CN109536964A - A kind of acid etching method of metal oxide electrode Titanium base - Google Patents
A kind of acid etching method of metal oxide electrode Titanium base Download PDFInfo
- Publication number
- CN109536964A CN109536964A CN201811616820.8A CN201811616820A CN109536964A CN 109536964 A CN109536964 A CN 109536964A CN 201811616820 A CN201811616820 A CN 201811616820A CN 109536964 A CN109536964 A CN 109536964A
- Authority
- CN
- China
- Prior art keywords
- titanium base
- metal oxide
- titanium
- oxide electrode
- etching method
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention belongs to the electrode material fields of Applied Electrochemistry and energy industry, are related to a kind of acid etching method of metal oxide electrode Titanium base, comprising: pre-process to metal oxide electrode Titanium base；Prepare mixing pickling solution；Pretreated Titanium base is placed in mixing pickling solution；Mixing pickling solution is placed in supersonic wave cleaning machine and is cleaned；Titanium base cleaning is taken out to dry.By the concentration and etch period of each acid in control mixing pickling solution, the advantages of adjusting ultrasonic cleaning frequency machine time appropriate can give full play to mixed acid and ultrasonic vibration, the infringement of high temperature and acid mist to operator is avoided.In addition, the pit of size and appropriate depth can be obtained using acid etching method provided by the invention, without sharp acute angle, no titanium oxide layer forms microcosmic uniform rough surface, specific surface area is increased, the binding force of coating and matrix is enhanced, improves sour treatment effeciency.
Description
Technical field
The invention belongs to the electrode material fields of Applied Electrochemistry and energy industry, are related to a kind of metal oxide electrode titanium
The acid etching method of matrix.
Background technique
Titanium-based oxide coated electrode is mainly made of Titanium base and surface precious metal oxide coating, abbreviation DSA or titanium
Electrode.So far from nineteen sixty-five H.Beer application ruthenium oxide coatings patent, titanium-based oxide coated electrode has more than 50 years history.By
In with conventional graphite electrodes, lead and the incomparable advantage of lead alloy, Ti electrode be widely used in chlorine industry,
The fields such as the electroextraction of non-ferrous metal or metal oxide, metal foil production and sewage treatment.
For the performance for improving oxide electrode, before metal oxide electrode Titanium base coats, it is necessary to carry out stringent pre-
Processing.On the one hand the binding force of matrix Yu metal oxide covering can be enhanced in pretreatment appropriate, so as to improve electric conductivity, prolong
Its long service life；On the other hand the roughness that matrix surface can be improved increases the specific surface area of electrode, reduces real current
Density improves the chemical property of electrode.Therefore, the method for substrate pretreated directly affects the surface shape of metal oxide electrode
Looks, microstructure, the stability of electro-chemical activity and electrode are a key steps in metal oxide electrode preparation process
Suddenly.
Currently, industrial common metal oxide electrode Titanium base acid etch processing method is using high-temperature water dissolution grass
Acid becomes certain density oxalic acid solution and carries out acid etching.This method needs the long period that could obtain appropriate roughness surface
Matrix, solution temperature-rise period and acid etching require the plenty of time, and operating environment is high temperature acid mist, strong to the body of operator
Health has compared with major injury.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, a kind of metal oxide electrode Titanium base is provided
Acid etching method avoids and boils the influence of high temperature and acid mist to operator's body in traditional oxalic acid etching process, operation
Environmental security, environmental protection, but also the binding force between metal oxide active coating and matrix can be improved, enhancing metal oxidation
The stability of object electrode improves the surface electrochemistry activity of oxide electrode and the utilization rate of reactive metal oxides.
To achieve the goals above, the present invention provides the following technical scheme that
A kind of acid etching method of metal oxide electrode Titanium base, specifically comprises the following steps:
1) metal oxide electrode Titanium base is pre-processed；
2) mixing pickling solution is prepared；
3) pretreated Titanium base is placed in mixing pickling solution；
4) mixing pickling solution is placed in supersonic wave cleaning machine and is cleaned；
5) Titanium base cleaning is taken out to dry.
Further, the pretreatment in the step 1) is blasting treatment, and the sand of the blasting treatment is steel sand, palm fibre is rigid
At least one of jade, white fused alumina, quartz sand obtain the surface of macroroughness, simultaneously by carrying out blasting treatment to Titanium base
The titanium oxide for removing Titanium base surface makes have good electrical conductance between Titanium base and metal oxide active layer.
