CN106637334B - A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film - Google Patents
A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film Download PDFInfo
- Publication number
- CN106637334B CN106637334B CN201610853280.XA CN201610853280A CN106637334B CN 106637334 B CN106637334 B CN 106637334B CN 201610853280 A CN201610853280 A CN 201610853280A CN 106637334 B CN106637334 B CN 106637334B
- Authority
- CN
- China
- Prior art keywords
- valve metal
- impurity element
- oxide film
- voltage
- anodic
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- 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
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention provides a kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film, the described method comprises the following steps：S1：The pretreatment of valve metal and its alloy；S2：Anodic oxidation is carried out to the processed valve metals of S1 and its alloy using pulse voltage；S3：Unreacted valve metal and its alloy are removed, anodic oxide film is obtained.The present invention is based on the nano aperture structure on valve metal anodic oxide film surface and pulse voltages to the disruption and recovery of Ion transfer, realizes increasing substantially for impurity content in valve metal anodic oxide film.The present invention also adjusts pulse voltage by systematicness, realizes the regulation and control to impurity element chemical bond ratio, prepares the serial anodic oxide film with different optics and mechanical property.The present invention has environment low stain, and production cost is low, application value is high, practicability is good, uses extensive advantage.
Description
Technical field
It is the invention belongs to electrochemistry preparing technical field, more particularly to miscellaneous in a kind of controlling valve metal-anodicoxide film
The method and products thereof of prime element ratio and chemical property.
Background technology
Electrochemical anodic oxidation refers to so that its surface is formed oxidation using the method for electrolysis using metal or alloy as anode
Object film.Metal-oxide film can change the state and performance of metal surface, if surface colours, improve corrosion resistance, increase
Strong wearability and hardness, protection metal surface etc..By taking metal anodizing of aluminium as an example, aluminium and its alloy are placed in corresponding electricity
It solves and is used as anode in liquid, be electrolysed under specified conditions and applied voltage effect, the aluminium of anode or its alloy oxidation, on surface
Aluminum oxide film is formed, aluminum oxide film has the characteristics that high temperature resistant, thermal stability are good, intensity is high, chemical property is stablized.
The technology that electrochemistry prepares metal oxide can also realize doping of the electrolyte intermediate ion to anodic oxide, from
And the oxide containing doped chemical is prepared, and anodic oxidation is carried out to metallic aluminium using the method for electrochemistry, it equally can be real
The doping of existing aluminum oxide film.The doping of ion can change the properties such as the physical property of oxide, such as chemistry, optics and mechanics.
Up to the present there is the doping of two kinds of forms, one is being doped using electrolyte, another kind is the conjunction directly to metal
Gold carries out anodic oxidation, realizes doping.
For the anodised aluminium of porous type, anodic oxidation reactions are happened at nano aperture bottom, i.e. metal and oxide
Interface on.During anodic oxidation, under the action of extra electric field, cation and anion in solution can be oriented and be moved
It moves, by the migration of ion, the acid ion in solution enters nano aperture along with negative oxygen ion and hydroxide ion and participates in
Anodic oxidation reactions, so as to which acid ion to be incorporated into anodic aluminum oxide film.The doping of acid ion depends on
The property of microfluid in hole, by adjusting anodic oxidation voltage, current density, temperature, the concentration of electrolyte and chemical property,
So as to adjust the doping of element.Under constant pressure anodic oxidation or constant current anodic oxidation condition, the migration of ion is by nanometer
The constraint of pipeline causes the doping of ion within the scope of 2at%-7at%.However, if the ion stream stablized is destroyed, that
Migration of the ion in nanotubes is disturbed, to be had an impact to the ion concentration for participating in anodic oxidation reactions, into
And the doping of changeable oxide intermediate ion.
The present invention carries out anodic oxidation using pulse voltage, can realize higher ions dosage to oxide, reach
20at% or so.Compared to constant pressure anodic oxidation, pulse voltage destroys the stable state of ion stream during pulse anodic oxidation,
The migration of ion is caused to disturb, and by the selective penetrated property of nanotubes, increases acid ion and reaches nano aperture bottom
Portion participates in the probability of anodic oxidation, so as to mix more acid ions in anodic oxide, improves miscellaneous in oxide
The doping ratio of prime element.In addition, pulse anodic oxidation combines the advantages of low-voltage anodic oxidation and high voltage anodization, energy gram
The shortcomings that taking low pressure and high voltage anodization.The present invention also adjusts pulse voltage by systematicness, realizes to impurity element chemistry
The serial anodic oxide film with different optics and mechanical property has been prepared in the regulation and control of key ratio.The present invention reports for the first time
The method and products thereof of impurity element ratio and chemical property in a kind of controlling valve metal-anodicoxide film in road.
