CN111020670A - Method for preparing green micro-arc oxidation ceramic film layer on surface of titanium alloy - Google Patents

Method for preparing green micro-arc oxidation ceramic film layer on surface of titanium alloy Download PDF

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Publication number
CN111020670A
CN111020670A CN201911376292.8A CN201911376292A CN111020670A CN 111020670 A CN111020670 A CN 111020670A CN 201911376292 A CN201911376292 A CN 201911376292A CN 111020670 A CN111020670 A CN 111020670A
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titanium alloy
arc oxidation
micro
film layer
preparing
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陈飞
李明泽
杨旭宁
吴敏宝
蒋欣运
苑宇骋
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Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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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
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention discloses a method for preparing a green micro-arc oxidation ceramic film layer 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; adopts dispersant and nano Cr2O3Mixing with deionized water to obtain colloid, and mixing the colloid with Na2SiO3、KOH、(NaPO3)6Mixing to prepare 1-2 g/L dispersant and nano Cr2O36 to 12g/L, Na2SiO34 to 10g/L, KOH of 0.4 to 2g/L, (NaPO)3)60.5-1.5 g/L of micro-arc oxidation electrolyte; and placing the pretreated titanium alloy workpiece in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, thereby preparing a green micro-arc oxidation ceramic film layer on the surface of the titanium alloy. The film formed by the invention is more compact, and has high hardness, good color retention, strong film/substrate binding force and ideal film performance.

Description

Method for preparing green micro-arc oxidation ceramic film layer on surface of titanium alloy
Technical Field
The invention relates to the technical field of metal coloring, in particular to a method for preparing a green micro-arc oxidation ceramic film layer on the surface of a titanium alloy.
Background
At present, in titanium and titanium alloy products treated by a surface engineering technology, a green ceramic layer has unique optical function and decorative performance, excellent corrosion resistance and good mechanical performance, so that the green ceramic layer has wide application prospect in the fields of aerospace, optical instruments, electronic devices and the like.
The use of conventional soluble chromium salts such as potassium dichromate as coloring agents poses a health hazard to humans, and thus the use of soluble chromium salts poses problems of waste disposal and waste water treatment. Trivalent chromium oxide pigments are chemically inert and environmentally friendly and are easier to handle in industrial practice and are therefore widely used as green colorants in the paint, construction, etc. industries.
In the prior art, the titanium alloy coloring technology mainly comprises anodic oxidation, sol-gel, electrochemical plating, vacuum coating and the like, but green film layers formed by the technologies in respective working environments are loose, have poor binding 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 preparing a green micro-arc oxidation ceramic film layer on the surface of a titanium alloy, and the formed film layer is more compact, high in hardness, good in color retention, strong in film/base binding force and very ideal in film layer performance.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a green micro-arc oxidation ceramic film layer on the surface of a titanium alloy comprises 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, adopting a dispersing agent and nano Cr2O3Is prepared with deionized waterPreparing colloid, grinding the colloid, and mixing the ground colloid with Na2SiO3、KOH、(NaPO3)6Mixing to prepare 1-2 g/L nano Cr dispersing agent2O36 to 12g/L, Na2SiO34 to 10g/L, KOH of 0.4 to 2g/L, (NaPO)3)60.5-1.5 g/L of micro-arc oxidation electrolyte;
and 3, placing the pretreated titanium alloy workpiece in the micro-arc oxidation electrolyte for micro-arc oxidation treatment, thereby preparing a green micro-arc oxidation ceramic film layer on the surface of the titanium alloy.
Preferably, the dispersant is sodium polyacrylate or carboxylate copolymer.
Preferably, said grinding said colloid comprises: and (3) placing the colloid in a plastic tank, and grinding for 36-48 hours by adopting alumina balls with the diameter of 6 mm.
Preferably, the micro-arc oxidation treatment adopts the following process parameters: under the constant current mode, the forward current density is 6-14A/dm2The negative current density is 1-6A/dm2The frequency is 400 Hz-1000 Hz, the positive duty ratio is 30% -70%, the negative duty ratio is 10% -30%, and the time is 5-20 min.
Preferably, the titanium alloy workpiece to be treated is a TC4 titanium alloy or a TC10 titanium alloy.
According to the technical scheme provided by the invention, the method for preparing the green micro-arc oxidation ceramic film layer on the surface of the titanium alloy adopts the micro-arc oxidation electrolyte with specific components to carry out micro-arc oxidation treatment, and the green ceramic film layer directly grows in situ on the surface of the titanium alloy under the action of micro-area instant high-temperature sintering by controlling various process parameters of the micro-arc oxidation treatment; the green 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 preparing a green micro-arc oxidation ceramic film layer on the surface of a titanium alloy in the 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 preparing the green micro-arc oxidation ceramic film layer on the surface of the titanium alloy 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 preparing a green micro-arc oxidation ceramic film layer on the surface of a titanium alloy comprises the following steps:
step 1, polishing the surface of a titanium alloy workpiece to be treated on silicon carbide abrasive paper and polishing cloth to achieve a mirror surface effect, and then ultrasonically cleaning and drying the titanium alloy workpiece by using deionized water and absolute ethyl alcohol to obtain a pretreated titanium alloy workpiece.
Step 2, adopting sodium polyacrylate or carboxylate copolymer (as dispersant), nano Cr2O3Preparing colloid (as a coloring agent) and deionized water, then placing the colloid in a plastic tank, grinding for 36-48 hours by adopting 6mm alumina balls, and then mixing the ground colloid with Na2SiO3、KOH、(NaPO3)6Mixing, using deionized water to fix the volume to a certain volume, and uniformly stirring to prepare 1-2 g/L of dispersing agent and nano Cr2O36 to 12g/L, Na2SiO34 to 10g/L, KOH of 0.4 to 2g/L, (NaPO)3)60.5-1.5 g/L of micro-arc oxidation electrolyte.
And 3, placing the pretreated titanium alloy workpiece in the micro-arc oxidation electrolyte for micro-arc oxidation treatment, thereby preparing a green micro-arc oxidation ceramic film layer on the surface of the titanium alloy.
Specifically, the method for preparing the green micro-arc oxidation ceramic film layer on the surface of the titanium alloy can comprise the following embodiments:
(1) the titanium alloy workpiece to be treated is TC4 titanium alloy or TC10 titanium alloy. In practical applications, the titanium alloy workpiece to be treated may be: a circular sheet with the diameter of 30mm and the thickness of 3 mm.
(2) The micro-arc oxidation treatment adopts the following process parameters: under the constant current mode, the forward current density is 6-14A/dm2The negative current density is 1-6A/dm2The frequency is 400 Hz-1000 Hz, the positive duty ratio is 30% -70%, the negative duty ratio is 10% -30%, and the time is 5-20 min. In practical application, the electrolytic bath used for the micro-arc oxidation treatment is connected with an ultrasonic power supply and is provided with a stirring and cooling device.
Further, the method for preparing the green micro-arc oxidation ceramic film layer on the surface of the titanium alloy 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 the interface of the film layer and the electrolyte forms a nano-Cr-containing film layer2O3Has certain color and luster. The green ceramic layer generated by micro-arc oxidation treatment is generated in situ on the surface of the titanium alloy substrate, so the green 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 scheme and the technical effects thereof provided by the present invention, the method for preparing the green micro-arc oxidized ceramic film layer on the surface of the titanium alloy provided by the present invention is described in detail with specific embodiments below.
Example 1
A method for preparing a green micro-arc oxidation ceramic film layer on the surface of a titanium alloy comprises the following steps:
step A, sequentially grinding the surface of a TC4 titanium alloy workpiece to be processed 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, adopting 5g of sodium polyacrylate (as a dispersing agent) and 40g of nano Cr2O3(as a colorant) and deionized water were made into 400mL of a colloid, which was then placed in a plastic jar and ground using 6mm alumina balls for 36 hours, and the ground colloid was mixed with 25g of Na2SiO35g of KOH, 5g of (NaPO)3)6Mixing, adding deionized water to make the final volume of the solution 5L, and stirring to obtain 1g/L nanometer Cr dispersant2O3Is 8g/L, Na2SiO35g/L, KOH of 1g/L, (NaPO)3)61g/L of micro-arc oxidation electrolyte.
And step C, placing the pretreated titanium alloy workpiece in the micro-arc oxidation electrolyte for micro-arc oxidation treatment, so as to prepare a green micro-arc oxidation ceramic film layer on the surface of the titanium alloy.
Specifically, the micro-arc oxidation treatment in the step C adopts the following process parameters: the forward current density is 9A/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 (5)

1. A method for preparing a green micro-arc oxidation ceramic film layer 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, adopting a dispersing agent and nano Cr2O3Preparing colloid with deionized water, grinding the colloid, and mixing the ground colloid with Na2SiO3、KOH、(NaPO3)6Mixing to prepare 1-2 g/L nano Cr dispersing agent2O36 to 12g/L, Na2SiO34 to 10g/L, KOH of 0.4 to 2g/L, (NaPO)3)60.5-1.5 g/L of micro-arc oxidation electrolyte;
and 3, placing the pretreated titanium alloy workpiece in the micro-arc oxidation electrolyte for micro-arc oxidation treatment, thereby preparing a green micro-arc oxidation ceramic film layer on the surface of the titanium alloy.
2. The method for preparing a green micro-arc oxidation ceramic film layer on the surface of a titanium alloy according to claim 1, wherein the dispersant is sodium polyacrylate or carboxylate copolymer.
3. The method for preparing a green micro-arc oxidation ceramic film layer on the surface of the titanium alloy according to claim 1 or 2, wherein the grinding the colloid comprises: and (3) placing the colloid in a plastic tank, and grinding for 36-48 hours by adopting alumina balls with the diameter of 6 mm.
4. According to the rightThe method for preparing the green micro-arc oxidation ceramic film layer on the surface of the titanium alloy according to claim 1 or 2, wherein the micro-arc oxidation treatment adopts the following process parameters: under the constant current mode, the forward current density is 6-14A/dm2The negative current density is 1-6A/dm2The frequency is 400 Hz-1000 Hz, the positive duty ratio is 30% -70%, the negative duty ratio is 10% -30%, and the time is 5-20 min.
5. The method for preparing the green micro-arc oxidation ceramic film layer on the surface of the titanium alloy as claimed in claim 1 or 2, wherein the titanium alloy workpiece to be treated is TC4 titanium alloy or TC10 titanium alloy.
CN201911376292.8A 2019-12-27 2019-12-27 Method for preparing green micro-arc oxidation ceramic film layer on surface of titanium alloy Pending CN111020670A (en)

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Cited By (1)

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CN114411221A (en) * 2021-12-21 2022-04-29 西安泰金工业电化学技术有限公司 Surface treatment method for improving corrosion resistance of titanium side plate of cathode roller

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411221A (en) * 2021-12-21 2022-04-29 西安泰金工业电化学技术有限公司 Surface treatment method for improving corrosion resistance of titanium side plate of cathode roller

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