CN114855105B - Titanium anode substrate pretreatment method - Google Patents
Titanium anode substrate pretreatment method Download PDFInfo
- Publication number
- CN114855105B CN114855105B CN202210122935.1A CN202210122935A CN114855105B CN 114855105 B CN114855105 B CN 114855105B CN 202210122935 A CN202210122935 A CN 202210122935A CN 114855105 B CN114855105 B CN 114855105B
- Authority
- CN
- China
- Prior art keywords
- titanium
- titanium material
- temperature
- electrolyte
- anode substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention discloses a pretreatment method of a titanium anode substrate, 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 cooling along with a furnace after heat preservation for 2-3 hours; and (3) carrying out electrochemical corrosion on the titanium material, wherein the electrolyte comprises the following components: 1 to 1.05mol/L NH 4 Br,0.1-0.15mol/L NaF,0.05-0.06mol/L HCL,2-5ppm polyethylene glycol-2000, and electrolyte pH=2=3, the temperature is 25-30 ℃; the electrolysis process comprises the following steps: the current density is 50-80A/m 2 The electrolysis time is 60-120min; and (3) ultrasonically oscillating the electrochemically corroded titanium material, cleaning with distilled water, and drying. According to the pretreatment method for the titanium anode substrate, the electrochemical corrosion technology is adopted to treat the oxide skin on the surface, so that the operation safety risk is low, the stability of the titanium anode plate material is good, the electrolyte can be reused, 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 existing titanium anode surface treatment process is to sand blast and coarsen the surface of the material, then anneal and level, and then remove oxide scale by oxalic acid washing. 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 2-3h. In the treatment process, a large amount of acid mist overflows due to the boiling state, the axial environment is corroded, and the working environment is poor;
(2) Oxalic acid is disposable and cannot be reused;
(3) Forming an oxide layer on the surface of the titanium material after surface treatment, and carrying out acid washing by oxalic acid, wherein the oxalic acid is difficult to react with titanium oxide at the temperature of 90-100 ℃; oxalic acid permeates the oxide layer to react with titanium, and the reaction is slower at low temperature, but the temperature reaches 50 DEG CThe dissolution rate of Ti is accelerated, and Ti is oxidized into Ti 3+ ，H + Is reduced into hydrogen, and has the chemical reaction formula: ti+C 2 H 2 0 4 ＝Ti(C 2 O 4 ) 2 +H 2 The corrosion rate of oxalic acid to titanium is uncontrollable, and the corrosion amount of titanium is large, so that the defect generated by the titanium is the influence on the quality of the titanium anode;
(4) Before the pickling treatment, the substrate must be roughened by sandblasting, which is too costly.
In view of the above, it is necessary to provide a new pretreatment method to solve the above-mentioned problems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a pretreatment method for a titanium anode substrate, which adopts an electrochemical corrosion process to treat oxide skin on the surface, has low operation safety hazard, good stability of the titanium anode plate material, reusable electrolyte and low treatment cost.
In order to solve the problems, the technical scheme of the invention is as follows:
a method for pretreating a titanium anode substrate, comprising the steps of:
step S1, selecting a titanium material;
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 a furnace after heat preservation for 2-3 hours;
step S3, carrying out electrochemical corrosion on the titanium material, wherein the electrolyte comprises the following components: 1 to 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=2-3 of electrolyte, the temperature is 25-30 ℃;
the electrolysis process comprises the following steps: the current density is 50-80A/m 2 The electrolysis time is 60-120min;
and S4, ultrasonically oscillating the electrochemically corroded titanium material, cleaning with distilled water, and drying.
Further, in step S3, the electrolysis process further includes:
the electrolysis temperature is 30-50 ℃, and the anode-cathode spacing is 80-100mm.
Further, in step S3, the power used in the electrolysis process is a positive and negative pulse power, and the parameters thereof are as follows:
rated voltage: 24v, rated current: 2000A, rated power: 48kw, pulse frequency: 1000HZ, duty cycle: 20%.
Further, in the step S1, the selected titanium material is TA1, the grain size is 6-9 grades, and the Rockwell hardness is HRC50-60.