Invention content
Present invention aims at impurity element ratio in a kind of controlling valve metal-anodicoxide film of offer and chemically
Method of matter and products thereof can prepare the anodic oxide film of highly doped amount using this method, and can regulate and control anode
The chemical property of impurity element in sull, obtains the anodic oxide film of different functionalities.
In order to achieve the above object, the present invention uses following technical scheme：
A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film,
It is characterized in that, includes the following steps：
S1：The pretreatment of valve metal and its alloy；
S2：Using the processed valve metals of S1 and its alloy as anode, inert electrode is cathode, in acidic electrolysis bath,
Using pulse voltage, anodic oxidation is carried out to it；
S3：Unreacted valve metal and its alloy are removed, anodic oxide film is obtained.
Preferably, the valve metal includes niobium, tantalum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, aluminium.
Preferably, the electrolyte is that sulfuric acid solution, phosphoric acid solution, ammonium fluoride solution, ammonium sulfate, selenic acid are molten
It is one or more etc. in liquid, chromic acid solution, boric acid solution, malonic acid solution, tartaric acid solution and etidronic acid solution.
Preferably, the impurity element includes carbon, element sulphur, P elements, fluorine element, selenium element, boron element, chromium
Element and other metallic elements.
Preferably, in the pulse voltage, oxidation voltage is 10V~300V, and rest voltage is 10~80V, oxidation electricity
Pressure holding is 3~10 seconds continuous, and rest voltage continues 3~10 seconds, and alternately, the time of pulse voltage anodic oxidation is 1-5 hours.
Preferably, the valve metal is aluminium, and the electrolyte is oxalic acid solution, and the impurity element is carbon, institute
In the pulse voltage stated, oxidation voltage 50V, rest voltage is 20V, and oxidation voltage is for 3 seconds, and rest voltage is for 3 seconds, is handed over
For progress, the time of pulse voltage anodic oxidation is 2.5 hours.
The method of impurity element ratio and chemical property in the controlling valve metal-anodicoxide film, when pulse electricity
When pressure changes, the chemical property of impurity element changes in valve metal anodic oxide film, obtained anodic oxygen
The mechanical property and optical property of compound film change.
The anodic oxide film being prepared according to the method.
The invention has the advantages that：
(1) the method energy of impurity element ratio and chemical bond in controlling valve metal-anodicoxide film proposed by the present invention
Enough contents by impurity element in anodic oxide film improve 3 times or more, then the physical property of the anodic oxide film will occur
Change, different functionality is presented.
(2) nano aperture structure and pulse voltage of the present invention for the first time based on valve metal anodic oxide surface move ion
The disruption and recovery of shifting realizes that impurity element ratio increases substantially in anodic oxide film, is different from the prior art and utilizes
The method of alloy anode oxidation, first mixes required impurity element in alloy, then carries out anodic oxidation acquisition to alloy again
The anodic oxide film of highly doped amount, cost is more expensive, and the method for the present invention is simple and cost is relatively low, is suitble to industrial
Extensive use.
(3) it using present invention may also be embodied in more impurity elements are mixed simultaneously in anodic oxide film, prepares
Go out multi-functional anodic oxide, disclosure satisfy that highly doped demand of the people to various elements.
(4) by regulating and controlling the period of pulse voltage, the duration of each period internal oxidition voltage and rest voltage, anode
The quantification doping of impurity element may be implemented in the parameters such as oxidization time, disturbance number.
