CN106367794A - Method for rapidly preparing ordered anodic titanium oxide nanotube array film - Google Patents
Method for rapidly preparing ordered anodic titanium oxide nanotube array film Download PDFInfo
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- CN106367794A CN106367794A CN201610802199.9A CN201610802199A CN106367794A CN 106367794 A CN106367794 A CN 106367794A CN 201610802199 A CN201610802199 A CN 201610802199A CN 106367794 A CN106367794 A CN 106367794A
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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
- 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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Abstract
The invention discloses a method for rapidly preparing an ordered anodic titanium oxide nanotube array film. The method comprises the following steps: taking a titanium foil subjected to polishing treatment as an anode, taking a fluorine-containing solution as an electrolyte, adding polyvinyl alcohol or polyethylene glycol as an additive, and carrying out constant-pressure or constant-current anodic oxidation treatment at an electrolysis temperature of 20+/-5 DEG C. With the adoption of the method disclosed by the invention, uniform, stable and rapid growth and no electric punch-through phenomenon of an oxide film can be ensured, and the growth speed of nanotubes can achieve 1.20[mu]m/min or above.
Description
Technical field
The invention belongs to technical field of electrochemistry, it is related to a kind of preparation side of orderly anodic titanium dioxide nanotube array film
Method is and in particular to a kind of quick preparation aligned orderly, the electrochemical method of the anodic titanium dioxide nanotube array film of structural integrity.
Background technology
Titanium oxide is a kind of N-shaped semiconductor material with wide forbidden band, and its energy gap is 3.0 ~ 3.2 ev, has excellent dielectric
Performance and opto-electronic conversion, unique physical and chemical performance such as photochromic.In recent years, the technology of preparing of nano material is constantly created
Newly, titanium oxide nanotubes, because having bigger specific surface area and specific surface energy, more preferable absorbability and electric transmission path, make
It has broad application prospects in fields such as DSSC, photocatalysis, ultracapacitors.And anode oxidation method
The titanium oxide nanotubes of preparation are evenly distributed, regular orderly, and by adjusting anodic oxidation condition, can conveniently control nanometer pipe range
Degree, caliber, wall thickness etc., become the effective ways preparing titanium oxide nanotubes.
At present, prepare the titanium oxide nanotubes of high length-diameter ratio it is ensured that the growth of its fast and stable using anodizing, also deposit
In very big difficulty.For example by titanium foil in conventional fluorine-containing electrolyte Anodic Oxidation 1 h, the TiOx nano length of tube of acquisition is only
6~15 μm (song c b, et al., applied surface science, 2014, 305: 792).When being grown
During time anodic oxidation, chemical attack effect can corrode a nanometer tube wall, leads to acicular texture to occur in nanotube top, finally
These structure collapses form " nanometer grass ", reduce the length of nanotube, lead to extend and the growth of nanotube with oxidization time
Speed is decreased obviously.The factors such as the pipe range of titanium oxide nanotubes and electrolyte component, oxidation voltage and temperature are related.Work as nanometer
When the chemical attack at the oxide growth of bottom of the tube and pipe top reaches dynamic equilibrium, thickness reaches highest, continues to extend oxidation
Time nor effectively increase pipe range (macak j m, et al., angewandte chemie international
edition, 2005, 44(45): 7463).Grimes etc. is contained by regulating and controlling fluorination ammonium concentration and water in ethylene glycol electrolyte
Amount, makes titanium foil complete oxidation generate titanium oxide nanotubes, when concurrently increasing now fluorination ammonium concentration, need to increase water content simultaneously,
Just overlength nanotube can be obtained, and using 1 mm thickness titanium foil under room temperature (22 ° of c), the ethylene glycol of 0.6 wt% ammonium fluoride
In (containing 3.5 vol% water) electrolyte, constant voltage 60 v anodic oxidation 216 h(9 days) prepare 1 mm length, the receiving of caliber 120 nm
Mitron (paulose m, et al., journal of physical chemistry c, 2007,111 (41):
14992).In the ethylene glycol electrolyte of Fluohydric acid., by the high pressure of long-time (15 h), (120 v) anodic oxidations, also can obtain
To overlength (261 μm) nanotube (albu s p, et al., physica status solidi (rrl), 2007,1
(2): r65).However, said method obtains long nanotube required time long (as 9 days), this is for production application
It is not worth.The growth rate of titanium oxide nanotubes must be accelerated to solve this problem, and nanotube growth speed will be increased
Rate, then must increase the electric field in anode oxide film.But in high electric field anodic oxygen, easily there is the electrical breakdown of oxide-film
Phenomenon, leads to electronic current titanium oxide nanotubes out of control to stop growing.Therefore, for realizing the mesh of titanium oxide nanotubes fast-growth
Mark is it is necessary to solve High-Field breakdown problem.
Content of the invention
It is an object of the invention to provide the anodic titanium nanotube battle array of a kind of quick preparation aligned orderly, structural integrity
The technology of row film.Using the method for the present invention, only polyvinyl alcohol or Polyethylene Glycol additive need to be added in fluorine-containing electrolyte, just
The fast and stable growth of the anodic titanium nanotube of aligned orderly, structural integrity can be realized.
The technical solution realizing the object of the invention is: one kind quickly prepares orderly anodic titanium dioxide nanotube array film
Method, with the titanium foil after polished process as anode, with fluorine-containing solution as electrolyte, add polyvinyl alcohol or Polyethylene Glycol to add
Plus agent, 20 ± 5°Under the electrolysis temperature of c, carry out the anodized of constant voltage or constant current.
In above-mentioned steps, the polishing of titanium foil adopts the polishing fluid of the Fluohydric acid. of volume ratio 1:1:2, nitric acid and water composition
Middle process 20 ~ 30 s.
In above-mentioned steps, fluorine-containing solution is the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% water.
In above-mentioned steps, the polyvinyl alcohol degree of polymerization is 1200 ~ 1700, and alcoholysis degree is 78 ~ 98 %.
In above-mentioned steps, molecular weight polyethylene glycol is 700 ~ 1500.
In above-mentioned steps, polyvinyl alcohol or Polyethylene Glycol additive concentration are in the range of 0.2 ~ 0.4 wt%.
In above-mentioned steps, constant voltage anodized is carried out under high pressure 120 v.
In above-mentioned steps, constant current anodized is in electric current density 40 ma cm2Under carry out.
In above-mentioned steps, using graphite cake as negative electrode.
Compared with prior art, its remarkable advantage is the present invention:
(1) pass through to add polyvinyl alcohol or Polyethylene Glycol additive in fluorine-containing electrolyte, interact with oxide surface, subtract
Lacked occur electrical breakdown initiating electron source, thus ensure oxide-film can uniform and stable fast-growth, constant voltage anodic oxidation can
To carry out under high pressure 120 v, constant current anodic oxidation can be in electric current density 40 ma cm2Under carry out, and will not shock by electricity
Wear phenomenon.The growth rate of oxide-film is 10 times under fluorine-containing electrolyte, and can keep receiving under Seedling height speed
Nanotube structures completely in order and do not generate nanometer grass.
(2) only need to carry out an anodic oxidation, and the preprocessing process of titanium foil is very simple, can be prepared in the short time
To orderly anodic titanium dioxide nanotube array film, growth rate all can reach 1.20 μm of min-1More than, reach as high as 1.90
μm min-1.
(3) electrolyte temperature adopts 20 ± 5°C, is in the range of room temperature, and temperature fluctuation within the specific limits,
The pattern of titanium oxide nanotubes is affected less.
Brief description
Fig. 1 is the constant voltage anode oxidation process electric current density versus time curve figure of comparative example 2 sample.
Fig. 2 is the constant voltage anode oxidation process electric current density versus time curve figure of embodiment 4 sample.
Fig. 3 is the constant current anode oxidation process voltage versus time curve figure of embodiment 8 sample.
Specific embodiment
Below the present invention is described in further detail.
The principle of the present invention is as follows: in order to quickly prepare anodic titanium dioxide nanotube array film it is necessary to increase anodic oxidation
Electric field in film, and under high field intensity, easily there is the breakdown problem of oxide-film, lead to nanotube to stop growing.Punch-through refers to
The phenomenon that anodized insulation performance is destroyed in high electric field anodic oxygen.After adding water soluble polymer additive, electricity
There is stronger interaction on macromolecule in solution liquid and oxide-film surface, decrease the defect it may happen that electrical breakdown, make oxidation
Film can bear higher oxidation voltage or electric current density, effectively suppression High-Field punch-through, thus ensureing that nanotube can be uniform
Stablize fast-growth, realize the quick preparation of anodic titanium dioxide nanotube array film.
The present invention through the following steps that realize:
Process 20 ~ 30 s in step 1, the polishing fluid of the Fluohydric acid. that titanium foil is immersed volume ratio 1:1:2, nitric acid and water composition, go
Except the Natural Oxide Film on its surface, the titanium foil of employing is high-purity titanium foil.
Step 2, contain the ethylene glycol solution of 0.3 wt% ammonium fluoride and 2 vol% water with fluorine-containing solution as electrolyte, add
Polyvinyl alcohol (degree of polymerization is 1200 ~ 1700, and alcoholysis degree is 78 ~ 98 %) or Polyethylene Glycol (molecular weight 700 ~ 1500) additive,
To polish titanium foil as anode, graphite cake, as negative electrode, carries out High-Field anodic oxidation, and wherein, additive concentration is 0.2 ~ 0.4
In the range of wt%, the anodised electrolyte temperature of High-Field controls 20 ± 5°C, constant voltage anodic oxidation is entered under high pressure 120 v
OK, constant current anodic oxidation is in electric current density 40 ma cm2Under carry out.
Further illustrate the present invention below by embodiment.
Comparative example 1
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Carry out constant voltage anodic oxidation reactionses, oxidation voltage is 60 v in electrolyte.The temperature of electrolyte passes through low-temperature cooling fluid circulating pump
It is maintained at 20°C, anodizing time is 30 min, and anodic titanium nanotube pipe range is about: 6.20 μm, caliber is about:
168 nm.About 0.21 μm of min of the average growth rate of oxide-film-1.
Comparative example 2
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Carry out constant voltage anodic oxidation reactionses, oxidation voltage is 120 v in electrolyte.The temperature of electrolyte passes through low-temperature cooling fluid circulating pump
It is maintained at 20°C, anodic oxidation reactionses are very violent under high pressure, and electric current persistently rises, and anode produces a large amount of bubbles, oxide-film
Partial breakdown, interface fuses and reaction terminating, and nano tube structure is also destroyed, and its voltage versus time curve figure is shown in
Fig. 1.
Embodiment 1
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Add 0.2 wt% Polyethylene Glycol (molecular weight 1500) in electrolyte, carry out constant voltage anodic oxidation reactionses, oxidation voltage is 120 v.
The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30 min, and anodic titanium is received
Mitron pipe range is about: 36.11 μm, caliber is about: 171 nm.About 1.20 μm of min of the average growth rate of oxide-film-1.
Embodiment 2
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Add 0.4 wt% Polyethylene Glycol (molecular weight 700) in electrolyte, carry out constant current anodic oxidation reactionses, electric current density is 40 ma
cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30 min, anodic oxidation
Titanium nanotube pipe range is about: 39.39 μm, caliber is about: 158 nm.About 1.31 μm of min of the average growth rate of oxide-film-1.
Embodiment 3
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.In electrolysis
Add 0.2 wt% Polyethylene Glycol (molecular weight 1000) in liquid, carry out constant current anodic oxidation reactionses, electric current density is 40 ma cm2.
The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30 min, and anodic titanium is received
Mitron pipe range is about: 46.82 μm, caliber is about: 178 nm.About 1.56 μm of min of the average growth rate of oxide-film-1.
Embodiment 4
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Add 0.2 wt% polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 98 %) in electrolyte, carry out constant voltage anodic oxidation reactionses, oxidation
Voltage is 120 v.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30 min,
Anodic titanium nanotube pipe range is about: 43.60 μm, caliber is about: 165 nm, and its voltage versus time curve figure is shown in
Fig. 2.About 1.45 μm of min of the average growth rate of oxide-film-1.
Embodiment 5
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Add 0.2 wt% polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 78 %) in electrolyte, carry out constant voltage anodic oxidation reactionses, oxidation
Voltage is 120 v.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30 min,
Anodic titanium nanotube pipe range is about: 40.37 μm, caliber is about: 155 nm.The average growth rate of oxide-film about 1.35
μm min-1.
Embodiment 6
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Add 0.4 wt% polyvinyl alcohol (degree of polymerization 1200, alcoholysis degree 98 %) in electrolyte, carry out constant current anodic oxidation reactionses, electric current
Density is 40 ma cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30
Min, anodic titanium nanotube pipe range is about: 48.33 μm, caliber is about: 182 nm.The average growth rate of oxide-film is about
1.61 μm min-1.
Embodiment 7
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Add 0.2 wt% polyvinyl alcohol (degree of polymerization 1500, alcoholysis degree 98 %) in electrolyte, carry out constant current anodic oxidation reactionses, electric current
Density is 40 ma cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30
Min, anodic titanium nanotube pipe range is about: 51.55 μm, caliber is about: 170 nm.The average growth rate of oxide-film is about
1.72 μm min-1.
Embodiment 8
First by purity 99.5%, 200 μm of thickness, 6 cm × 1 cm titanium foil bar, the immersion Fluohydric acid. of volume ratio 1:1:2, nitre
Process 20 ~ 30 s in the polishing fluid of acid and water composition, remove the oxide-film on titanium surface.Then deionized water is rinsed well, with
As anode, using the graphite flake of another same size as negative electrode, electrode spacing is 2 cm and keeping parallelism to this titanium foil.Fluorine-containing
Add 0.2 wt% polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 98 %) in electrolyte, carry out constant current anodic oxidation reactionses, electric current
Density is 40 ma cm2.The temperature of electrolyte is maintained at 20 by low-temperature cooling fluid circulating pump°C, anodizing time is 30
Min, anodic titanium nanotube pipe range is about: 57.67 μm, caliber is about: 163 nm, its electric current density changes over song
Line chart is shown in Fig. 3.About 1.90 μm of min of the growth rate of oxide-film-1, it is 9 times of comparative example 1.
