CN106525953A - Method for accurately determining quality of titanium dioxide nanotube array - Google Patents
Method for accurately determining quality of titanium dioxide nanotube array Download PDFInfo
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- CN106525953A CN106525953A CN201611109424.7A CN201611109424A CN106525953A CN 106525953 A CN106525953 A CN 106525953A CN 201611109424 A CN201611109424 A CN 201611109424A CN 106525953 A CN106525953 A CN 106525953A
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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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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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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Abstract
The invention relates to a method for accurately determining the quality of a titanium dioxide nanotube array, and belongs to the technical field of metal material measurement. The method comprises the following steps: pre-treating a titanium substrate and weighting, thereby acquiring mass a; anodizing a titanium sheet after being pre-treated in an organic solution system containing fluorine ions, so as to acquire a titanium dioxide nanotube, thermally treating at 300-500 DEG C, keeping the temperature for 1-3h, carrying out furnace cooling to the room temperature, taking out the sample and weighting, thereby acquiring mass b; adopting thermally treated ICP (Inductively Coupled Plasma) for determining titanium element concentration, and converting into the total mass c of the titanium element in the organic solution containing fluorine ions after the ending of anodizing process; and acquiring the mass d of the oxygen element in titanium dioxide according to the formula: c+b-a=d, thereby calculating the mass of titanium dioxide. According to the technical scheme provided by the invention, the repeatability is high, the effect is excellent and obvious, and the accuracy is high.
Description
Technical field
A kind of accurate method for determining Nano tube array of titanium dioxide quality, belongs to metal material field of measuring technique.
Background technology
Titanium dioxide is as with good stability, avirulence, acid-fast alkali-proof are cheap, cause people very big
Concern.Result of study shows, the titanium dioxide (microgranule, nano wire, nanotube etc.) of nanoscale with big specific surface area,
Its surface atom number, surface energy and surface tension are sharply increased with the decline of particle diameter, due to the granular of its size, are showed
Unique physics and chemical characteristic, cause the aspects such as heat, light, sensitivity characteristic and the surface stability of nano titanium dioxide particles not
Conventional particle is same as, this causes it to have wide application front in environment, information, material, the energy, medical treatment and the field such as health
Scape.In recent years, titania nanotube is directly prepared in titanium substrate using anodizing more than people, and in titanium sheet directly
The nanotube of growth is linked together with substrate, and its weight is difficult to determine.According to the achievement in research delivered, nano-tube array
Growth be F- constantly etch bottom of the tube with dissolving pipe at the top of dynamic process, oxidization time within 1h, thin film of titanium oxide thickness
Increase sharply, between 1h-2h, film thickness is basically unchanged, between 2h-4h, film thickness presence to a certain degree declines,
After 4h, thickness is held essentially constant, F-The etching to nanotube and dissolving reach dynamic equilibrium [Wang Hong .TiO2Nanotube
Controllable standby and its photovoltaic property research [D]. Beijing University of Technology, 2014.].Meanwhile, it is organic molten in the faintly acid of fluoride ion
In agent system, the oxidation voltage of 10V-50V can form nano-tube array structure, but the pattern difference of array it is very big [Wang H,
Li H,Wang J,et al.Influence of applied voltage on anodized TiO2nanotube
arrays and their performance on dye sensitized solar cells[J].Journal of
nanoscience and nanotechnology,2013,13(6):4183-4188.], the matter of upper nanotube every square centimeter
Amount difference is also very big.Therefore the first stage that this patent is held essentially constant using length of tube, that is, 2h is aoxidized as Research foundation.
In 10-50V in the range of tube voltage, the titanium dioxide that tri- kinds of different parameters of 10V, 30V and 50V prepare different structure is selected to receive
Mitron, accurately determines the weight of titania nanotube using the method weighed with reference to ICP.Method is simple and effective, as a result accurately,
It is reproducible.
The content of the invention
A kind of accurate method for determining Nano tube array of titanium dioxide quality, using pulse anodic oxidation technology in thickness be
The Nano tube array of titanium dioxide of high-sequential is prepared in 0.2mm titanium sheet, anodic oxidation voltage is 10V, 30V and 50V totally 3 seed ginseng
Number, resulting samples weighing, and reaction solution is done into icp analysis, wherein titanium elements content can be accurately obtained, final to calculate
Obtain the weight of titania nanotube in titanium substrate under different oxidation voltages.The anodizing that the present invention is provided prepares dioxy
Change the quality determination technology of titanium nanotube, can accurately determine the quality of titania nanotube, after being solution ultrasonic Separation, claim
The problem that the inaccurate traditional method of weight result is present provides new effective measures, in multiple fields (such as lithium-ion electric
The determination of electrode material quality in pond) application be significant.