(5) anodised aluminium for utilizing the high carbon content of the method for the present invention preparation, compared to constant pressure anodic oxidation, the present invention
Pulse anodic oxidation during pulse voltage can destroy the stable state of ion stream, the migration of ion is caused to disturb, and lead to
The selective penetrated property for crossing nanotubes increases acid ion and reaches the probability that nano aperture bottom participates in anodic oxidation, to
More acid ions can be mixed in anodic oxide, improve the doping ratio of impurity element in oxide.When pulse electricity
When pressure increases to 150V-20V from 50V-20V, the chemical bond sp of carbon in prepared anodic aluminum oxide film2/sp3Ratio
Value increases 3 times or so, and the ratio of C-O/C=O keys increases 2 times or so, and the color of sample is from water white transparency to dark brown
A series of variation has occurred in color, shows that its optical property changes.In addition to this, using nano-hardness tester to prepared
Sample carries out Mechanics Performance Testing, and the data of test show that the Young's modulus of sample reduces 60%, and hardness reduces a number
Magnitude.
(6) present invention can technically realize low stain, and low cost, and application value is high, and practicability is good, using wide
It is general.
Description of the drawings
Fig. 1 is the electrochemical experimental device figure of the present invention；
Fig. 2 is the prepared anodic aluminum oxide film under constant pressure 50V anodic oxidation conditions in the oxalic acid solution of 0.4mol/L
Carbon peak XPS spectrum figure；
Fig. 3 is the prepared anodic oxygen under 50V-20V pulse voltage anodic oxidation conditions in the oxalic acid solution of 0.4mol/L
Change the carbon peak XPS spectrum figure of aluminium film；
Fig. 4 is the prepared anodic oxygen under 50V-20V pulse voltage anodic oxidation conditions in the oxalic acid solution of 0.4mol/L
Change the load loop line of aluminium film, Young's modulus and hardness data figure；
Fig. 5 is the prepared anode under 150V-20V pulse voltage anodic oxidation conditions in the oxalic acid solution of 0.4mol/L
The carbon peak XPS spectrum figure of aluminum oxide film；
Fig. 6 is the prepared anode under 150V-20V pulse voltage anodic oxidation conditions in the oxalic acid solution of 0.4mol/L
The load loop line of aluminum oxide film, Young's modulus and hardness data figure；
Fig. 7 is the different angle shooting photograph of prepared sample under different pulse voltages in the oxalic acid solution of 0.4mol/L
Piece.
Specific implementation mode
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent.But examples are merely exemplary, and it is not intended to limit the scope of the present invention in any way.Those skilled in the art answer
It should be appreciated that can be repaiied without departing from the spirit and scope of the invention to the details and form of technical solution of the present invention
Change or replace, but these modifications and replacement are each fallen in protection scope of the present invention.
1 constant pressure of embodiment prepares carbon containing anodic aluminum oxide film
Such as Fig. 1, the present invention prepares the electrochemical appliance of carbon containing porous anodic alumina film, and specific operating procedure is such as
Under：
(1) pretreatment of aluminium flake
Cleaning：It is 99.99% all to select purity, and thickness is 0.4 millimeter of aluminium flake, is cut into appropriately sized, uses pure water
It carries out after simply cleaning, by aluminium flake, ultrasonic machine cleans 20 minutes in acetone soln, removal surface and oil contaminant, with pure after ultrasound
Water is rinsed well.Aluminium flake is cleaned by ultrasonic 20 minutes in absolute ethyl alcohol again, removes other spots of surface, cold wind dries up aluminium flake table
Face.
Electrochemical polish：Since electrochemical polish will produce a large amount of heat, polishing beaker is placed in 0 DEG C of environment and is carried out instead
It answers.Polishing fluid is volume ratio 1:4 perchloric acid and absolute ethyl alcohol mixed solution cannot have water in polishing fluid, otherwise will produce big
Calorimetric bubble, influences polishing effect.It is cathode that electrochemical polish, which is with platinum electrode, and aluminium flake is anode, and constant pressure 18V persistently polishes 5
Minute.The polishing fluid of aluminum flake surface is rinsed well with pure water after polishing and is dried up with cold wind, anodic oxidation is waited for.
(2) constant pressure prepares carbon containing anodic aluminum oxide film
Anodic oxidation is carried out using H-type electrolytic cell as shown in Figure 1, source surveys unit and surveys table using 2636 source of Keithley, cloudy
Aluminium flake is placed among H-type electrolytic cell, as anode by extremely inert electrode platinum electrode.It is poured into right amount in the side of H-type electrolytic cell
0.4mol/L oxalic acid solutions as electrolyte, the pressure in order to ensure aluminium flake both sides is equal, and the pure water of equivalent is poured into the other side,
All anodic oxidation experiments of the present invention carry out in 10 DEG C of insulating boxs.The present embodiment uses the constant voltage of 50V, anodic oxygen
It is 2.5 hours to change the time.
(3) removal aluminium substrate obtains self-holding aluminum oxide film
After anodic oxidation, the aluminum oxide film bottom of preparation remains attached in aluminium substrate, in order to observe film bottom
The pattern in portion, or realize other functional purposes, it needs to remove aluminium substrate, obtains self-holding anodic aluminum oxide film.Side
Method is as follows, is contacted with aluminium substrate with saturation copper chloride solution, solution and metal reactive aluminum, but copper chloride not with aoxidize reactive aluminum,
Self-holding anodic aluminum oxide film is can be obtained to the end of reaction.Wherein saturation copper chloride solution configures with the following method, in body
Product is than being 3:20 perchloric acid (HClO4) copper chloride is added in aqueous solution, until the saturated crystallization of solution bottom.
XPS tests are carried out to prepared anodic aluminum oxide film, obtain carbon atom hundred in anodic aluminum oxide film
Divide than being 7.53at%, as shown in Figure 2.
2 50V-20V pulse voltages of embodiment prepare the anodic aluminum oxide film of high carbon content
Such as Fig. 1, the present invention prepares the electrochemical appliance of carbon containing porous anodic alumina film, and specific operating procedure is such as
Under：
The present embodiment and the step (2) that differs only in of embodiment 1 do not use constant voltage, but use " 50V oxidation electricity
The pulse voltage (abbreviation 50V-20V pulse voltages) that pressure " is combined with " 20V rests voltage ", oxidation voltage is for 3 seconds, rest electricity
Press it is for 3 seconds, alternately.The time of pulse voltage anodic oxidation is 2.5 hours.
XPS tests are carried out to anodic aluminum oxide film prepared under this condition, obtain carbon atomic percent in sample
Than for 19.8at%, as shown in Figure 3.
Compared with the case where constant pressure prepares anodic aluminum oxide film, using the anode of technical solution provided by the invention preparation
The content of carbon improves about 3 times in aluminum oxide film, and the results show pulse anodic oxidation method can improve anodic oxygen
Change the content of carbon in aluminium.The reason of this phenomenon is to will produce electric double layer at the interface of solid and liquid, and double
The main reason for charge layer formation is the selection absorption of ion, and the charge adsorbed is located at the surface of solids, it is assumed that solid is easy to lose
De-electromation is positively charged, then it can at solid liquid interface adsorpting anion, formed electric double layer.The effective thickness of electric double layer claims
Be Debye length, length is about hundred nanometers, related to the ionic strength of solution, and ion concentration height, Debye length is small.In macroscopic view
Liquid in, interfacial effect caused by electric double layer can be ignored, but the electrolyte in nanotubes, double charge
Layer plays a crucial role the migratory behaviour of zwitterion in liquid, can not ignore.Electrolyte in nano aperture
Electrical ion of the same race can be repelled, this reduces nanometers due to the presence of electric double layer by the driving directional migration of electric field
Hole it is effective by diameter, when being effectively less than the Debye length of effects of ion by diameter, nanotubes will produce choosing
Permeability is selected, then ion cannot largely pass through nano aperture.Under the action of nanotubes selective penetrated property, in solution oxygen from
Son or hydroxide ion, oxalate denominationby can enter and participate in anodic oxidation reactions in nanotubes.When application pulse voltage
When, anode oxidation process mesohigh is carried out with low pressure alternating cyclical, can be disturbed the distribution of ion stream, be in turn resulted in more acid
Radical ion enters in anodised aluminium to get to the higher anodic aluminum oxide film of impurity element ratio.
The present invention handles data using XPS swarming fitting software XPSPEAK41, deducts back end first, double according to theory
Peak is formed by stacking by 4 characteristic peaks, i.e. carbon SP2Hybrid characteristics peak position is 284eV, SP3Hybrid characteristics peak position is
The feature peak position of 284.8eV, carbon oxygen singly-bound C-O are 286eV and the feature peak position of C=O bond C=O is 289eV.With this four
A peak carries out swarming fitting to data, and the peak position at four peaks is constant, and peak area ratio is close.Wherein, carbon oxygen singly-bound C-O and carbon
The peak area of oxygen double bond C=O is close, illustrates that the content of carbon oxygen singly-bound C-O and C=O bond C=O are close, and content ratio is close to 1:
1.Carbon SP2Hydridization and SP3The ratio of hydridization is close to 0.24.
The load for being illustrated in figure 4 prepared anodic aluminum oxide film under 50V-20V pulse voltage anodic oxidation conditions is returned
Line, Young's modulus and hardness data figure.By data processing, the Young's modulus E=of prepared anodic aluminum oxide film can be obtained
88.458GPa hardness H=5.424GPa.
3 150V-20V pulse voltages of embodiment prepare the anodic aluminum oxide film of high carbon content
By the constant voltage of (2) the step of embodiment 1, it is changed to that " 150V oxidation voltages " is used to tie with " 20V rests voltage "
The pulse voltage (abbreviation 150V-20V pulse voltages) of conjunction, oxidation voltage is for 3 seconds, and rest voltage is for 3 seconds, alternately.
The time of pulse voltage anodic oxidation is 2.5 hours.
XPS tests equally are carried out to anodic aluminum oxide film prepared under this condition, as shown in figure 5, according to carbon peak
The atomic percent that area obtains carbon in sample is the anodic oxidation prepared under 19.73at%, with 50V-20V impulsive conditions
Aluminium film is compared, and the content of carbon is held essentially constant.Swarming fitting is carried out to carbon spectrogram, obtain carbon oxygen singly-bound C-O,
C=O bond C=O, SP2Key and SP3The content of four characteristic peaks of key.Wherein, carbon oxygen singly-bound C-O and C=O bond C=O contents
Ratio is about 2:1, carbon SP2Hydridization and SP3The ratio of hydridization is close to 0.55.The experimental results showed that when pulse voltage from
When 50V-20V increases to 150V-20V, the chemical bond sp of carbon in prepared anodic aluminum oxide film2/sp3Ratio increase
3 times or so are added, the ratio of C-O/C=O keys increases 2 times or so.
The load for being illustrated in figure 6 prepared anodic aluminum oxide film under 150V-20V pulse voltage anodic oxidation conditions is returned
Line, Young's modulus and hardness data figure.By data processing, the Young's modulus E=of prepared anodic aluminum oxide film can be obtained
33.952GPa hardness H=0.364GPa.
The Young's modulus and hardness of the anodic aluminum oxide film prepared under the conditions of comparison action of low-voltage pulse and high-voltage pulse, can obtain
With the raising of pulse voltage, Young's modulus has dropped 60%, and hardness has dropped an order of magnitude, illustrates with pulse voltage
It improves, significant changes occur for the mechanical property of prepared sample.
The color change of prepared anodic aluminum oxide film under the different pulse voltages of embodiment 4
Fig. 7 is the different angle shooting photograph of prepared sample under different pulse voltages in the oxalic acid solution of 0.4mol/L
Piece.Experimental result also found the raising with pulse voltage, the color of prepared anodic aluminum oxide film from water white transparency to
Systematic change is presented in dark-brown, and the color of these samples does not change with the change of viewing angle, can tentatively sentence
The color of these disconnected samples belongs to the intrinsic color of sample itself.In order to further confirm, we are with the method for an anodic oxidation
It is prepared for that surface hole defect distribution is unordered, and pore size differs greatly with visible wavelength, and thickness of sample is much larger than visible light
Wavelength, so the color of these samples is unlikely due schemochrome caused by Fabry-Perot interference.In pulse anodic oxidation
During, the duration of oxidation voltage and rest voltage is 3 seconds, and prepared anodic aluminum oxide film does not have layer
The color of shape structure, i.e. sample is also impossible to schemochrome caused by coming from layer structure.It, can be with by above experimental analysis
Confirm that the color of these samples comes from intrinsic color.The color of sample is possible as a series of variations are presented in the increase of pulse voltage
It is the chemical bond sp due to carbon in sample2/sp3Caused by increasing with C-O/C=O ratios, illustrate the variation of color sample with
The variation of carbon chemical bond is related.It is possible to change anodic oxide film by the bonding situation for changing impurity element
Optical property.
Due to the chemical bond SP of the carbon element content and carbon that are adulterated in aluminum oxide film2/SP3With the ratio of C-O/C=O
Value changes, and other than its optics and mechanical property change, their chemistry, the properties such as electrically and thermally also must be with
And change.
