CN108166039B - A kind of method that the anodic oxidation of two steps prepares titania nanotube - Google Patents
A kind of method that the anodic oxidation of two steps prepares titania nanotube Download PDFInfo
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- CN108166039B CN108166039B CN201711014417.3A CN201711014417A CN108166039B CN 108166039 B CN108166039 B CN 108166039B CN 201711014417 A CN201711014417 A CN 201711014417A CN 108166039 B CN108166039 B CN 108166039B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C25D11/26—Anodisation of refractory metals or alloys based thereon
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Abstract
The invention discloses a kind of methods that two-step anodization prepares Nano tube array of titanium dioxide, it is characterized by: obtain newborn titanium using the method boiled of acid, by the array for being electrolysed to obtain caliber and the uniform titania nanotube and marshalling of length twice.The preparation method is as follows: the titanium sheet after polishing successively to be carried out to organic solution ultrasound, acid is boiled, and washes drying and processing；Will treated titanium sheet as anode, ruthenium titanium tin electrode is assembled into two electrode system of standard as cathode, successively constant current and constant potential anodic oxidation.This method can obtain caliber in titanium plate surface and length is uniform, the high Nano tube array of titanium dioxide of bond strength.By combining constant current oxidation and constant potential oxidation, solve the problems, such as that nanotube surface is irregular, bond strength is lower, obtained Nano tube array of titanium dioxide has good application prospect in the fields such as photoelectrocatalysis and the energy.
Description
Technical field:
The present invention relates to a kind of methods that two-step anodization prepares Nano tube array of titanium dioxide
Background technique:
Self-organizing nano-porous materials with high aspect ratio are due to its unique performance, in electricity, magnetics and optics
Equal multiple fields are widely used.The poriferous titanium dioxide nano-tube array structure that anodizing is prepared is whole
Together, uniform, there are excellent semiconductor and photoelectrochemical behaviour.In addition, anodizing also has easy to operate, inexpensive, energy
The advantages of enough adapting to various complicated metal surfaces, the titania nanotube morphology controllable prepared by this method is strong, with titanium-based
The bond strength of body is high.
Although anodizing prepares titania nanotube and has the advantages that very much, but there are also permitted on traditional preparation methods
The place more needed to be improved.Such as since impedance layer growth unevenly leads to the titania nanotube obtained from growth course
Caliber is inhomogenous with length.One step anodic oxidation is divided into two steps and carries out being a kind of effective solution method.Patent
CN102220616B discloses a kind of preparation method of Nano tube array of titanium dioxide, is solved using the two steps constant pressure anodic oxidation
Pipe diameter size is uneven, nanotube surface is uneven, the irregular problem of display, obtains the more regular titanium dioxide of pattern and receives
Mitron array.
Summary of the invention:
The object of the invention: bond strength height is obtained with constant current and two step anode oxidation method of constant potential, surface topography is advised
Whole and caliber and the uniform titania nanotube of length.The present invention is prepared in tradition and is added in titania nanotube method
The step of two simple processes, solves the problems, such as that nanotube surface is irregular, bond strength is lower, realizes the industry of low cost
Metaplasia produces
For this purpose, the invention adopts the following technical scheme:
A kind of method that the anodic oxidation of two steps prepares titania nanotube, it is characterised in that: the following steps are included:
(1) pre-treatment of Titanium base
Ultrapure water is used using organic solution ultrasound 10min using sand paper polishing Titanium base；
(2) preparation of newborn titanium
Titanium base obtained by step (1) is immersed in hydrochloric acid, its 30~60min that boils is made, taking-up Titanium base is put into ultrapure
It is saved in water, using preceding in N2Under the conditions of it is dry；
(3) electrolyte configures
Electrolyte is made of 89~89.5wt.% ethylene glycol, 0.5~1wt.% fluoride and 10wt.% ultrapure water；
(4) first step anodic oxidation
The Titanium base being dried to obtain in step (2) is placed in two electrode anode oxidation units, Titanium base as anode,
Ruthenium titanium tin electrode carries out constant current anode oxidation as cathode, and the current density of constant current anode oxidation is 2~3mA/cm2, oxygen
Change the time 3~5 minutes, carries out at room temperature；
(5) second step anodic oxidation
It is ultrasonic in 2M hydrochloric acid that obtained Titanium base will be aoxidized in step (4), is carried out in two electrode anode oxidation units permanent
Current potential anodic oxidation, wherein oxidation voltage is 60~80V, and oxidization time is 2~4h, is carried out at room temperature；
(6) it makes annealing treatment
By the titanium sheet ultrapure water after oxidation, it is ultrasonically treated 1min, it is cold with 10 DEG C/min in 450 DEG C of roasting 1.5h
But titania nanotube is obtained.
Organic solution is acetone: the mixed solution of ethyl alcohol vt.%=1:1 in the step (1).
The concentration of hydrochloric acid of immersion used in the step (2) is 12M.
Fluoride described in the step (3) is ammonium fluoride.
Beneficial effects of the present invention:
Titanium base is handled by the method that acid boils, is beneficial to completely remove the passivation layer on Titanium base surface, obtains newborn titanium,
Make finally to aoxidize obtained titania nanotube surface topography regular.Using two-step electrochemical anodizing method, constant current is used first
Oxidation forms uniform impedance layer on newborn titanium surface, and it is more equal that this is beneficial to the titania nanotube caliber and length to be formed
One, while enhancing the bond strength of titania nanotube and Titanium base.This titanium/titania nanotube photoelectrocatalysis,
Lithium battery and biological implantation material field have more wide application prospect.
Detailed description of the invention
Fig. 1: the scanning electron microscope (SEM) photograph of embodiment 1
Fig. 2: the X-ray diffractogram of embodiment 1
Specific embodiment:
Below with reference to embodiment, the present invention will be further described:
Embodiment 1
The titanium sheet emery paper sanding and polishing that granularity is 800 mesh for being 10mm*10mm*1mm by size uses third later
Ketone: then the mixed solution ultrasound 10min of ethyl alcohol=1:1 (volume ratio) is impregnated the titanium sheet after cleaning using ultrapure water
In the 12M HCl solution of 20mL, 110 DEG C are warming up to using temperature programming 10 DEG C/min speed, acid boils the time for 30min, so
Room temperature is down to 10 DEG C/min afterwards, by obtained newborn titanium in N2Under the conditions of dry, obtain newborn Ti electrode.
Obtained newborn Ti electrode is placed in two electrode anode oxidation units, to make ruthenium titanium tin electrode by oneself as cathode,
100mL is prepared by 89.5wt.% ethylene glycol, 0.5wt.%NH4The electrolyte of F and 10wt.% ultrapure water composition, logical direct current exist
Anodic oxidation is carried out at room temperature, and control current density is 1mA/cm2, oxidization time 5min；Electrode after taking out oxidation uses
The 2M HCl solution ultrasound 10min of 10mL；Electrode is placed in above-mentioned apparatus, logical direct current carries out anodic oxygen at room temperature
Change, control voltage is 60V, oxidization time 3h；Electrode is taken out, with ultrapure water and drying for standby.
Obtained titania nanotube is placed in Muffle furnace, 450 DEG C of roastings are warming up to using 10 DEG C/min of temperature programming
Then 90min is cooled to room temperature with 10 DEG C/min, obtains anatase type titanium dioxide nano tube.
Embodiment 2
The titanium sheet emery paper sanding and polishing that granularity is 800 mesh for being 10mm*10mm*1mm by size uses third later
Ketone: then the mixed solution ultrasound 10min of ethyl alcohol=1:1 (volume ratio) is impregnated the titanium sheet after cleaning using ultrapure water
In the 12M HCl solution of 20mL, 110 DEG C are warming up to using temperature programming 10 DEG C/min speed, acid boils the time as 1h, then drops
To room temperature, by obtained newborn titanium in N2Under the conditions of dry, obtain newborn Ti electrode.
Obtained newborn Ti electrode is placed in two electrode anode oxidation units, to make ruthenium titanium tin electrode by oneself as cathode,
100mL is prepared by 89wt.% ethylene glycol, 1wt.%NH4The electrolyte of F and 10wt.% ultrapure water composition leads to direct current in room temperature
Lower carry out anodic oxidation, control current density are 1mA/cm2, oxidization time 5min；Electrode after taking out oxidation, uses 10mL
2M HCl solution ultrasound 10min；Electrode is placed in above-mentioned apparatus, logical direct current carries out anodic oxidation at room temperature, controls
Voltage processed is 60V, oxidization time 3h；Electrode is taken out, with ultrapure water and drying for standby.
Obtained titania nanotube is placed in Muffle furnace, 450 DEG C of roastings are warming up to using 10 DEG C/min of temperature programming
Then 90min is cooled to room temperature with 10 DEG C/min, obtains anatase type titanium dioxide nano tube.
Embodiment 3
The titanium sheet emery paper sanding and polishing that granularity is 800 mesh for being 10mm*10mm*1mm by size uses third later
Ketone: then the mixed solution ultrasound 10min of ethyl alcohol=1:1 (volume ratio) is impregnated the titanium sheet after cleaning using ultrapure water
In the 12M HCl solution of 20mL, 110 DEG C are warming up to using temperature programming 10 DEG C/min speed, for 1min, then acid boils the time
It is down to room temperature, by obtained newborn titanium in N2Under the conditions of dry, obtain newborn Ti electrode.
Obtained newborn Ti electrode is placed in two electrode anode oxidation units, to make ruthenium titanium tin electrode by oneself as cathode,
100mL is prepared by 89.5wt.% ethylene glycol, 0.5wt.%NH4F and 10wt.% ultrapure water composition electrolyte, lead to direct current into
Row anodic oxidation, control current density are 2mA/cm2, oxidization time 5min；Electrode after taking out oxidation, uses the 2M of 10mL
HCl solution ultrasound 10min；Electrode is placed in above-mentioned apparatus, leads to direct current and carries out anodic oxidation, control voltage is 80V, oxygen
The change time is 2h；Electrode is taken out, with ultrapure water and drying for standby.
Obtained titania nanotube is placed in Muffle furnace, 450 DEG C of roastings are warming up to using 2 DEG C/min of temperature programming
Then 90min is cooled to room temperature, obtain anatase type titanium dioxide nano tube.
The Titanium base arrived in example 1,2 and 3 is subjected to SEM test, XRD test and extension test, obtained caliber point
Not Wei 75,80 and 100nm, pipe range is respectively 600nm, 800nm and 1.2 μm.The surface topography of nanotube pipe as shown in Figure 1 is compared
More regular in arriving for a step anodizing, array arrangement is more neat, and extension test is the result shows that nano titania
The bond strength of pipe and Titanium base is greater than 15MPa.XRD test shows that the titania nanotube arrived after annealing is rutile titania
Mine structure, as shown in Figure 2.
Finally it should be noted that: the above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, to the greatest extent
Invention is explained in detail referring to above-described embodiment for pipe, it should be understood by those ordinary skilled in the art that: still
It can be with modifications or equivalent substitutions are made to specific embodiments of the invention, and without departing from any of spirit and scope of the invention
Modification or equivalent replacement, are intended to be within the scope of the claims of the invention.
Claims (4)
1. a kind of method that two step anodic oxidations prepare titania nanotube, it is characterised in that: the following steps are included:
(1) pre-treatment of Titanium base
Ultrapure water is used using organic solution ultrasound 10min using sand paper polishing Titanium base；
(2) preparation of newborn titanium
Titanium base obtained by step (1) is immersed in hydrochloric acid, makes its 30~60min that boils, to completely remove Titanium base surface
Then passivation layer is down to room temperature, taking-up Titanium base, which is put into ultrapure water, to be saved, using preceding in N2Under the conditions of it is dry；
(3) electrolyte configures
Electrolyte is made of 89~89.5wt.% ethylene glycol, 0.5~1wt.% fluoride and 10wt.% ultrapure water；
(4) first step anodic oxidation
The Titanium base being dried to obtain in step (2) is placed in two electrode anode oxidation units, Titanium base is as anode, ruthenium titanium
Tin electrode carries out constant current anode oxidation as cathode to form uniform impedance layer on Titanium base surface, wherein constant current is positive
The current density of pole oxidation is 1~2mA/cm2, oxidization time 3~5 minutes, carry out at room temperature；
(5) second step anodic oxidation
It is ultrasonic in 2M hydrochloric acid that obtained Titanium base will be aoxidized in step (4), carries out constant potential in two electrode anode oxidation units
Anodic oxidation, wherein oxidation voltage is 60~80V, and oxidization time is 2~4h, is carried out at room temperature；
(6) it makes annealing treatment
By the titanium sheet ultrapure water after oxidation, it is ultrasonically treated 1min, in 450 DEG C of roasting 1.5h, is dropped so that 10 DEG C/min is cooling
To room temperature, titania nanotube is obtained.
2. the method that a kind of two steps anodic oxidation according to claim 1 prepares titania nanotube, it is characterised in that:
Organic solution is acetone: the mixed solution of ethyl alcohol vt.%=1:1 in the step (1).
3. the method that a kind of two steps anodic oxidation according to claim 1 prepares titania nanotube, it is characterised in that:
The concentration of hydrochloric acid of immersion used in the step (2) is 12M.
4. the method that a kind of two steps anodic oxidation according to claim 1 prepares titania nanotube, it is characterised in that:
Fluoride described in the step (3) is ammonium fluoride.
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| CN109216681B (en) * | 2018-09-21 | 2022-02-11 | 合肥工业大学 | Based on TiO2Lithium metal cathode material of nanotube array/titanium foam and preparation method thereof |
| CN110436575A (en) * | 2019-07-25 | 2019-11-12 | 天津大学 | Remove the electric filter formula apparatus and system of pollutant |
| CN111408360A (en) * | 2020-03-12 | 2020-07-14 | 安徽大学 | Photocatalytic material and preparation method and application thereof |
| CN113433579B (en) * | 2021-05-18 | 2023-01-20 | 中国工程物理研究院激光聚变研究中心 | Large-sensitive-surface X-ray spectrum flat response diode detector |
| CN113539866B (en) * | 2021-07-09 | 2022-08-26 | 西南交通大学 | Method for preparing memristor through ultrasonic-assisted brazing |
| CN113754026B (en) * | 2021-10-13 | 2023-05-16 | 东莞理工学院 | High-stability SnO for water treatment 2 Preparation method of-Sb electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514471A (en) * | 2009-02-27 | 2009-08-26 | 哈尔滨工业大学 | Method for preparing TiO2 nanotube array film |
| CN102220616A (en) * | 2011-05-26 | 2011-10-19 | 东南大学 | Method for preparing titanium dioxide nanotube array |
| CN105088312A (en) * | 2015-08-20 | 2015-11-25 | 东北大学 | Method for preparing titania nanotube allay films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101514471A (en) * | 2009-02-27 | 2009-08-26 | 哈尔滨工业大学 | Method for preparing TiO2 nanotube array film |
| CN102220616A (en) * | 2011-05-26 | 2011-10-19 | 东南大学 | Method for preparing titanium dioxide nanotube array |
| CN105088312A (en) * | 2015-08-20 | 2015-11-25 | 东北大学 | Method for preparing titania nanotube allay films |
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