Further, in step S4, the drying temperature is 110-130 ℃ and the drying time is 10-20min.
Compared with the prior art, the pretreatment method for the titanium anode substrate has the beneficial effects that:
1. according to the pretreatment method for the titanium anode substrate, after high-temperature heat treatment, the titanium crystal grains can form a recrystallization structure again, and the grain size is more refined and uniform; and then the oxide layer generated on the surface of the titanium material is corroded through an electrochemical corrosion process, so that the uniformity of the roughness of the surface of the titanium material after electrochemical corrosion is ensured. In the electrochemical corrosion process, the electrochemical corrosion rate can be regulated and controlled according to the current and voltage values by optimizing the formula of the electrolyte, so that corrosion is carried out along grain gaps to carry out grain boundary corrosion, the surface of the titanium material is enabled to form honeycomb pore shapes, the uniformity of the surface roughness of the titanium material after electrochemical corrosion is further ensured, the production of a titanium anode coating is facilitated, the material stability is improved, and the operation safety risk is low.
2. The pretreatment method for the titanium anode substrate adopts the positive and negative pulse power supply in the electrochemical corrosion process, and the anode and the cathode can be treated simultaneously in the treatment process, so that the production efficiency is improved, and the cost is reduced. The electrolyte can be added according to the component change for repeated use, and the environmental protection cost is reduced.
3. According to the pretreatment method for the titanium anode substrate, after the electrochemical corrosion process, the ultrasonic vibration is adopted to remove residual impurities on the surface of the titanium material, so that environmental pollution caused by the pickling process is avoided.
Detailed Description
In order to better understand the technical solution in the embodiments of the present invention and make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the present invention will be further described.
The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
A method for pretreating a titanium anode substrate, comprising the steps of:
step S1, selecting a titanium material;
the material selection method has the following steps: material TA1, grain size 6-9 grade, rockwell hardness: HRC50-60. The material is selected to have grain boundary corrosion by electrochemical corrosion, and the corrosion can ensure the uniformity of the roughness of the material.
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 a furnace after heat preservation for 2-3 hours;
the surface heat treatment process makes the material surface form one layer of passivation film and grain form once again, and this can inhibit the corrosion rate in the electrolytic process.
Step S3, carrying out electrochemical corrosion on the titanium material, wherein the electrolyte comprises the following components: 1 to 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=2-3 of electrolyte, the temperature is 25-30 ℃;
the electrolysis 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 distance is 80-100mm, and the phase change frequency is as follows: 1-2 min/time, the voltage is more than 12v;
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 is more than 12v, ti+4Cl - ＝TiCl 4 +4e
The electrochemical reaction is carried out under the condition of low current density, the titanium material is not easy to be passivated, 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%. 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, cleaning the titanium material subjected to electrochemical corrosion by distilled water after ultrasonic oscillation, and drying;
wherein, ultrasonic oscillation is carried out for 1h, and residue impurities invisible to naked eyes are removed; the drying condition is that the temperature is 110-130 ℃ and the time is 10-20min.
Compared with the prior art, the pretreatment method for the titanium anode substrate has the beneficial effects that:
1. according to the pretreatment method for the titanium anode substrate, after high-temperature heat treatment, the titanium crystal grains can form a recrystallization structure again, and the grain size is more refined and uniform; and then the oxide layer generated on the surface of the titanium material is corroded through an electrochemical corrosion process, so that the uniformity of the roughness of the surface of the titanium material after electrochemical corrosion is ensured. In the electrochemical corrosion process, the electrochemical corrosion rate can be regulated and controlled according to the current and voltage values by optimizing the formula of the electrolyte, so that corrosion is carried out along grain gaps to carry out grain boundary corrosion, the surface of the titanium material is enabled to form honeycomb pore shapes, the uniformity of the surface roughness of the titanium material after electrochemical corrosion is further ensured, the production of a titanium anode coating is facilitated, the material stability is improved, and the operation safety risk is low.