In addition, the present invention can not only utilize oxalic acid solution to mix more carbons, can also be regulated and controled by this method
The doping of other elements, it is a variety of for example, by using sulfuric acid, phosphoric acid, selenic acid, chromic acid, malonic acid, tartaric acid and etidronic acid etc.
Acid is used as electrolyte, and the regulation and control to the different element doping amounts such as sulphur, phosphorus, selenium, chromium, fluorine may be implemented.Electrolyte can not only select
Mixed acid can also be selected with single acid.It selects containing there are many doping that multiple element then may be implemented in the electrolyte of doped chemical
And a variety of doping are carried out at the same time, so the present invention can also realize the regulation and control to Determination of Multi-Impurities content simultaneously.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that, to preceding
It states the technical solution recorded in embodiment to modify or equivalent replacement of some of the technical features, these modifications
Or it replaces, the spirit and scope for technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (8)
1. a kind of method of impurity element ratio and chemical property in controlling valve metal-anodicoxide film, which is characterized in that
Include the following steps：
S1：The pretreatment of valve metal and its alloy；
S2：Using the processed valve metals of S1 and its alloy as anode, inert electrode is cathode, in acidic electrolysis bath, is utilized
Pulse voltage carries out anodic oxidation to it；
S3：Unreacted valve metal and its alloy are removed, anodic oxide film is obtained；
Wherein, the oxidation voltage of the pulse voltage is 10V~300V, and rest voltage is 10~80V, oxidation voltage continues 3~
10 seconds, rest voltage continued 3~10 seconds, and alternately, the time of pulse voltage anodic oxidation is 1-5 hours.
2. the side of impurity element ratio and chemical property in controlling valve metal-anodicoxide film according to claim 1
Method, which is characterized in that nano aperture structure and pulse voltage of the method based on valve metal anodic oxide film surface
To the disruption and recovery of Ion transfer.
3. the side of impurity element ratio and chemical property in controlling valve metal-anodicoxide film according to claim 1
Method, which is characterized in that the valve metal includes niobium, tantalum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, aluminium.
4. the side of impurity element ratio and chemical property in controlling valve metal-anodicoxide film according to claim 1
Method, which is characterized in that the electrolyte be sulfuric acid solution, phosphoric acid solution, ammonium fluoride solution, ammonium sulfate, selenic acid solution,
It is one or more in chromic acid solution, boric acid solution, malonic acid solution, tartaric acid solution and etidronic acid solution.
5. the side of impurity element ratio and chemical property in controlling valve metal-anodicoxide film according to claim 1
Method, which is characterized in that the impurity element includes carbon, element sulphur, P elements, fluorine element, selenium element, boron element, chromium
Element and other metallic elements.
6. the side of impurity element ratio and chemical property in controlling valve metal-anodicoxide film according to claim 1
Method, which is characterized in that the valve metal is aluminium, and the electrolyte is oxalic acid solution, and the impurity element is carbon, described
In pulse voltage, oxidation voltage 50V, rest voltage be 20V, oxidation voltage is for 3 seconds, and rest voltage is for 3 seconds, alternately into
The time of row, pulse voltage anodic oxidation is 2.5 hours.
7. the side of impurity element ratio and chemical property in controlling valve metal-anodicoxide film according to claim 1
Method, which is characterized in that when pulse voltage changes, the chemical bond of impurity element occurs in valve metal anodic oxide film
Change, color, mechanical property and the optical property of obtained anodic oxide film change.
8. the anodic oxide film being prepared according to claim 1-7 any one of them methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610853280.XA CN106637334B (en) | 2016-09-26 | 2016-09-26 | A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610853280.XA CN106637334B (en) | 2016-09-26 | 2016-09-26 | A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106637334A CN106637334A (en) | 2017-05-10 |
| CN106637334B true CN106637334B (en) | 2018-09-18 |
Family
ID=58853455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610853280.XA Expired - Fee Related CN106637334B (en) | 2016-09-26 | 2016-09-26 | A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106637334B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109652838B (en) * | 2018-12-27 | 2021-05-18 | 浙江工业大学 | Titanium-niobium alloy surface anodic oxidation coloring method |
| CN109680316B (en) * | 2019-02-28 | 2020-10-09 | 安徽工业大学 | Method for preparing structural color film layer on surface of zirconium-based metal glass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837121A (en) * | 1997-10-10 | 1998-11-17 | Kemet Electronics Corporation | Method for anodizing valve metals |
| US6235181B1 (en) * | 1999-03-10 | 2001-05-22 | Kemet Electronics Corporation | Method of operating process for anodizing valve metals |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6802951B2 (en) * | 2002-01-28 | 2004-10-12 | Medtronic, Inc. | Methods of anodizing valve metal anodes |
| JP2009507752A (en) * | 2005-09-09 | 2009-02-26 | ユニバーシティ・オブ・ネバダ・リノ | Production of nanotube-like titania substrates with oxygen vacancies and their use in photoelectrolysis of water |
| CN101307480A (en) * | 2008-02-05 | 2008-11-19 | 哈尔滨工业大学 | Titanium alloy surface high temperature oxidation corrosion resistance coatings preparation method |
| CN102251266B (en) * | 2011-07-07 | 2013-05-22 | 北京工业大学 | Method for preparing nano platinum/titanium dioxide nanotube electrode by pulse electrodeposition |
| CN103255457B (en) * | 2013-04-28 | 2016-07-06 | 北京工业大学 | A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium |
-
2016
- 2016-09-26 CN CN201610853280.XA patent/CN106637334B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837121A (en) * | 1997-10-10 | 1998-11-17 | Kemet Electronics Corporation | Method for anodizing valve metals |
| CN1218848A (en) * | 1997-10-10 | 1999-06-09 | 凯米特电子公司 | Method and electrolyte for anodizing valve metals |
| US6235181B1 (en) * | 1999-03-10 | 2001-05-22 | Kemet Electronics Corporation | Method of operating process for anodizing valve metals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106637334A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI564437B (en) | Non-metallic coating and method of its production | |
| US9006147B2 (en) | Electrochemical system and method for electropolishing superconductive radio frequency cavities | |
| CN106119927B (en) | The method that electrochemical treatments prepare anisotropy water-oil separating copper mesh | |
| CN103643278B (en) | A kind of method of auto parts machinery aluminium differential arc oxidation | |
| KR100736252B1 (en) | Fabrication of mesoporous metal electrodes in non-liquid-crystalline phase and its application | |
| Yao et al. | Influence of ZrO2 particles on fluorine-doped lead dioxide electrodeposition process from nitrate bath | |
| KR102176791B1 (en) | Method for manufacturing aluminum anodic oxide film having pillar-on-pore structure using phosphoric acid | |
| CN102230204A (en) | Method for preparing aluminum oxidation film by combination of ultrasonic waves and microarc oxidation | |
| CN101792920A (en) | Sulfuric acid-boric acid-additive ternary anodizing fluid | |
| CN106637334B (en) | A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film | |
| CN103643279A (en) | Preparation and application of hourglass-shaped aluminum oxide nanometer channel film | |
| CN102797024A (en) | Method for carrying out micro-arc oxidation on blue-colored film layer by aluminum alloy | |
| SE444585B (en) | MATERIALS FOR SELECTIVE ABSORPTION OF SOLAR ENERGY AS WELL AS MANUFACTURING THE MATERIAL | |
| DE102016202202B4 (en) | Apparatus and method for expanding graphite into graphene | |
| CN104562097B (en) | A kind of preparation method of self-supporting nickel nano tube/linear array film | |
| CN109898122A (en) | Magnesium alloy surface micro-arc oxidation/graphene oxide composite film preparation method | |
| CN108642544B (en) | Method for preparing oxide film on surface of magnesium alloy by utilizing micro-arc oxidation | |
| Vasyliev et al. | Influence of polarization curve slope on the accuracy of local copper electrodeposition from sulphate electrolyte | |
| Kalska-Szostko | Electrochemical methods in nanomaterials preparation | |
| CN102586836A (en) | Preparation method for mesoporous titanium dioxide thin film | |
| Macák | Growth of anodic self-organized titanium dioxide nanotube layers | |
| CN105683423A (en) | Method for structuring layers of oxidizable materials by means of oxidation and substrate having a structured coating | |
| US10287694B2 (en) | Amalgam electrode, method for manufacturing the same, and method for electrochemical reduction of carbon dioxide using the same | |
| Chung et al. | On characteristics of pore size distribution in hybrid pulse anodized high-aspect-ratio aluminum oxide with Taguchi method | |
| CN102627002A (en) | Preparation method of aluminum-base lead and lead alloy composite material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180918 Termination date: 20200926 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |