CN114855105A - Pretreatment method of titanium anode base material - Google Patents
Pretreatment method of titanium anode base material Download PDFInfo
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- CN114855105A CN114855105A CN202210122935.1A CN202210122935A CN114855105A CN 114855105 A CN114855105 A CN 114855105A CN 202210122935 A CN202210122935 A CN 202210122935A CN 114855105 A CN114855105 A CN 114855105A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/02—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by distortion, beating, or vibration of the surface to be cleaned
- B08B7/026—Using sound waves
- B08B7/028—Using ultrasounds
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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
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/08—Etching of refractory metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a pretreatment method of a titanium anode base material, which comprises the following steps: selecting a titanium material; carrying out surface heat treatment, recrystallization and annealing on the titanium material, wherein the heat treatment temperature is 650-680 ℃, and carrying out heat preservation for 2-3h and then cooling along with the furnace; carrying out electrochemical corrosion on the titanium material, wherein the electrolyte comprises the following components: 1-1.05mol/L NH 4 Br, 0.1-0.15mol/L NaF, 0.05-0.06mol/L HCL, 2-5ppm polyethylene glycol-2000, pH 2-3 of electrolyte, and temperature 25-30 ℃; the electrolytic process comprises the following steps: the current density is 50-80A/m 2 The electrolysis time is 60-120 min; ultrasonically vibrating the electrochemically corroded titanium materialCleaning with distilled water, and oven drying. According to the pretreatment method of the titanium anode substrate, provided by the invention, the oxide skin on the surface is treated by adopting an electrochemical corrosion process, so that the operation safety and risk are low, the stability of the titanium anode plate material is good, the electrolyte can be repeatedly used, and the treatment cost is low.
Description
Technical Field
The invention relates to the technical field of titanium anode plate production, in particular to a titanium anode substrate pretreatment method.
Background
The prior titanium anode surface treatment process comprises the steps of sand blasting and coarsening the surface of a material, then annealing and leveling, and then carrying out oxalic acid pickling to remove oxide skin. The process has the following problems:
(1) the oxalic acid concentration of the oxalic acid pickling process is 8%, the working temperature is 90-100 ℃, and the pickling time is 2-3 h. In the treatment process, because the acid mist is in a boiling state, a large amount of acid mist overflows, the shaft position environment is corroded, and the working environment is poor;
(2) the oxalic acid is disposable and can not be used repeatedly;
(3) forming an oxide layer on the surface of the titanium material after surface treatment, pickling by oxalic acid, and hardly reacting with titanium oxide at the temperature of 90-100 ℃; oxalic acid can penetrate the oxide layer to react with titanium slowly at low temperature, but when the temperature reaches above 50 ℃, the dissolution speed of titanium is accelerated, and Ti is oxidized into Ti 3+ ，H + Is reduced into hydrogen, and the chemical reaction formula is as follows: ti + C 2 H 2 0 4 ＝Ti(C 2 O 4 ) 2 +H 2 The titanium anode has the advantages that the titanium corrosion rate of oxalic acid is uncontrollable, and the corrosion amount of the titanium material is large, so that the titanium material has defects to influence the quality of the titanium anode;
(4) before pickling, the substrate must be subjected to sand blasting surface roughening treatment, which is too high in cost.
In view of the above, it is necessary to provide a new pretreatment method to solve the above technical problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a titanium anode substrate pretreatment method, which adopts an electrochemical corrosion process to treat oxide skin on the surface, and has the advantages of safe operation, low risk, good stability of titanium anode plate materials, reusable electrolyte and low treatment cost.
In order to solve the problems, the technical scheme of the invention is as follows:
a pretreatment method of a titanium anode base material comprises the following steps:
step S1, selecting a titanium material;
step S2, carrying out surface heat treatment, recrystallization and annealing on the titanium material, wherein the heat treatment temperature is 650-680 ℃, and carrying out heat preservation for 2-3h and then cooling along with the furnace;
step S3, carrying out electrochemical corrosion on the titanium material, wherein the electrolyte comprises the following components: 1-1.05mol/L NH 4 Br, 0.1-0.15mol/L NaF, 0.05-0.06mol/L HCL, 2-5ppm polyethylene glycol-2000, and the pH value of the electrolyte is 2-3, and the temperature is 25-30 ℃;
the electrolytic process comprises the following steps: the current density is 50-80A/m 2 Electrolyzing for 60-120 min;
and step S4, ultrasonically vibrating the electrochemically corroded titanium material, washing the titanium material with distilled water, and drying the titanium material.
Further, in step S3, the electrolysis process further includes:
the electrolysis temperature is 30-50 ℃, and the distance between the anode and the cathode is 80-100 mm.
Further, in step S3, the power supply used in the electrolysis process is a positive and negative pulse power supply, and the parameters thereof are as follows:
rated voltage: 24v, rated current: 2000A, rated power: 48kw, pulse frequency: 1000HZ, duty cycle: 20 percent.
Further, in the step S1, the selected titanium material is TA1, the grain size is 6-9 grades, and the Rockwell hardness is HRC 50-60.
Further, in step S4, the drying temperature is 110-.
Compared with the prior art, the pretreatment method of the titanium anode substrate has the beneficial effects that:
according to the pretreatment method of the titanium anode substrate, provided by the invention, after high-temperature heat treatment, titanium material grains can form a recrystallization structure again, and the grain size is more refined and uniform; and then, an oxide layer generated on the surface of the titanium material is corroded by an electrochemical corrosion process, so that the uniformity of the surface roughness of the titanium material after electrochemical corrosion is ensured. In the electrochemical corrosion process, the formula of the electrolyte is optimized, so that the electrochemical corrosion rate can be adjusted and controlled according to the current and voltage value, the grain boundary corrosion is carried out along the grain gap, the surface of the titanium material is in a honeycomb pore shape, the uniformity of the surface roughness of the titanium material after the electrochemical corrosion is further ensured, the production of a titanium anode coating is facilitated, the material stability is improved, and the operation safety and the risk are low.
In the pretreatment method of the titanium anode substrate, the electrochemical corrosion process adopts a positive and negative pulse power supply, and the anode and the cathode can be simultaneously treated in the treatment process, so that the production efficiency is improved, and the cost is reduced. The electrolyte can be added for repeated use according to the change of components, and simultaneously, the environmental protection cost is reduced.
And thirdly, after the electrochemical corrosion process, the titanium anode substrate pretreatment method provided by the invention removes residual impurities on the surface of the titanium material by adopting ultrasonic oscillation, thereby avoiding environmental pollution caused by the acid washing process.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
A pretreatment method of a titanium anode base material comprises the following steps:
step S1, selecting a titanium material;
has the following material selection requirements: material TA1, grain size grade 6-9, Rockwell hardness: HRC 50-60. The material is selected to be grain boundary etched by electrochemical etching, and the grain boundary etched by electrochemical etching can ensure the uniformity of the roughness of the material.
Step S2, carrying out surface heat treatment, recrystallization and annealing on the titanium material, wherein the heat treatment temperature is 650-680 ℃, and cooling along with the furnace after heat preservation for 2-3 h;
the surface heat treatment process can form a layer of passive film on the surface of the material and form crystal grains again, and can inhibit the corrosion rate from being too high in the electrolytic process.
Step S3, carrying out electrochemical corrosion on the titanium material, wherein the electrolyte comprises the following components: 1-1.05mol/L NH 4 Br, 0.1-0.15mol/L NaF, 0.05-0.06mol/L HCL, 2-5ppm polyethylene glycol-2000, and the pH value of the electrolyte is 2-3, and the temperature is 25-30 ℃;
the electrolytic process comprises the following steps: the current density is 50-80A/m 2 The electrolysis time is 60-120min, the electrolysis temperature is 30-50 ℃, the anode-cathode spacing is 80-100mm, and the phase change frequency is as follows: 1-2 min/time, and the voltage is more than 12 v;
in the electrolyte environment, Br, Cl ions and Ti ions form soluble TiBr 4 And TiCl 4 The reaction formula is as follows:
Ti+4Br - ＝TiBr 4 +4e；
when the chloride ion is more than 1000ppm and the voltage exceeds 12v, Ti +4Cl - ＝TiCl 4 +4e
The electrochemical reaction is carried out under the condition of low current density, the titanium material is not suitable for passivation, and the reaction speed can be controlled by the current density.
The battery used for electrolysis is a positive and negative pulse power supply, and the parameters are as follows: rated voltage: 24v, rated current: 2000A, rated power: 48kw, pulse frequency: 1000HZ, duty cycle: 20 percent. In the treatment process, the anode and the cathode can be treated simultaneously, so that the production efficiency is improved, and the cost is reduced.
