CN109825867A - A kind of titanium alloy anode oxidation self assembly preparation TiO2The method of film of Nano tube array - Google Patents
A kind of titanium alloy anode oxidation self assembly preparation TiO2The method of film of Nano tube array Download PDFInfo
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- CN109825867A CN109825867A CN201910282984.XA CN201910282984A CN109825867A CN 109825867 A CN109825867 A CN 109825867A CN 201910282984 A CN201910282984 A CN 201910282984A CN 109825867 A CN109825867 A CN 109825867A
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Abstract
The invention discloses a kind of titanium alloy anode oxidation self assemblies to prepare TiO2The method of film of Nano tube array, this method is using liquid polyethylene glycol as solvent, using fluoride as corrosive agent, and adds suitable water adjustment electrolysis fluid viscosity.Different from organic solvent ethylene glycol in the prior art, liquid polyethylene glycol has broader range of viscosities because polymerizable molecular amount is different, it is larger that freedom degree may be selected, therefore can suitably increase water, provides and generates TiO2Necessary oxygen is to improve TiO2Film of Nano tube array formation speed；And various polyethylene glycol can also be mixed mutually by different proportion, or be mixed with ethylene glycol, freely adjusted electrolysis fluid viscosity to reach, guaranteed that electrolyte has mild corrosiveness, flexibly control anode oxidation process.Therefore, which is that anodizing prepares TiO2Nano-tube array provides new way.
Description
Technical field
The invention belongs to a kind of inorganic functional membrane field of material preparation, and in particular to a kind of titanium alloy anode oxidation preparation
TiO2The method of nano-tube array.
Background technique
TiO2Film of Nano tube array is widely noticed in recent ten years, just in the functional material of developmental research, because it compares TiO2
Nano particle, nanometer film have bigger specific surface area and stronger adsorption ability, thus have bigger reactivity
Area can preferably play TiO2The function of semiconductor material.Recent studies have shown that its gas sensor, photolysis water hydrogen,
Many aspects such as photocatalysis, dye-sensitized solar cells and microelectronic field have extensive potential application foreground；Simultaneously
Special nano-tube array structure can assign TiO again2New functional characteristic, thus preparation method is concerned and (is one to grind
The hot spot studied carefully).Currently, preparation TiO2Nano-tube array most efficient method is anodizing, it is to be with titanium or titanium alloy
Anode is obtained in the acidic electrolysis bath containing fluorine ion by electrochemical anodic oxidation.
The TiO initially prepared with anodizing research2Film of Nano tube array, since hydrofluoric acid in aqueous solution is to TiO2
With stronger solvability, cause the TiO to be formed2The limiting length very little of nanotube, even if in weakly acidic fluorine ion electricity
It solves in liquid, the nanotube limiting length of synthesis is also no more than 5 μm.U.S. Grimes (Paulose M, Shankar in 2006
K,Yoriya S,et al.Anodic Growth of Highly Ordered TiO2Nanotube Arrays to 134μm
In Length [J] .J.Phys.Chem.B, 2006,110 (33): 16179-16184.) and Schmuki Research Team, Germany
(Albu S P,Ghicov A,Macak J M,Schmuki P.250μm long anodic TiO2nanotubes with
Hexagonal self-ordering [J] .Phys.Stat.Sol, 2007,1 (2): R65-R67.) be successively with ethylene glycol
The nanometer that length is 134 μm and 250 μm has been respectively synthesized in the mixed electrolytic solution that the fluoride of solvent and a small amount of water is characterized
Pipe, has established the comparatively gentle new preparation method of electrolyte based on organic solvent ethylene glycol.In this electrolyte system
In, since solution viscosity increases, slow down the diffusion rate of fluorine ion, F-To the TiO of generation2Etching speed is slower, can be for a long time
Carry out anodic oxidation, thus obtained orifice configuration rule, uniform diameter, tube wall smoothly, the TiO of high length-diameter ratio2Nanotube battle array
Column.
In conclusion to realize above-mentioned TiO2Function possessed by film of Nano tube array requires to must be able to prepare first
With certain thickness and complete TiO2Film of Nano tube array.Therefore, further develop the electrolyte based on organic solvent
System, optimizes and improves anodic oxidation preparation means, can flexibly control anode oxidation process, self assembly preparation is more regular and meets
It is required that the TiO of thickness2The new process of film of Nano tube array is very necessary.
Summary of the invention
For the deficiency of the existing electrolysis of fluorides liquid system based on single ethylene glycol organic solvent, the present invention is mentioned
TiO is prepared for a kind of anodic oxidation2The electrolyte system that the new organic solvent of film of Nano tube array and fluoride are prepared, i.e., with
Polyethylene glycol is solvent, using fluoride as corrosive agent, and adds suitable water adjustment electrolysis fluid viscosity.With it is in the prior art
Organic solvent ethylene glycol is different, and polyethylene glycol has broader range of viscosities because polymerizable molecular amount is different, may be selected freedom degree compared with
Greatly, it therefore can suitably increase water, provide and generate TiO2Necessary oxygen is to improve TiO2Film of Nano tube array formation speed；And
And various polyethylene glycol can also be mixed mutually by different proportion, or be mixed with ethylene glycol, freely adjust electrolysis fluid viscosity to reach,
Guarantee that electrolyte has mild corrosiveness, flexibly controls anode oxidation process.Therefore, which is anodic oxidation
Method prepares TiO2Nano-tube array provides new way.