Claims (9)
1. a kind of quick method preparing orderly anodic titanium dioxide nanotube array film it is characterised in that with polished process after
Titanium foil be anode, with fluorine-containing solution as electrolyte, add polyvinyl alcohol or Polyethylene Glycol additive, 20 ± 5°The electrolysis of c
At a temperature of, carry out the anodized of constant voltage or constant current.
2. the method for claim 1 is it is characterised in that the polishing of titanium foil is the hydrogen fluorine using volume ratio 1:1:2
20 ~ 30 s are processed in the polishing fluid of acid, nitric acid and water composition.
3. the method for claim 1 is it is characterised in that fluorine-containing solution is containing 0.3 wt% ammonium fluoride and 2 vol% water
Ethylene glycol solution.
4. the method for claim 1 it is characterised in that the polyvinyl alcohol degree of polymerization be 1200 ~ 1700, alcoholysis degree be 78 ~
98 %.
5. the method for claim 1 is it is characterised in that molecular weight polyethylene glycol is 700 ~ 1500.
6. the method for claim 1 is it is characterised in that polyvinyl alcohol or Polyethylene Glycol additive concentration are 0.2 ~ 0.4
In the range of wt%.
7. the method for claim 1 is it is characterised in that constant voltage anodized is carried out under high pressure 120 v.
8. the method for claim 1 is it is characterised in that constant current anodized is in electric current density 40 ma cm2Under enter
OK.
9. the method for claim 1 is it is characterised in that adopt graphite cake as negative electrode.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546971A (en) * | 2018-05-11 | 2018-09-18 | 南京理工大学 | The method for improving binding force between anodic titanium dioxide nanotube array film and titanium substrate |
| CN109338435A (en) * | 2018-12-07 | 2019-02-15 | 五邑大学 | A kind of preparation method of titania nanotube array film |
| CN109825867A (en) * | 2019-04-10 | 2019-05-31 | 东北大学 | A kind of titanium alloy anode oxidation self assembly preparation TiO2The method of film of Nano tube array |
| CN110344097A (en) * | 2019-07-26 | 2019-10-18 | 南京理工大学 | A method of preparing anodic titanium nano flower electrode |
| CN112144088A (en) * | 2020-08-21 | 2020-12-29 | 南京理工大学 | Method for rapidly preparing anodic titanium oxide nanotube array film |
| CN113403661A (en) * | 2021-06-17 | 2021-09-17 | 中国计量大学 | Preparation method and application of titanium alloy anodic oxidation super-hydrophobic coating |
| CN113430618A (en) * | 2021-06-22 | 2021-09-24 | 江苏城乡建设职业学院 | Method for preparing porous layer of titanium dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546971A (en) * | 2018-05-11 | 2018-09-18 | 南京理工大学 | The method for improving binding force between anodic titanium dioxide nanotube array film and titanium substrate |
| CN108546971B (en) * | 2018-05-11 | 2020-01-24 | 南京理工大学 | Method for improving binding force between anodic titanium oxide nanotube array film and titanium substrate |
| CN109338435A (en) * | 2018-12-07 | 2019-02-15 | 五邑大学 | A kind of preparation method of titania nanotube array film |
| CN109825867A (en) * | 2019-04-10 | 2019-05-31 | 东北大学 | A kind of titanium alloy anode oxidation self assembly preparation TiO2The method of film of Nano tube array |
| CN110344097A (en) * | 2019-07-26 | 2019-10-18 | 南京理工大学 | A method of preparing anodic titanium nano flower electrode |
| CN110344097B (en) * | 2019-07-26 | 2021-04-27 | 南京理工大学 | Method for preparing anodic titanium oxide nanoflower electrode |
| CN112144088A (en) * | 2020-08-21 | 2020-12-29 | 南京理工大学 | Method for rapidly preparing anodic titanium oxide nanotube array film |
| CN113403661A (en) * | 2021-06-17 | 2021-09-17 | 中国计量大学 | Preparation method and application of titanium alloy anodic oxidation super-hydrophobic coating |
| CN113430618A (en) * | 2021-06-22 | 2021-09-24 | 江苏城乡建设职业学院 | Method for preparing porous layer of titanium dioxide |
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