Step S4, ultrasonically vibrating the titanium material after electrochemical corrosion, cleaning the titanium material with distilled water, and drying the titanium material;
wherein, ultrasonic oscillation is carried out for 1h to remove residue impurities which can not be seen by naked eyes; the drying condition is temperature of 110 ℃ and 130 ℃, and the time is 10-20 min.
Compared with the prior art, the pretreatment method of the titanium anode substrate has the beneficial effects that:
according to the pretreatment method of the titanium anode substrate, provided by the invention, after high-temperature heat treatment, titanium material grains can form a recrystallization structure again, and the grain size is more refined and uniform; and then, an oxide layer generated on the surface of the titanium material is corroded by an electrochemical corrosion process, so that the uniformity of the surface roughness of the titanium material after electrochemical corrosion is ensured. In the electrochemical corrosion process, the formula of the electrolyte is optimized, so that the electrochemical corrosion rate can be adjusted and controlled according to the current and voltage value, the grain boundary corrosion is carried out along the grain gap, the surface of the titanium material is in a honeycomb pore shape, the uniformity of the surface roughness of the titanium material after the electrochemical corrosion is further ensured, the production of a titanium anode coating is facilitated, the material stability is improved, and the operation safety and the risk are low.
In the pretreatment method of the titanium anode substrate, the electrochemical corrosion process adopts a positive and negative pulse power supply, and the anode and the cathode can be simultaneously treated in the treatment process, so that the production efficiency is improved, and the cost is reduced. The electrolyte can be added for repeated use according to the change of components, and simultaneously, the environmental protection cost is reduced.
And thirdly, after the electrochemical corrosion process, the titanium anode substrate pretreatment method provided by the invention removes residual impurities on the surface of the titanium material by adopting ultrasonic oscillation, thereby avoiding environmental pollution caused by the acid washing process.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (5)
1. A pretreatment method of a titanium anode base material is characterized by comprising the following steps:
step S1, selecting a titanium material;
step S2, carrying out surface heat treatment, recrystallization and annealing on the titanium material, wherein the heat treatment temperature is 650-680 ℃, and carrying out heat preservation for 2-3h and then cooling along with the furnace;
step S3, carrying out electrochemical corrosion on the titanium material, wherein the electrolyte comprises the following components: 1-1.05mol/LNH 4 Br, 0.1-0.15mol/L NaF, 0.05-0.06mol/L HCL, 2-5ppm polyethylene glycol-2000, and the pH value of the electrolyte is 2-3, and the temperature is 25-30 ℃;
the electrolytic process comprises the following steps: the current density is 50-80A/m 2 Electrolyzing for 60-120 min;
and step S4, ultrasonically vibrating the electrochemically corroded titanium material, washing the titanium material with distilled water, and drying the titanium material.
2. The method for pretreating a titanium anode substrate according to claim 1, wherein the electrolysis process further comprises, in step S3:
the electrolysis temperature is 30-50 ℃, and the distance between the anode and the cathode is 80-100 mm.
3. The method for pretreating a titanium anode substrate according to claim 1, wherein in step S3, the power supply used in the electrolysis process is a positive and negative pulse power supply, and the parameters are as follows:
rated voltage: 24v, rated current: 2000A, rated power: 48kw, pulse frequency: 1000HZ, duty cycle: 20 percent.
4. The method as claimed in claim 1, wherein the titanium material selected in step S1 is TA1, the grain size is 6-9 grade, and the Rockwell hardness is HRC 50-60.
5. The method as claimed in claim 1, wherein the drying temperature is 110-130 ℃ and the time is 10-20min in step S4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537895A (en) * | 2022-10-14 | 2022-12-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of pure titanium surface colorful anodic oxide film |
| CN117646270A (en) * | 2024-01-29 | 2024-03-05 | 宝鸡钛普锐斯钛阳极科技有限公司 | Titanium anode suitable for organic additive application system and manufacturing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115537895A (en) * | 2022-10-14 | 2022-12-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of pure titanium surface colorful anodic oxide film |
| CN117646270A (en) * | 2024-01-29 | 2024-03-05 | 宝鸡钛普锐斯钛阳极科技有限公司 | Titanium anode suitable for organic additive application system and manufacturing method thereof |
| CN117646270B (en) * | 2024-01-29 | 2024-04-12 | 宝鸡钛普锐斯钛阳极科技有限公司 | Titanium anode suitable for organic additive application system and manufacturing method thereof |
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