The invention is realized by the following technical scheme:
A kind of anodic oxidation preparation TiO2The method of nano-tube array, includes the following steps:
1) degreasing degreasing: degreaser is prepared by metal cleaner and water by mass fraction 3%~5%, by titanium or titanium alloy
Sample is placed in the degreaser, washs 10-30min at 30-60 DEG C of temperature；
2) anodic oxidation: by after degreasing titanium or titanium alloy be placed in organic solvent electrolyte, 20~40 DEG C of temperature, electricity
Anodic oxidation 4~24 hours under the conditions of 60~80V of pressure, the TiO of time longer acquisition2Film of Nano tube array is thicker；Described has
Solvent electrolyte composition has: liquid polyethylene glycol, water and corrosive agent；Wherein the volume fraction of water is 5%~20%, corrosive agent
For ammonium acid fluoride or ammonium fluoride, concentration is 0.005~0.05mol/L, remaining is polyethylene glycol；
3) cleaning treatment: titanium or Oxide scale on Ti base alloys sample that anodic oxidation obtains are put into ethanol solution, then ultrasound
Cleaning 30 minutes obtains TiO to remove surface attachments2Film of Nano tube array.
Further above-mentioned polyethylene glycol is: average molecular weight is respectively 200,400,600 three kinds of liquid polyethylene glycols
One or more of mixing.
Preparation TiO in the method for the present invention2Film of Nano tube array anodic oxidation electrolyte and disclosed organic solvent are electrolysed
Liquid document compares, the difference is that using main solvent of the organic chemical reagent liquid polyethylene glycol as electrolyte, liquid
State polyethylene glycol has different viscosity because of molecular weight difference the experiment has found that and the oxidation electrolyte of preparation can increase water, thus
Preparation TiO can be shortened2The film of Nano tube array time.The present invention is not only applicable to pure titanium metal, is also applied for titanium alloy material.
Detailed description of the invention
Fig. 1 is embodiment 1TiO2Film of Nano tube array surface topography map.
Fig. 2 is embodiment 2TiO2Film of Nano tube array surface topography map.
Fig. 3 is embodiment 3TiO2Film of Nano tube array surface topography map.
Fig. 4 is embodiment 4TiO2Film of Nano tube array surface topography map.
Specific embodiment
Titanium alloy material employed in following embodiment is TC4 titanium alloy plate, with a thickness of 3mm, surface 1200# gold
The polishing of phase sand paper；Preparing chemical reagent used in electrolyte is chemically pure reagent.
Embodiment 1
1) ungrease treatment: carrying out degreasing degreasing to the TC4 titanium alloy plate of polishing first, and degreaser is cleaned for commercial metals
Agent is prepared, and taking mass fraction is that 3% metal cleaner is dissolved in water, and is impregnated 20min under temperature 50 C, is taken out and brushed
It washes, then washes, pure water is washed；
2) anodic oxidation: 1) the TC4 titanium alloy test piece after degreasing is placed in electrolyte, in 25 DEG C of temperature, voltage 80V item
Part anodic oxygenization 4 hours.Electrolyte composition are as follows: organic solvent is the polyethylene glycol (200) of molecular weight 200, adds pure water amount
For 10% (volume fraction), ammonium acid fluoride 0.01mol/L.
3) cleaning treatment: the TiO that step 2) is obtained2Film of Nano tube array is put into ethanol solution, in ultrasonic cleaning
It cleans 30 minutes in device, is saved in hermetic bag after dry.The TiO of acquisition2Nano-tube array environmental microbes are as shown in Figure 1.
Embodiment 2
1) ungrease treatment: carrying out degreasing degreasing to the TC4 titanium alloy plate of polishing first, and degreaser is cleaned for commercial metals
Agent is prepared, and taking mass fraction is that 3% metal cleaner is dissolved in water, and is impregnated 20min under temperature 50 C, is taken out and brushed
It washes, then washes, pure water is washed；
2) anodic oxidation: 1) the TC4 titanium alloy test piece after degreasing is placed in electrolyte, in 25 DEG C of temperature, voltage 80V item
Part anodic oxygenization 4 hours.Electrolyte composition are as follows: organic solvent is the polyethylene glycol (400) of molecular weight 400, adds pure water amount
For 12% (volume fraction), ammonium acid fluoride 0.01mol/L.
3) cleaning treatment: the TiO that step 2) is obtained2Film of Nano tube array is put into ethanol solution, in ultrasonic cleaning
It cleans 30 minutes in device, is saved in hermetic bag after dry.The TiO of acquisition2Nano-tube array environmental microbes are as shown in Figure 2.