Further, the Titanium base in the step 1) be national standard TA1 or TA2 pure titanium, or for titanium plate, titanium net, titanium tube,
Stud, titanium silk for preventing Titanium base from electrochemical corrosion occurs, and can enhance the binding force between Titanium base and coating.
Further, the mixing pickling solution in the step 2) includes at least the hydrofluoric acid that concentration is 1%~5%, dense
The nitric acid that degree is 10%~50%, the hydrochloric acid that concentration is 1%~10%, any two in hydrogen peroxide that concentration is 1%~30%
Kind.
Further, the supersonic wave cleaning machine in the step 4), cleaning frequency are 20kHz~30kHz, scavenging period
For 10~60min.
Further, the cleaning of Titanium base selects deionized water to be cleaned in the step 5).
Compared with prior art, technical solution provided by the invention includes following the utility model has the advantages that the present invention is mixed by control
The concentration and etch period of each acid in pickling solution are closed, the adjusting ultrasonic cleaning frequency machine time appropriate can give full play to mixing
The advantages of acid and ultrasonic vibration, avoid the infringement of high temperature and acid mist to operator.In addition, using metal oxygen provided by the invention
The acid etching method of compound electrode Titanium base, can obtain the pit of size and appropriate depth, without sharp acute angle, no titanyl
Layer forms microcosmic uniform rough surface, increases specific surface area, enhance the binding force of coating and matrix, improve sour place
Manage efficiency.Finally, using thermolysis process on the Titanium base that the acid etching method by Titanium base of the present invention is handled
The metal oxide electrode of preparation has good electro catalytic activity and electrochemical stability.
Detailed description of the invention
Fig. 1 is the flow diagram of the acid etching method of metal oxide electrode Titanium base provided by the invention；
Fig. 2 is the structural representation of Titanium base surface under the microscope under room temperature after coated titanium electrode matrix acid etching
Figure.
Specific embodiment
Example embodiments are described in detail here, embodiment described in following exemplary embodiment
Do not represent all embodiments consistented with the present invention.On the contrary, they be only with it is being described in detail in the appended claims,
The example of the consistent method of some aspects of the invention.
In order to make those skilled in the art more fully understand technical solution of the present invention, with reference to the accompanying drawings and embodiments
Present invention is further described in detail.
Embodiment 1
It is shown in Figure 1, it is a kind of stream of the acid etching method of metal oxide electrode Titanium base provided by the invention
Journey schematic diagram, specifically comprises the following steps:
1) metal oxide electrode Titanium base is pre-processed；
2) mixing pickling solution is prepared；
3) pretreated Titanium base is placed in mixing pickling solution；
4) mixing pickling solution is placed in supersonic wave cleaning machine and is cleaned；
5) Titanium base cleaning is taken out to dry.
Further, the pretreatment in the step 1) is blasting treatment, and the sand of the blasting treatment is steel sand, palm fibre is rigid
At least one of jade, white fused alumina, quartz sand obtain the surface of macroroughness, simultaneously by carrying out blasting treatment to Titanium base
The titanium oxide for removing Titanium base surface makes have good electrical conductance between Titanium base and metal oxide active layer.
Further, the Titanium base in the step 1) be national standard TA1 or TA2 pure titanium, or for titanium plate, titanium net, titanium tube,
Stud, titanium silk for preventing Titanium base from electrochemical corrosion occurs, and can enhance the binding force between Titanium base and coating.
Further, the mixing pickling solution in the step 2) includes at least the hydrofluoric acid that concentration is 1%~5%, dense
The nitric acid that degree is 10%~50%, the hydrochloric acid that concentration is 1%~10%, any two in hydrogen peroxide that concentration is 1%~30%
Kind.
Further, the supersonic wave cleaning machine in the step 4), cleaning frequency are 20kHz~30kHz, scavenging period
For 10~60min.
Further, the cleaning of Titanium base selects deionized water to be cleaned in the step 5).
