CN110552044A - Steel anodic oxidation electrolyte and anodic oxidation method thereof - Google Patents
Steel anodic oxidation electrolyte and anodic oxidation method thereof Download PDFInfo
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- CN110552044A CN110552044A CN201910971791.5A CN201910971791A CN110552044A CN 110552044 A CN110552044 A CN 110552044A CN 201910971791 A CN201910971791 A CN 201910971791A CN 110552044 A CN110552044 A CN 110552044A
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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
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
Abstract
The invention belongs to the technical field of metal anodic oxidation, and particularly relates to steel anodic oxidation electrolyte and an anodic oxidation method thereof. The electrolyte includes: 0.2-1mol/L citric acid, 0.01-0.15mol/L ammonium fluoride, 0.01-1g/L glycerol, 0.01-1g/L alkylphenol polyoxyethylene and water. The anodic oxidation method comprises the following steps: and grinding, polishing and cleaning the surface of the steel workpiece, then taking the steel workpiece as an anode and taking a graphite plate or a lead plate as a cathode, and carrying out anodic oxidation treatment by using the electrolyte to generate a layer of oxide film on the surface of the steel workpiece. The steel anodic oxidation electrolyte and the surface oxide obtained by the anodic oxidation method have the advantages of strong binding force, wear resistance and corrosion resistance, and the problem that the steel anodic oxidation treatment is difficult in the prior art is solved.
Description
Technical Field
The invention belongs to the technical field of metal anodic oxidation, and particularly relates to steel anodic oxidation electrolyte and an anodic oxidation method thereof.
Background
Anodizing is a widely used metal surface treatment technique, but anodizing is often limited to treating aluminum alloys. With the development of the technology, anodic oxidation technology of magnesium alloy and titanium alloy has also been developed. Like aluminum alloy, magnesium alloy and titanium alloy also belong to self-passivation type metal, and can generate a compact oxide film in air so as to protect a matrix, and the metal is easy to carry out anodic oxidation treatment and grow a thicker oxide layer under the condition of external current. Steel materials are difficult to anodize due to their own electrochemical properties. In the anodic oxidation treatment of aluminum alloys, an aqueous solution of sulfuric acid or oxalic acid is generally used as an electrolyte, and particularly, a sulfuric acid-based electrolyte is mainly used. Therefore, the industry does not anodize steel.
The aluminum alloy anodic oxide film has excellent characteristics such as wear resistance, corrosion resistance, insulation and the like, and is therefore often used as a surface functional coating for engineering structural members or mechanical parts; the aluminum alloy anodic oxide film can also be colored and thus can be used as a decorative coating; in addition, the aluminum alloy anodic oxide film has a special micro-or nano-structure, such as micro-pores or nano-pores, so that the aluminum alloy anodic oxide film can be used in the field of nano-materials, for example, can be used as a template for preparing the nano-materials, and can also be used as a separation film.
The ferrous material contains iron as the main component. Iron metal is not self-passivating, unlike aluminum. Iron also loses electrons in solutions of sulfuric acid, phosphoric acid, etc. to become iron ions and likewise reacts to form oxides, but iron ions dissolve too quickly and the oxides are also prone to dissolution or further reaction, eventually resulting in corrosion of the iron rather than the formation of a dense protective oxide film.
It would be of great benefit to the development of surface treatments for steel materials if the steel could also be anodized and achieved similar performance and application as the anodized film of aluminum alloy.
In view of the above, the present invention is directed to an anodizing solution for steel and an anodizing method thereof.
Disclosure of Invention
In order to solve the problem that steel is difficult to carry out anodic oxidation treatment in the prior art, the invention provides steel anodic oxidation electrolyte and an anodic oxidation method thereof, and an oxide film obtained on the surface of the steel has the characteristics of wear resistance, corrosion resistance, strong binding force with a matrix and the like.
The invention is realized by the following technical scheme:
The steel anodic oxidation electrolyte comprises the following components: 0.2-1mol/L citric acid, 0.01-0.15mol/L ammonium fluoride, 0.01-1g/L glycerol, 0.01-1g/L alkylphenol polyoxyethylene and water.
Preferably, the steel anodizing electrolyte comprises the following components: 0.7mol/L citric acid, 0.08mol/L ammonium fluoride, 0.02g/L glycerol, 0.03g/L alkylphenol polyoxyethylene and water.
Preferably, the steel anodizing electrolyte comprises the following components: 0.6mol/L citric acid, 0.05mol/L ammonium fluoride, 0.1g/L glycerol, 0.04g/L alkylphenol polyoxyethylene and water.
Preferably, the steel anodizing electrolyte comprises the following components: 0.2mol/L citric acid, 0.15mol/L ammonium fluoride, 0.9g/L glycerol, 0.8g/L alkylphenol polyoxyethylene and water.
The invention also provides a steel anodic oxidation method adopting the electrolyte, which comprises the following steps:
(1) Surface pretreatment: sequentially grinding, polishing and cleaning the surface of the steel workpiece, and then drying the steel workpiece;
(2) Anodic oxidation treatment: and (2) taking the steel workpiece pretreated in the step (1) as an anode, immersing the anode and a cathode in the electrolyte, connecting the anode with a positive electrode of a power supply, and connecting the cathode with a negative electrode of the power supply, and carrying out anodic oxidation treatment.
Preferably, in the step (1), the grinding is performed by using sand paper, the polishing is performed by using a polishing machine for mechanical polishing, and the cleaning is performed by using deionized water.
Preferably, the anodic oxidation in step (2) is performed under the condition of mechanical stirring or gas stirring, and the speed of the mechanical stirring is 500-.
Preferably, the anodizing conditions are as follows: voltage of 5-30V, time of 5-60min, and electrolyte temperature of 0-25 deg.C. When the anodic oxidation voltage is too high (>30V), the corrosion dissolution speed is accelerated, and an oxide film formed on the surface of a steel workpiece is easy to dissolve too fast, is difficult to thicken and is not dense; if the voltage for anodic oxidation is too low (<5V), the growth of the oxide film on the surface of the steel workpiece is not facilitated. Too long an anodic oxidation time also causes the formed oxide film to dissolve and become loose. Too high electrolyte temperature also causes the oxide film to dissolve too fast and become loose.
Preferably, the cathode in step (2) is a graphite plate or a lead plate.
Preferably, the steel anodizing method further comprises the steps of washing the workpiece subjected to the anodizing treatment in the step (2) with deionized water and drying the workpiece with cold air.
The invention has the beneficial effects that:
(1) The invention provides steel anodic oxidation electrolyte aiming at the problem that the prior anodic oxidation technology is limited to aluminum alloy and can not treat steel materials, so that the steel materials as the anode are placed in the electrolyte and are easy to generate an oxide film under the action of current, the growth speed of the film layer is greater than the dissolution speed, and the film layer is favorably thickened. The citric acid in the electrolyte formula is not used as an additive of a chelating agent in the prior art, under the condition of not adding sulfuric acid or phosphoric acid, the citric acid enables iron to lose electrons and become iron ions, and the iron ions are oxidized, and the oxidation and dissolution processes of an oxide film on the surface of steel can be regulated, so that a compact oxide film is controlled and obtained.
(2) in the steel anodic oxidation electrolyte, the ammonium fluoride is ionized into fluorine ions and ammonia ions in water, the fluorine ions have the etching effect on steel materials, the anodic oxidation process can be controlled by controlling the adding amount, and a microstructure with a certain shape can be etched.
(3) In the steel anodic oxidation electrolyte, the glycerol and the alkylphenol polyoxyethylene ether are used as surfactants and play a role in anodic polarization, in an anodic oxidation system, a steel piece is placed at an anode, and the glycerol and the alkylphenol polyoxyethylene ether promote the anodic polarization of the steel piece and slow down corrosion and dissolution.
(4) The invention also provides a method for carrying out anodic oxidation treatment on steel by using the steel anodic oxidation electrolyte, and the obtained steel surface oxide film has the advantages of strong binding force, wear resistance and corrosion resistance by controlling the technological parameters of anodic oxidation; meanwhile, the method has the characteristics of simple and convenient operation and remarkable effect.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of an anodic oxide film on the surface of Q235 steel obtained in example 1;
Fig. 2 is a polarization curve of anodized Q235 steel and non-anodized Q235 steel in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples, but is not limited thereto.
Example 1: anodic oxidation of Q235 steel
The electrolyte formula is as follows: an aqueous solution containing 0.7mol/L citric acid, 0.08mol/L ammonium fluoride, 0.2g/L glycerol and 0.03g/L alkylphenol polyoxyethylene.
An anodic oxidation step: the surface of a steel workpiece (in this example, Q235 steel) is polished by sand paper, the polished surface is mechanically polished by a polishing machine, and then the surface of the workpiece is cleaned by deionized water and dried by cold air. Immersing the workpiece with the surface pretreatment in the anodic oxidation electrolyte for anodic oxidation treatment. The oxidation voltage is 20V, the temperature of the electrolyte is 20 ℃, the mechanical stirring is 1000r/min, and the oxidation time is 20 min. And after the anodic oxidation is finished, cleaning the surface of the workpiece by using deionized water, and drying by cold air to obtain the anodized Q235 steel.
Scanning electron microscope tests are carried out on the surface of the anodized Q235 steel obtained in the embodiment, and as shown in fig. 1, it can be seen that an oxide film formed on the surface of the Q235 steel is dense and has no holes and cracks.
When the anodized Q235 steel sample obtained in this example was subjected to a polarization curve test, as shown in fig. 2, it was found that the corrosion potential of the anodized Q235 steel sample was shifted forward and the self-corrosion current density was decreased, as compared with the non-anodized Q235 steel, indicating that the corrosion tendency was decreased, the corrosion rate was decreased, and the corrosion resistance was improved.
Example 2: anodic oxidation of 45 steel
The electrolyte formula is as follows: an aqueous solution containing 0.6mol/L of citric acid, 0.05mol/L of ammonium fluoride, 0.1g/L of glycerol and 0.04g/L of alkylphenol polyoxyethylene.
An anodic oxidation step: the surface of a steel workpiece (45 steel in this example) is polished by sand paper, the polished surface is mechanically polished by a polishing machine, and then the surface of the workpiece is cleaned by deionized water and dried by cold air. And immersing the workpiece subjected to surface pretreatment in an anodic oxidation electrolyte for anodic oxidation treatment. The oxidation voltage is 30V, the temperature of the electrolyte is 20 ℃, the mechanical stirring is 1200r/min, and the oxidation time is 50 min. And after the anodic oxidation is finished, cleaning the surface of the workpiece by using deionized water, and drying by cold air to obtain the anodized 45 steel.
Example 3: anodic oxidation of Q235 steel
The electrolyte formula is as follows: an aqueous solution containing 0.2mol/L citric acid, 0.15mol/L ammonium fluoride, 0.9g/L glycerol and 0.8g/L alkylphenol polyoxyethylene.
An anodic oxidation step: the surface of a steel workpiece (in this example, Q235 steel) is polished by sand paper, the polished surface is mechanically polished by a polishing machine, and then the surface of the workpiece is cleaned by deionized water and dried by cold air. Immersing the workpiece with the surface pretreatment in the anodic oxidation electrolyte for anodic oxidation treatment. The oxidation voltage is 10V, the temperature of the electrolyte is 10 ℃, the mechanical stirring is 2000r/min, and the oxidation time is 5 min. And after the anodic oxidation is finished, cleaning the surface of the workpiece by using deionized water, and drying by cold air to obtain the anodized Q235 steel.
Comparative example 1: anodic oxidation of Q235 steel
The electrolyte formulation was the same as in example 1.
The anodization step was substantially the same as in example 1, except that: the oxidation voltage was 35V. The resulting oxide film on the surface of the Q235 steel was very thin and had holes distributed.
comparative example 2: anodic oxidation of Q235 steel
the electrolyte formulation was the same as in example 1.
The anodization step was substantially the same as in example 1, except that: the oxidation voltage was 3V. The resulting oxide film on the surface of the Q235 steel was thin, incomplete, and had holes distributed.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. the steel anodic oxidation electrolyte is characterized by comprising the following components: 0.2-1mol/L citric acid, 0.01-0.15mol/L ammonium fluoride, 0.01-1g/L glycerol, 0.01-1g/L alkylphenol polyoxyethylene and water.
2. The steel anodizing electrolyte of claim 1, comprising the following components: 0.7mol/L citric acid, 0.08mol/L ammonium fluoride, 0.02g/L glycerol, 0.03g/L alkylphenol polyoxyethylene and water.
3. The steel anodizing electrolyte of claim 1, comprising the following components: 0.6mol/L citric acid, 0.05mol/L ammonium fluoride, 0.1g/L glycerol, 0.04g/L alkylphenol polyoxyethylene and water.
4. The steel anodizing electrolyte of claim 1, comprising the following components: 0.2mol/L citric acid, 0.15mol/L ammonium fluoride, 0.9g/L glycerol, 0.8g/L alkylphenol polyoxyethylene and water.
5. A steel anodizing method using the electrolyte according to any one of claims 1 to 4, comprising the steps of:
(1) Surface pretreatment: sequentially grinding, polishing and cleaning the surface of the steel workpiece, and then drying the steel workpiece;
(2) Anodic oxidation treatment: and (2) taking the steel workpiece pretreated in the step (1) as an anode, immersing the anode and a cathode in the electrolyte, connecting the anode with a positive electrode of a power supply, and connecting the cathode with a negative electrode of the power supply, and carrying out anodic oxidation treatment.
6. the steel anodizing method of claim 5, wherein in step (1), the polishing is performed by using sand paper, the polishing is performed by using a polishing machine for mechanical polishing, and the cleaning is performed by using deionized water.
7. The steel anodizing method of claim 5, wherein the anodizing in step (2) is performed under mechanical stirring or gas stirring, and the mechanical stirring rate is 500-.
8. A steel anodizing method according to claim 5, wherein said anodizing conditions are as follows: voltage of 5-30V, time of 5-60min, and electrolyte temperature of 0-25 deg.C.
9. A steel anodizing process according to claim 5 wherein in step (2) said cathode is a graphite or lead plate.
10. the steel anodizing method of any one of claims 5-9, further comprising the step of deionized water cleaning and cold air blow drying the workpiece anodized in step (2).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110965099A (en) * | 2019-12-31 | 2020-04-07 | 苏州市科渠金属制品有限公司 | Aluminum alloy mirror surface anodic oxidation method |
| CN114574924A (en) * | 2022-03-30 | 2022-06-03 | 西安优耐特容器制造有限公司 | Integrated clean anodic oxidation method |
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| JP3484525B2 (en) * | 2001-07-06 | 2004-01-06 | 株式会社ケミカル山本 | Stainless steel surface cleaning and passivation treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110965099A (en) * | 2019-12-31 | 2020-04-07 | 苏州市科渠金属制品有限公司 | Aluminum alloy mirror surface anodic oxidation method |
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