Embodiment 3
1) ungrease treatment: carrying out degreasing degreasing to the TC4 titanium alloy plate of polishing first, and degreaser is cleaned for commercial metals
Agent is prepared, and taking mass fraction is that 3% metal cleaner is dissolved in water, and is impregnated 20min under temperature 50 C, is taken out and brushed
It washes, then washes, pure water is washed；
2) anodic oxidation: 1) the TC4 titanium alloy test piece after degreasing is placed in electrolyte, in 25 DEG C of temperature, voltage 80V item
Part anodic oxygenization 4 hours.Electrolyte composition are as follows: organic solvent is the polyethylene glycol (600) of molecular weight 600, adds pure water amount
For 15% (volume fraction), ammonium acid fluoride 0.01mol/L.
3) cleaning treatment: the TiO that step 2) is obtained2Film of Nano tube array is put into ethanol solution, in ultrasonic cleaning
It cleans 30 minutes in device, is saved in hermetic bag after dry.The TiO of acquisition2Nano-tube array environmental microbes are as shown in Figure 3.
Embodiment 4
1) ungrease treatment: carrying out degreasing degreasing to the TC4 titanium alloy plate of polishing first, and degreaser is cleaned for commercial metals
Agent is prepared, and taking mass fraction is that 3% metal cleaner is dissolved in water, and is impregnated 20min under temperature 50 C, is taken out and brushed
It washes, then washes, pure water is washed；
2) anodic oxidation: 1) the TC4 titanium alloy test piece after degreasing is placed in electrolyte, in 25 DEG C of temperature, voltage 80V item
Part anodic oxygenization 4 hours.Electrolyte composition are as follows: organic solvent is the polyethylene glycol (200) of molecular weight 200, adds pure water amount
For 10% (volume fraction), ammonium fluoride 0.05mol/L.
3) cleaning treatment: the TiO that step 2) is obtained2Film of Nano tube array is put into ethanol solution, in ultrasonic cleaning
It cleans 30 minutes in device, is saved in hermetic bag after dry.The TiO of acquisition2Nano-tube array environmental microbes are as shown in Figure 4.
Claims (2)
1. a kind of anodic oxidation prepares TiO2The method of nano-tube array, which comprises the steps of:
1) degreasing degreasing: degreaser is prepared by metal cleaner and water by mass fraction 3%~5%, by titanium or titanium alloy sample
It is placed in the degreaser, washs 10-30min at 30-60 DEG C of temperature；
2) anodic oxidation: by after degreasing titanium or titanium alloy be placed in organic solvent electrolyte, at 20~40 DEG C of temperature, voltage 60
Anodic oxidation 4~24 hours under the conditions of~80V；The organic solvent electrolyte ingredient has: liquid polyethylene glycol, water and corrosion
Agent；Wherein the volume fraction of water is 5%~20%, and corrosive agent is ammonium acid fluoride or ammonium fluoride, and concentration is 0.005~0.05mol/
L, remaining is polyethylene glycol；
3) cleaning treatment: titanium or Oxide scale on Ti base alloys sample that anodic oxidation obtains being put into ethanol solution, then are cleaned by ultrasonic,
To remove surface attachments, TiO is obtained2Film of Nano tube array.
2. a kind of anodic oxidation according to claim 1 prepares TiO2The method of nano-tube array, which is characterized in that described
Polyethylene glycol is: average molecular weight is respectively one or more of 200,400,600 three kinds of liquid polyethylene glycols
Mixing.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884630A (en) * | 2006-06-01 | 2006-12-27 | 厦门大学 | High length-diameter ratio titania nanometer tube array preparation method |
| CN101781788A (en) * | 2010-04-22 | 2010-07-21 | 兰州大学 | Method for preparing specially-shaped titanium dioxide nano-tube films |
| JP2011111660A (en) * | 2009-11-27 | 2011-06-09 | National Institute Of Advanced Industrial Science & Technology | Titania nanotube array and method for producing the same |
| CN102260897A (en) * | 2011-06-13 | 2011-11-30 | 武汉科技大学 | Titanium dioxide nanotube array film and preparation method thereof |
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
-
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- 2019-04-10 CN CN201910282984.XA patent/CN109825867A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884630A (en) * | 2006-06-01 | 2006-12-27 | 厦门大学 | High length-diameter ratio titania nanometer tube array preparation method |
| JP2011111660A (en) * | 2009-11-27 | 2011-06-09 | National Institute Of Advanced Industrial Science & Technology | Titania nanotube array and method for producing the same |
| CN101781788A (en) * | 2010-04-22 | 2010-07-21 | 兰州大学 | Method for preparing specially-shaped titanium dioxide nano-tube films |
| CN102260897A (en) * | 2011-06-13 | 2011-11-30 | 武汉科技大学 | Titanium dioxide nanotube array film and preparation method thereof |
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
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