Embodiment 2
A kind of acid etching method of metal oxide electrode Titanium base provided by the invention, specific process flow is such as
Under: 1) using the pure titanium of national standard TA1, TA2 as matrix, macroroughness surface is formed by blasting treatment；2) it is molten to prepare mixing acid etching
Liquid, the hydrofluoric acid for the use of concentration being 1%~5%, the nitric acid that concentration is 10%~50%, the hydrochloric acid that concentration is 1%~10% are dense
Degree is configured to mixing pickling solution for 1%~30% hydrogen peroxide and pure water；3) storage is mixed into pickling solution at normal temperature
Container be put into supersonic wave cleaning machine, Titanium base starts supersonic wave cleaning machine, etch period after being put into mixing acid etching solution container
For 10~60min, supersonic wave cleaning machine selects the cleaning frequency within the scope of 20kHz~30kHz, completes metal oxide electrode titanium
The acid etching of matrix.
Embodiment 3
A kind of acid etching method of metal oxide electrode Titanium base provided by the invention, specific process flow is such as
Under: 1) using titanium plate as matrix, macroroughness surface is formed by grit blasting processing；2) hydrofluoric acid for being 1% by concentration, concentration are
20% nitric acid adds deionized water to be configured to mixing pickling solution；3) the non-glass container of the mixing pickling solution will be held
It is placed in supersonic wave cleaning machine, sets 20kHz for cleaning frequency, by grit blasting treated titanium that 2mm titanium plate is drawn into
Vertical net is placed in mixing pickling solution, is opened supersonic wave cleaning machine and is reacted 15min, is taken out Titanium base and is rushed at once with deionized water
It washes and dries, obtain surface without titanium oxide layer, be in ash gray titanium net.After acid etching, with micro- sem observation, it is seen that titanium-based
The pit in body surface face is uniform in size consistent, and has no in grains of sand insertion mesh or pit, and Substrate Surface Roughness is suitable for.In addition,
After carrying out coating treatment to Titanium base surface with thermal decomposition method, through testing: wiping surface with white filter paper, applied on filter paper without obvious
Layer falls ash；After 180 ° of Titanium base bending, thus coating illustrates that the binding force of Titanium base surface and coating is good without obviously falling off
It is good.
Embodiment 4
A kind of acid etching method of metal oxide electrode Titanium base provided by the invention, specific process flow is such as
Under: 1) using titanium plate as matrix, macroroughness surface is formed by grit blasting processing；2) hydrofluoric acid for being 3% by concentration, concentration are
30% nitric acid, the hydrogen peroxide that concentration is 20% add deionized water to be configured to mixing pickling solution；3) mixed acid will be held
The non-glass container of erosion solution is placed in supersonic wave cleaning machine, sets 20kHz for cleaning frequency, treated by grit blasting
6mm titanium plate is placed in mixing pickling solution, is opened supersonic wave cleaning machine and is reacted 30min, is taken out Titanium base and is used deionization at once
Water flushing is dried, and obtains surface without titanium oxide layer, in the light gray titanium plate of unobvious metallic luster.After acid etching, use
Micro- sem observation, it is seen that the pit on Titanium base surface is uniform in size consistent, and has no in grains of sand insertion mesh or pit, matrix table
Surface roughness is suitable.In addition, after carrying out coating treatment to Titanium base surface with thermal decomposition method, through testing: with white filter paper wiping
Ash is fallen without obvious coating on filter paper in surface；After 180 ° of Titanium base bending, thus coating illustrates titanium-based body surface without obviously falling off
The binding force of face and coating is good.
Various acid proportions used in above example are that the surface of the base body of acid etching as needed and physical form calculating are matched
System overcomes the unicity of traditional oxalic acid etching, saves raw material, the matrix that improves that acid etching efficiency, operating environment are friendly, and treated
Surface roughness is suitble to thermal decomposition method sintered surface coating.
The above is only a specific embodiment of the invention, is made skilled artisans appreciate that or realizing this hair
It is bright.Various modifications to these embodiments will be apparent to one skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.
It should be understood that the invention is not limited to above contents, and can carry out without departing from the scope it is various
Modifications and changes.The scope of the present invention is limited only by the attached claims.
Claims (7)
1. a kind of acid etching method of metal oxide electrode Titanium base, which is characterized in that specifically comprise the following steps:
1) metal oxide electrode Titanium base is pre-processed；
2) mixing pickling solution is prepared；
3) pretreated Titanium base is placed in mixing pickling solution；
4) mixing pickling solution is placed in supersonic wave cleaning machine and is cleaned；
5) Titanium base cleaning is taken out to dry.
2. the acid etching method of metal oxide electrode Titanium base according to claim 1, which is characterized in that the step
It is rapid 1) in pretreatment be blasting treatment.
3. the acid etching method of metal oxide electrode Titanium base according to claim 2, which is characterized in that the spray
The sand of sand processing is at least one of steel sand, Brown Alundum, white fused alumina, quartz sand.
4. the acid etching method of metal oxide electrode Titanium base according to claim 1, which is characterized in that the step
It is rapid 1) in Titanium base be national standard TA1 or TA2 pure titanium, or be titanium plate, titanium net, titanium tube, stud, titanium silk.
5. the acid etching method of metal oxide electrode Titanium base according to claim 1, which is characterized in that the step
It is rapid 2) in mixing pickling solution include at least concentration be 1%~5% hydrofluoric acid, concentration be 10%~50% nitric acid, it is dense
The hydrochloric acid that degree is 1%~10%, any two kinds in hydrogen peroxide that concentration is 1%~30%.
6. the acid etching method of metal oxide electrode Titanium base according to claim 1, which is characterized in that the step
It is rapid 4) in supersonic wave cleaning machine cleaning frequency be 20kHz~30kHz, scavenging period be 10~60min.
7. the acid etching method of metal oxide electrode Titanium base according to claim 1, which is characterized in that the step
It is rapid 5) in Titanium base cleaning select deionized water cleaned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811616820.8A CN109536964A (en) | 2018-12-27 | 2018-12-27 | A kind of acid etching method of metal oxide electrode Titanium base |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811616820.8A CN109536964A (en) | 2018-12-27 | 2018-12-27 | A kind of acid etching method of metal oxide electrode Titanium base |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109536964A true CN109536964A (en) | 2019-03-29 |
Family
ID=65858019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811616820.8A Pending CN109536964A (en) | 2018-12-27 | 2018-12-27 | A kind of acid etching method of metal oxide electrode Titanium base |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109536964A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144607A (en) * | 2019-07-08 | 2019-08-20 | 西安泰金工业电化学技术有限公司 | A kind of preparation method of the anti-deformation Ni―Ti anode of hydrometallurgy |
| CN110823667A (en) * | 2019-11-18 | 2020-02-21 | 燕山大学 | Metallographic corrosive agent for high-strength titanium alloy and preparation method of metallographic sample of high-strength titanium alloy |
| CN114712555A (en) * | 2022-04-12 | 2022-07-08 | 四川亿诺森生物科技有限公司 | Hard tissue repair material and preparation method and application thereof |
| CN115213819A (en) * | 2022-06-20 | 2022-10-21 | 华南师大(清远)科技创新研究院有限公司 | Copper material surface micro-nano composite structure and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880509A (en) * | 2005-06-14 | 2006-12-20 | 中国船舶重工集团公司第七二五研究所 | Method for preprocessing metal oxide anode substrate |
| CN103006339A (en) * | 2012-12-13 | 2013-04-03 | 大连理工（营口）新材料工程中心有限公司 | Preparation method of multilevel cellular structure for medical pure titanium implant surface |
| CN104499023A (en) * | 2014-12-16 | 2015-04-08 | 广州中国科学院先进技术研究所 | Anodic oxidation method of spare part containing blind hole |
| CN105624753A (en) * | 2015-12-24 | 2016-06-01 | 广州中国科学院先进技术研究所 | Technology for uniform deposition of HA (hydroxyapatite) coatings on medical porous titanium and titanium alloy |
| CN108525019A (en) * | 2018-03-27 | 2018-09-14 | 浙江大学 | A method of forming the compound grade porous structure of Sr/Zn codope micrometer/nanometers in titanium plate surface |
-
2018
- 2018-12-27 CN CN201811616820.8A patent/CN109536964A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880509A (en) * | 2005-06-14 | 2006-12-20 | 中国船舶重工集团公司第七二五研究所 | Method for preprocessing metal oxide anode substrate |
| CN103006339A (en) * | 2012-12-13 | 2013-04-03 | 大连理工（营口）新材料工程中心有限公司 | Preparation method of multilevel cellular structure for medical pure titanium implant surface |
| CN104499023A (en) * | 2014-12-16 | 2015-04-08 | 广州中国科学院先进技术研究所 | Anodic oxidation method of spare part containing blind hole |
| CN105624753A (en) * | 2015-12-24 | 2016-06-01 | 广州中国科学院先进技术研究所 | Technology for uniform deposition of HA (hydroxyapatite) coatings on medical porous titanium and titanium alloy |
| CN108525019A (en) * | 2018-03-27 | 2018-09-14 | 浙江大学 | A method of forming the compound grade porous structure of Sr/Zn codope micrometer/nanometers in titanium plate surface |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144607A (en) * | 2019-07-08 | 2019-08-20 | 西安泰金工业电化学技术有限公司 | A kind of preparation method of the anti-deformation Ni―Ti anode of hydrometallurgy |
| CN110144607B (en) * | 2019-07-08 | 2020-06-12 | 西安泰金工业电化学技术有限公司 | Preparation method of anti-deformation titanium anode for hydrometallurgy |
| CN110823667A (en) * | 2019-11-18 | 2020-02-21 | 燕山大学 | Metallographic corrosive agent for high-strength titanium alloy and preparation method of metallographic sample of high-strength titanium alloy |
| CN110823667B (en) * | 2019-11-18 | 2021-02-26 | 燕山大学 | Metallographic corrosive agent for high-strength titanium alloy and preparation method of metallographic sample of high-strength titanium alloy |
| CN114712555A (en) * | 2022-04-12 | 2022-07-08 | 四川亿诺森生物科技有限公司 | Hard tissue repair material and preparation method and application thereof |
| CN115213819A (en) * | 2022-06-20 | 2022-10-21 | 华南师大(清远)科技创新研究院有限公司 | Copper material surface micro-nano composite structure and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109536964A (en) | A kind of acid etching method of metal oxide electrode Titanium base | |
| CN105967281B (en) | A kind of titanium-based Asia Titanium oxide electrode preparation method | |
| CN104973662B (en) | Oxide anode for treatment of ship domestic sewage and preparation method thereof | |
| CN104562128B (en) | A kind of method for preparing thermal protection ceramic layer on metal or metallic composite surface | |
| CN106637337A (en) | Method for improving compactness of aluminum alloy micro-arc oxide coating | |
| CN103726093B (en) | A kind of environment-friendly type that adopts contains nickel electrolyte is prepared differential arc oxidation film layer method at Mg alloy surface | |
| CN101276916A (en) | Preparation technique for anti-corrosion fuel cell stainless dual-polar plate | |
| CN108441918A (en) | A kind of aluminum alloy surface treatment process | |
| CN105483744B (en) | A kind of porous liberation of hydrogen catalyst and preparation method thereof and the electrode containing the liberation of hydrogen catalyst | |
| CN112609218A (en) | Preparation method of super-hydrophobic micro-arc oxidation composite membrane | |
| CN106245091A (en) | Composite titania material and its preparation method and application | |
| CN111172577A (en) | Preparation method of magnesium alloy surface low-porosity micro-arc oxidation film | |
| CN1694282A (en) | Electrode for all-vanadium redox flow battery and preparation method thereof | |
| CN104087935B (en) | A kind of preparation method of titanium nickel medical implant material | |
| CN108624925A (en) | A kind of composite preparation process of Mg alloy surface super-drainage structure | |
| CN109440179A (en) | A kind of metal tantalum matrix of roughing in surface and preparation method thereof | |
| CN104480490B (en) | Ballast Management system cold water type oxide anode and preparation method | |
| CN107974693B (en) | The oxide anode material and its preparation process of anti-manganese ion pollution | |
| Lei et al. | Performance and corrosion resistance mechanism of SA-Al composite hydrophobic coating on electrolytic manganese surface | |
| Li et al. | The growth rate of nanotubes and the quantity of charge during anodization | |
| CN104451819A (en) | Method for constructing superhydrophobic aluminum surface with high stability | |
| CN106191902A (en) | A kind of method preparing hydrogen doping oxide ceramics micro Nano material | |
| CN109252200A (en) | A kind of aluminum alloy die casting surface treatment method | |
| CN101358356A (en) | Method for preparing high specific surface diamond electrode | |
| CN102943246B (en) | Method for preparing metal surface super-hydrophobicity aluminum coating |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190329 |