation treatment in the step B adopts the following process parameters: the forward current density is 12A/dm in a constant current mode2A negative current density of 4A/dm2The frequency is 500Hz, the positive duty ratio is 40%, the negative duty ratio is 20%, and the time is 15 min.
In conclusion, the film formed by the embodiment of the invention is more compact, and has high hardness, good color retention, strong film/substrate bonding force and ideal film performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. A method for in-situ growth of a black ceramic film on the surface of a titanium alloy is characterized by comprising the following steps:
step 1, polishing the surface of a titanium alloy workpiece to be treated, cleaning and drying to obtain a pretreated titanium alloy workpiece;
step 2, placing the pretreated titanium alloy workpiece in electrolyte, and adding a coloring agent and a stabilizing agent into the electrolyte to perform micro-arc oxidation treatment, so as to obtain an in-situ grown black ceramic film layer on the surface of the titanium alloy;
wherein the electrolyte comprises 8-12 g/L of Na2SiO32-6 g/L KOH and 2-8 g/L (NaPO)3)6(ii) a The colorant comprises 6-12 g/L of Na2WO48 to 12g/L of Na3VO44-8 g/L of FeSO44-8 g/L of Ni (CH)3COO)2And 1-3 g/L of Cu (CH)3COO)2(ii) a The stabilizing agent is 3-8 g/L sodium citrate.
2. The method for in-situ growth of the black ceramic film on the surface of the titanium alloy according to claim 1, wherein the micro-arc oxidation treatment adopts the following process parameters: under the constant current mode, the forward current density is 8-14A/dm2The negative current density is 2-6A/dm2The frequency is 500 Hz-1000 Hz, the positive duty ratio is 30% -70%, the negative duty ratio is 10% -30%, and the time is 10-20 min.
3. The method for in-situ growth of the black ceramic film on the surface of the titanium alloy as claimed in claim 1 or 2, wherein the titanium alloy workpiece to be treated is Ti6Al4V alloy and Ti6Al7Nb alloy.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112981494A (en) * | 2021-02-08 | 2021-06-18 | 深圳市钧诚精密制造有限公司 | Titanium alloy micro-arc oxidation process with high light absorption rate |
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| US20190054671A1 (en) * | 2016-01-28 | 2019-02-21 | Hewlett-Packard Development Company, L.P. | Metal-plastic composite structure for electronic devices |
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| CN112981494A (en) * | 2021-02-08 | 2021-06-18 | 深圳市钧诚精密制造有限公司 | Titanium alloy micro-arc oxidation process with high light absorption rate |
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Application publication date: 20200414 |