2. The pretreatment method for the titanium anode substrate adopts the positive and negative pulse power supply in the electrochemical corrosion process, and the anode and the cathode can be treated simultaneously in the treatment process, so that the production efficiency is improved, and the cost is reduced. The electrolyte can be added according to the component change for repeated use, and the environmental protection cost is reduced.
3. According to the pretreatment method for the titanium anode substrate, after the electrochemical corrosion process, the ultrasonic vibration is adopted to remove residual impurities on the surface of the titanium material, so that environmental pollution caused by the pickling process is avoided.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims (5)
1. A method for pretreating a titanium anode substrate, comprising the steps of:
step S1, selecting a titanium material;
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 a furnace after heat preservation for 2-3 hours;
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=2-3 of electrolyte, the temperature is 25-30 ℃;
the electrolysis process comprises the following steps: the current density is 50-80A/m 2 The electrolysis time is 60-120min;
and S4, ultrasonically oscillating the electrochemically corroded titanium material, cleaning with distilled water, and drying.
2. The method for pretreating a titanium anode substrate according to claim 1, wherein in step S3, the electrolytic process further comprises:
the electrolysis temperature is 30-50 ℃, and the anode-cathode spacing is 80-100mm.
3. The method according to claim 1, wherein in step S3, the power source used in the electrolysis process is a positive and negative pulse power source, and the parameters are as follows:
rated voltage: 24v, rated current: 2000A, rated power: 48kw, pulse frequency: 1000HZ, duty cycle: 20%.
4. The method according to claim 1, wherein the titanium material selected in step S1 is TA1, the grain size is 6 to 9, and the rockwell hardness is HRC50-60.
5. The method according to claim 1, wherein in step S4, the drying temperature is 110 to 130 ℃ and the time is 10 to 20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210122935.1A CN114855105B (en) | 2022-02-09 | 2022-02-09 | Titanium anode substrate pretreatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210122935.1A CN114855105B (en) | 2022-02-09 | 2022-02-09 | Titanium anode substrate pretreatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114855105A CN114855105A (en) | 2022-08-05 |
| CN114855105B true CN114855105B (en) | 2023-10-13 |
Family
ID=82628012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210122935.1A Active CN114855105B (en) | 2022-02-09 | 2022-02-09 | Titanium anode substrate pretreatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114855105B (en) |
Families Citing this family (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 |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH535072A (en) * | 1967-02-10 | 1973-03-31 | Chemnor Ag | Electrode, process for its manufacture and its use as an anode |
| US4581077A (en) * | 1984-04-27 | 1986-04-08 | Nippon Mining Co., Ltd. | Method of manufacturing rolled titanium alloy sheets |
| CN101775633A (en) * | 2010-01-18 | 2010-07-14 | 哈尔滨工业大学 | Method for preparing black titanium oxide coating on titanium surface |
| CN105374566A (en) * | 2015-10-10 | 2016-03-02 | 华北电力大学（保定） | Preparation method of titanium dioxide photo-anode |
| CN105965211A (en) * | 2016-06-22 | 2016-09-28 | 宝鸡钛产业研究院有限公司 | Preparation method of colorful titanium punching board for architectural ornament |
| CN106567122A (en) * | 2017-02-17 | 2017-04-19 | 大博医疗科技股份有限公司 | Electrochemical polishing electrolyte and polishing method for titanium and titanium alloy |
| CN108455709A (en) * | 2018-04-11 | 2018-08-28 | 北京工业大学 | A kind of preparation method of three indium oxides modifying titanium dioxide nanometer pipe array electrode |