The method of a kind of accurate measure Nano tube array of titanium dioxide quality that the present invention is provided, it is characterised in that include
Following steps：
(1) titanium substrate pretreatment：Using the metal titanium sheet of certain thickness such as 0.2mm, certain area is processed into, such as 4
The rectangle of × 10cm；Titanium metal plate substrate surface oily matter is super by physics with the oxide layer that storage process is produced with rolling
Sound is removed with chemical pickling process, specially using acetone, ethanol, deionized water ultrasound, takes out pickling after drying, preferred pickling
Liquid is HF (analysis is pure), HNO3(analysis is pure), H2O (preferably 1：3：6 volume ratios) mixed solution, after pickling in deionized water
Ultrasonic 5-30min, dries, weighing obtains quality a；
(2) pretreated titanium sheet in the organic solution system containing fluorion carries out anodic oxidation and obtains titanium dioxide
Nanotube；Sample is taken out after terminating by oxidizing process, and deionized water and dehydrated alcohol are rinsed, drying, having containing fluorion
Machine solution system is containing NH4HF2, ethylene glycol and H2The mixed solution of O；
Above-mentioned anodic oxidation can adopt constant voltage or pulse voltage；
Such as one kind, under permanent 10V, sample directly carries out 2h anodic oxidations；One kind sample under 30V adopts pulse oxidizes, point
Three phases aoxidize 30min, 10min and 2h under voltage 30V, 10V, 30V respectively；One kind sample under 50V adopts pulse oxygen
Change, point three phases aoxidize 30min, 10min and 2h under voltage 50V, 10V, 50V respectively.
(3) heat treatment：Sample after step (2) is aoxidized carries out heat treatment at 300-500 DEG C, is incubated 1-3h, Ran Housui
Stove is cooled to room temperature, and sample is weighed after taking out and obtains quality b；
(4) ICP after heat treatment determines titanium elements concentration：Every 1L after anode oxidation process terminates contains having for fluorion
Correspondence addition 1-5ml HF solution in machine solution, and 10-60min is reacted under magnetic stirring, take out 10ml solution and be diluted to
It is sufficiently mixed in 190ml deionized waters, titanium elements mass concentration in diluent is detected by ICP, anodic oxidation is converted into
Journey terminate after in the organic solution containing fluorion titanium elements gross mass c；According to formula：
C+b-a=d
Oxygen element quality d in titanium dioxide is obtained, and then calculates titanium dioxide quality.
Principle of the invention schematic diagram is shown in Fig. 1.
Compared with prior art, the invention has the beneficial effects as follows：
The Nano tube array of titanium dioxide of high-sequential is prepared in titanium substrate using pulse anodic oxidation, is tied using ICP
The method for being collectively referred to as weight carries out titanium elements measure to the sample (such as 10V, 30V and 50V) after anodic oxidation, and by calculating final essence
The quality of titania nanotube in titanium substrate is obtained really.Organic solution (NH used by step (2)4HF2, ethylene glycol and water mixing
Solution) Nano tube array of titanium dioxide for preparing has very strong adhesion with Titanium base, and nanotube is difficult from matrix to come off.
The ICP adopted in step (4) combines the method weighed, and element determination in below 10ppm solution is still had very high
Precision.Technical scheme is reproducible, and substantially, accuracy is high for excellent effect.
Description of the drawings
The present invention has five accompanying drawings, is now respectively described below：
Fig. 1：Schematic diagram of the present invention；
Fig. 2：The titanium dioxide SEM figures of oxidation voltage 10V；
Fig. 3：The titanium dioxide SEM figures of oxidation voltage 30V；
Fig. 4：The titanium dioxide SEM figures of oxidation voltage 50V；
Fig. 5：The XRD diffracting spectrums of three kinds of samples.
Specific embodiment
Anodizing of the present invention illustrated below prepares the concrete reality of titania nanotube weight method for measuring
Mode is applied, but the present invention is not limited to following examples.
In following examples, pretreated titanium sheet adopts pulse anodic oxidation：In the organic solution system containing fluorion
In carry out anodic oxidation；Three kinds of different anodic oxidations in following examples are respectively：One kind sample under permanent 10V directly enters
Row 2h anodic oxidations；One kind sample under 30V adopts pulse oxidizes, and point three phases distinguish oxygen under voltage 30V, 10V, 30V
Change 30min, 10min and 2h；One kind sample under 50V adopts pulse oxidizes, and point three phases divide under voltage 50V, 10V, 50V
Yang Hua not 30min, 10min and 2h.
Sample is taken out after terminating by oxidizing process, and deionized water and dehydrated alcohol are rinsed, drying, having containing fluorion
Machine solution system is NH4HF2, ethylene glycol and H2(the organic solution system such as containing fluorion is every 3gNH to the mixed solution of O4HF2
Correspondence 1L ethylene glycol, 50mlH2O)。
Embodiment 1
By 0.2mm thickness, the rectangle titanium sheet ultrasound 5min of 4 × 10cm, pickling processes, organic molten containing fluorion
Carry out three kinds of different anodic oxidations, 400 DEG C of heat treatment post-dryings of Jing in liquid system respectively；After anode oxidation process terminates, instead
Add 1ml HF in answering solution, and react 10min under magnetic stirring, take out 10ml solution and be diluted in 190ml deionized waters
It is sufficiently mixed, titanium elements concentration in diluent is detected by ICP, is converted into after anode oxidation process terminates containing fluorion
The gross mass of titanium elements in organic solution；Oxygen element quality in titanium dioxide is obtained, and then calculates titanium dioxide quality.
Embodiment 2
By 0.2mm thickness, the rectangle titanium sheet ultrasound 15min of 4 × 10cm, pickling processes, containing the organic of fluorion
Carry out three kinds of different anodic oxidations, 450 DEG C of heat treatment post-dryings of Jing in solution system respectively；After anode oxidation process terminates,
Add 2ml HF in reaction solution, and react 30min under magnetic stirring, take out 10ml solution and be diluted to 190ml deionized waters
In be sufficiently mixed, titanium elements concentration in diluent is detected by ICP, is converted into after anode oxidation process terminates and is contained fluorion
Organic solution in titanium elements gross mass；Oxygen element quality in titanium dioxide is obtained, and then calculates titanium dioxide matter
Amount.
Embodiment 3
By 0.2mm thickness, the rectangle titanium sheet ultrasound 30min of 4 × 10cm, pickling processes, containing the organic of fluorion
Carry out three kinds of different anodic oxidations, 500 DEG C of heat treatment post-dryings of Jing in solution system respectively；After anode oxidation process terminates,
Add 5ml HF solution in reaction solution, and react 60min under magnetic stirring, take out 10ml solution be diluted to 190ml go from
It is sufficiently mixed in sub- water, titanium elements concentration in diluent is detected by ICP, is converted into after anode oxidation process terminates and contains fluorine
The gross mass of titanium elements in the organic solution of ion；Oxygen element quality in titanium dioxide is obtained, and then calculates titanium dioxide
Titanium quality.
2 oxidation voltage of embodiment is shown in Fig. 2～Fig. 4 respectively for the titanium dioxide SEM figures of 10V, 30V and 50V, three kinds of samples
XRD diffracting spectrums are shown in Fig. 5.
List 1：2 nanotube weight summary sheet of embodiment
Embodiment 1 and 3 is substantially achieved the result consistent with embodiment 2, and above-described embodiment is reproducible, the basic phase for obtaining
Same technique effect.
Claims (4)
1. it is a kind of it is accurate determine Nano tube array of titanium dioxide quality method, it is characterised in that comprise the following steps：
(1) titanium substrate pretreatment：Using certain thickness metal titanium sheet, certain area is processed into；Titanium metal plate substrate surface
The oxide layer that oily matter is produced with storage process with rolling is removed by physics ultrasound and chemical pickling process, is specially adopted
Acetone, ethanol, deionized water ultrasound, take out pickling after drying, and ultrasound 5-30min in deionized water after pickling is dried, weighed
Obtain quality a；
(2) pretreated titanium sheet in the organic solution system containing fluorion carries out anodic oxidation and obtains nano titania
Pipe；Sample is taken out after terminating by oxidizing process, and deionized water and dehydrated alcohol are rinsed, and drying is organic molten containing fluorion
Liquid system is containing NH4HF2, ethylene glycol and H2The mixed solution of O；
(3) heat treatment：Sample after step (2) is aoxidized carries out heat treatment at 300-500 DEG C, is incubated 1-3h, then cold with stove
But to room temperature, sample is weighed after taking out and obtains quality b；
(4) ICP after heat treatment determines titanium elements concentration：Every 1L after anode oxidation process terminates contains the organic molten of fluorion
Correspondence addition 1-5ml HF solution in liquid, and 10-60min is reacted under magnetic stirring, take out 10ml solution and be diluted to 190ml
It is sufficiently mixed in ionized water, titanium elements mass concentration in diluent is detected by ICP, is converted into after anode oxidation process terminates
Gross mass c of titanium elements in organic solution containing fluorion；According to formula：
C+b-a=d
Oxygen element quality d in titanium dioxide is obtained, and then calculates titanium dioxide quality.
2. according to the method for claim 1, it is characterised in that the pickle of pickling is HF (analysis is pure), HNO3(analysis is pure), H2O
Mixed solution.
3. according to the method for claim 1, it is characterised in that anodic oxidation can adopt constant voltage or pulse voltage.
4. according to the method for claim 1, it is characterised in that per 3gNH4HF2Correspondence 1L ethylene glycol, 50mlH2O。
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Cited By (1)
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| CN106978619A (en) * | 2017-04-10 | 2017-07-25 | 四川理工学院 | A kind of enhancing titania nanotube is to visible light-responded preparation method |
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| CN104198466A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院城市环境研究所 | Method for determining content of Ti in TiO2 photocatalyst |
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| CN106978619A (en) * | 2017-04-10 | 2017-07-25 | 四川理工学院 | A kind of enhancing titania nanotube is to visible light-responded preparation method |
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