| CN111020671A (en) * | 2020-01-16 | 2020-04-17 | 西安庄信新材料科技有限公司 | Method for forming oxide film on surface of titanium product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101526298B1 (en) * | 2013-04-22 | 2015-06-10 | 서울대학교산학협력단 | Method of manufacturing a titanium oxide electrode, system for generating oxidative reactive species, system for generating chlorine, dye-sensitized solar cell, and electric double-layer capacitor including the same |
-
2022
- 2022-02-09 CN CN202210122935.1A patent/CN114855105B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH535072A (en) * | 1967-02-10 | 1973-03-31 | Chemnor Ag | Electrode, process for its manufacture and its use as an anode |
| US4581077A (en) * | 1984-04-27 | 1986-04-08 | Nippon Mining Co., Ltd. | Method of manufacturing rolled titanium alloy sheets |
| CN101775633A (en) * | 2010-01-18 | 2010-07-14 | 哈尔滨工业大学 | Method for preparing black titanium oxide coating on titanium surface |
| CN105374566A (en) * | 2015-10-10 | 2016-03-02 | 华北电力大学（保定） | Preparation method of titanium dioxide photo-anode |
| CN105965211A (en) * | 2016-06-22 | 2016-09-28 | 宝鸡钛产业研究院有限公司 | Preparation method of colorful titanium punching board for architectural ornament |
| CN106567122A (en) * | 2017-02-17 | 2017-04-19 | 大博医疗科技股份有限公司 | Electrochemical polishing electrolyte and polishing method for titanium and titanium alloy |
| CN108455709A (en) * | 2018-04-11 | 2018-08-28 | 北京工业大学 | A kind of preparation method of three indium oxides modifying titanium dioxide nanometer pipe array electrode |
| CN111020671A (en) * | 2020-01-16 | 2020-04-17 | 西安庄信新材料科技有限公司 | Method for forming oxide film on surface of titanium product |
Non-Patent Citations (1)
| Title |
|---|
| 湿法冶金中新型铅基阳极材料的研究进展;张璋;陈步明;郭忠诚;黄惠;徐瑞东;;材料导报(第19期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114855105A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114855105B (en) | Titanium anode substrate pretreatment method | |
| US7052592B2 (en) | Chromium plating method | |
| EP2054539B1 (en) | Method for deposition of chromium layers as hard- chrome plating, electroplating bath and hard- chrome surfaces | |
| CA1105878A (en) | Method for stripping tungsten carbide from titanium or titanium alloy substrates | |
| CN107338469A (en) | A kind of method of ironware surface zinc layers and chromium passivating layer electrolytic deplating process | |
| JP5688161B2 (en) | Electrolytic dissolution of chromium from a chromium electrode. | |
| CN102787346B (en) | Plasma cleaning process before clean and environment-friendly plated film | |
| JP3955933B2 (en) | Method for adjusting the outer surface of a continuous casting mold made of copper or a copper alloy including a nickel plating step and a nickel removal step | |
| US3627654A (en) | Electrolytic process for cleaning high-carbon steels | |
| CN101698955A (en) | Stainless steel, titanium and titanium alloy electromechanical blackening method | |
| RU2556251C1 (en) | Method for electrolyte-plasma removal of polymer coatings from surface of laminated torsion bar of helicopter main rotor | |
| CN109267142A (en) | A kind of PH stainless steel room temperature electrolytic pickling method | |
| CN104195559A (en) | Method for performing deplating and recovering zinc from zinc layer on steel tube surface | |
| RU2357019C2 (en) | Method of electrolyte-plasma treatment of details | |
| JP3792335B2 (en) | Finishing electrolytic pickling method in descaling of stainless steel strip | |
| CA1077433A (en) | Roughening aluminium plate electrochemically in neutral salt solution | |
| JPH11323565A (en) | Pretreatment of electroless nickel plating | |
| JPH0472098A (en) | Production of aluminum substrate for printing plate | |
| CN111621829A (en) | Method and equipment for ceramic surface treatment of aluminum alloy with high Cu content and/or Si content | |
| JP2517353B2 (en) | Descaling method for stainless steel strip | |
| JPH03173800A (en) | Production of substrate for printing plate | |
| CN107419308A (en) | A kind of surface treatment method of stainless steel electric cooker lid | |
| CN114457337A (en) | Chemical method for ultrasonic-assisted removal of platinum metal on stainless steel surface under cathodic protection | |
| JP4672309B2 (en) | Alkaline zinc plating method on cast iron | |
| JPS5818434B2 (en) | Aluminum Zaino Tosohouhouhou |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |