CN101768769B - Method for regulating and controlling filming speed of scheelite film - Google Patents
Method for regulating and controlling filming speed of scheelite film Download PDFInfo
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- CN101768769B CN101768769B CN 201010034421 CN201010034421A CN101768769B CN 101768769 B CN101768769 B CN 101768769B CN 201010034421 CN201010034421 CN 201010034421 CN 201010034421 A CN201010034421 A CN 201010034421A CN 101768769 B CN101768769 B CN 101768769B
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- scheelite
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- speed
- molybdate
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Abstract
The invention discloses a method for regulating and controlling filming speed of scheelite film, belonging to the technical field of oxide film preparation. In the invention, the original system is adopted, oxidant is added at cathode or in cathode electrolyte, and type and concentration of oxidant is changed to control the reaction speed of anode tungsten or molybdenum to form tungstate or molybdate film layer. The method is carried out at room temperature without heat treatment, thus avoiding flaws caused in heat treatment crystallization process, quickly synthesizing tungstate and molybdate polycrystal films with good luminous performance. The invention dispenses with heating procedure and external electrochemical equipment, and has the characteristic of zero energy consumption.
Description
Technical field
The present invention relates to a kind of tungstate, molybdate polycrystalline film method of velocity of regulating and control original battery electrochemistry deposition scheelite-type structure, belong to the film preparing technology field, especially a kind of method of regulating and controlling filming speed of scheelite film.
Background technology
The tungstate of scheelite-type structure, molybdate are one type of important photoelectric functional materials, have important use in fields such as laser, demonstration, detections.
The tungstate of electrochemical preparation scheelite-type structure, molybdate polycrystalline film can be divided into electrolysis-type (like methods such as continuous current, constant potentials) and galvanic cell type two lines.For the electrolysis-type electrochemical techniques, the galvanic cell type route is a kind of emerging electrochemical filming technology, has advantages such as zero energy consumption, conversion unit is simple, deposition film quality is better.But there are a serious deficiency in the galvanic cell type path of preparing tungstate that adopts at present, molybdate polycrystalline film: speed of response is too slow and can not control, and is consuming time often at tens to up to a hundred hours.This seriously limited should technology in the further popularization in film preparation field.Therefore, how to realize the control of original battery electrochemistry deposits tungsten hydrochlorate, molybdate polycrystalline film speed, become the gordian technique that this method really has practical value.Develop and a kind ofly can under room temperature environment, regulate and control original battery electrochemistry deposits tungsten hydrochlorate, molybdate polycrystalline film method of velocity easily, have great importance undoubtedly.
Summary of the invention
Problem to the prior art existence; The object of the present invention is to provide a kind of method of regulating and controlling filming speed of scheelite film; This method has proposed design cathodic reaction method; Through changing the control of the electrochemical reaction realization response speed that takes place on the negative electrode, tungstate, the molybdate polycrystalline film of having inherited galvanic cell route synthetic scheelite ore deposit structure has and do not heat, no power consumption, need not anneal can directly obtain well-crystallized's advantages such as polycrystalline film.
For realizing above-mentioned purpose; The method of a kind of regulating and controlling filming speed of scheelite film of the present invention adopts the galvanic cell system, in the electrolytic solution of negative electrode or negative electrode, adds oxygenant; Through changing the kind and the concentration of oxygenant, form the speed of response of tungstate, molybdate rete with control anodic tungsten or molybdenum.
Further, contain oxidisability ion MnO in the said oxygenant
4 -, Fe
3+, Cu
2+, Au
+, Ag
+, CrO
4 -, Co
3+, Ni
2+, Pb
2+, Cd
2+, Eu
3+, Sm
3+, Tb
4+, Pr
4+, Ce
4+
Further, said negative electrode is C piece or Pt sheet or is by the conductive electrode of said oxidizer treatment, modified.
Further, said negative electrode is the conductive electrode that contains above-mentioned oxygenant.
Further, said anode is immersed in and contains respective metal positively charged ion Ca
2+, Ba
2+, Sr
2+, Na
+Basic soln in.
Further, said negative electrode, anode connect with fixed value resistance, connect with salt bridge between the electrolytic solution.
The present invention at room temperature carries out, need not thermal treatment, avoided in the thermal treatment crystallization process, producing the problem of defective, and can synthesize the good tungstate of luminescent properties, molybdate polycrystalline film fast.The present invention need not heat and outside electrochemical apparatus, has the characteristics of zero energy consumption.
Embodiment
The present invention adopts the galvanic cell system of band salt bridge, and as anode, Ag/AgCl (interior reference solution is saturated KCl) is as reference electrode with tungsten sheet or molybdenum sheet, is immersed in to contain Ba
2+, Sr
2+, Ca
2+In the isoionic basic soln; Negative electrode is C piece or Pt sheet or is that it is immersed in and contains MnO by the conductive electrode of said oxidizer treatment, modified
4 -, Fe
3+, Cu
2+, Au
+, Ag
+, CrO
4 -, Co
3+, Ni
2+, Pb
2+, Cd
2+, Eu
3+, Sm
3+, Tb
4+, Pr
4+, Ce
4+In the oxidisability ion solution, connect with salt bridge, fixed value resistance respectively between electrolytic solution and electrode.The spontaneous corrosion of tungsten or molybdenum takes place on the anode, because corresponding M nO on the negative electrode
4 -/ MnO
2, Fe
3+/ Fe
2+Deng the right reduction potential of electricity far above H
2O/H
2, therefore, when in cathode side electrolytic solution, having added oxygenant, the terminal voltage of galvanic cell increases, the also corresponding increase of current in loop, and the anodic dissolving is accelerated, thereby can accelerate AMO
4(A=Ca, Ba, Sr; M=W, Mo) sedimentation velocity of rete.
With deposition CaWO
4The speed control of polycrystalline film is an example:
Embodiment 1.MnO
4 -Ionic concn is to the influence of speed of response
Tungsten sheet (25*15*0.1mm through abrasive paper for metallograph corase grind, the pre-treatments such as decontamination of deoiling
3) be immersed in saturated Ca (OH)
2In the solution, platinized platinum (2.0*2.0*0.1mm
3About) be immersed in and contain MnO
4 -In the ionic electrolytic solution (conducting electrolyte is the NaCl solution of 0.1mol/l), salt bridge is saturated Repone K/agar, and fixed value resistance is 82.3 ohm, then anodic surface current density and MnO
4 -Following relation (as shown in table 1) is arranged between the ionic concn
MnO in table 1 anodic surface current density and the cathode solution
4 -Relation between the ionic concn
| [Mn0 4 -](mol/l) | 0 | 0.00001 | 0.0001 | 0.001 | 0.01 | 0.1 | 0.3 |
| Average current density (the A/m of 0-300s 2) | 1.282 | 1.245 | 1.529 | 3.576 | 5.295 | 4.598 | 6.127 |
Embodiment 2. is through the tungsten sheet (25*15*0.1mm of abrasive paper for metallograph corase grind, the pre-treatments such as decontamination of deoiling
3) be immersed in Ca
2+Ionic concn is the basic soln (the pH value is about 12.2) of 0.2mol/l, is negative electrode with the C piece, is immersed in the kMnO of 0.1mol/l
4In the solution, salt bridge is saturated Repone K/agar, and fixed value resistance is 82.3 ohm, and then anodic surface current density (MV of 0-200 between second) can reach 21-26A/m
2
Embodiment 3.Cu
2+Ionic concn is to the influence of speed of response
Tungsten sheet (25*15*0.1mm through abrasive paper for metallograph corase grind, the pre-treatments such as decontamination of deoiling
3) be immersed in saturated Ca (OH)
2In the solution, platinized platinum (2.0*2.0*0.1mm
3About) be immersed in and contain Cu
2+In the ionic electrolytic solution (conducting electrolyte is the NaCl solution of 0.1mol/l), salt bridge is saturated Repone K/agar, and fixed value resistance is 82.3 ohm, then anodic surface current density and Cu
2+Following relation (as shown in table 2) is arranged between the ionic concn.
Cu in table 2 anodic surface current density and the cathode solution
2+Relation between the ionic concn
| [Cu 2+](mol/l) | 0 | 0.0001 | 0.001 | 0.01 | 0.1 | 0.5 | 1 |
| Average current density (the A/m of 0-300s 2) | 1.151 | 1.239 | 2.414 | 3.257 | 3.464 | 4.869 | 5.306 |
Claims (4)
1. the method for a regulating and controlling filming speed of scheelite film is characterized in that, this method adopts the galvanic cell system, in the electrolytic solution of negative electrode or negative electrode, adds and contains oxidisability ion MnO
4 -Or Cu
2+Oxygenant, through changing the concentration of oxygenant, form the speed of response of tungstate, molybdate rete with control anodic tungsten or molybdenum.
2. the method for regulating and controlling filming speed of scheelite film as claimed in claim 1 is characterized in that, said negative electrode is C piece or Pt sheet or the conductive electrode for being crossed by said oxidizer treatment.
3. the method for regulating and controlling filming speed of scheelite film as claimed in claim 1 is characterized in that, said anode is immersed in and contains Ca
2+, Ba
2+, Sr
2+, Na
+Basic soln in.
4. the method for regulating and controlling filming speed of scheelite film as claimed in claim 1 is characterized in that, said negative electrode, anode connect with fixed value resistance, connect with salt bridge between the electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010034421 CN101768769B (en) | 2010-01-19 | 2010-01-19 | Method for regulating and controlling filming speed of scheelite film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010034421 CN101768769B (en) | 2010-01-19 | 2010-01-19 | Method for regulating and controlling filming speed of scheelite film |
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|---|---|
| CN101768769A CN101768769A (en) | 2010-07-07 |
| CN101768769B true CN101768769B (en) | 2012-08-01 |
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|---|---|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201117051D0 (en) * | 2011-10-04 | 2011-11-16 | Uni I Oslo | Carbonic anhydrase inhibitors |
| CN113061954A (en) * | 2021-03-15 | 2021-07-02 | 深圳大学 | Method for preparing metal molybdate by anodic oxidation method, metal molybdate and application thereof |
-
2010
- 2010-01-19 CN CN 201010034421 patent/CN101768769B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 刘庆友等.流动体系下黄铁矿-方铅矿原电池反应实验研究.《地球与环境》.2006,第34卷(第2期),第89-94页. * |
| 陈连平.白钨矿多晶膜的电化学制备技术及其光致发光性能的研究.《四川大学博士学位论文》.2008,第81-85、109-126页. * |
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| CN101768769A (en) | 2010-07-07 |
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Effective date of registration: 20160330 Address after: 341000 Jiangxi city of Ganzhou province Ganxian Chu Tan Xiang Tan Cun reservoir Patentee after: GANZHOU SEADRAGON W & MO CO., LTD. Address before: 86 No. 341000 Jiangxi city of Ganzhou province Zhanggong District Hongqi Avenue Patentee before: Jiangxi University of Science and Technology |
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Denomination of invention: A method for controlling the film forming rate of Scheelite Effective date of registration: 20220517 Granted publication date: 20120801 Pledgee: Ganzhou Bank Co.,Ltd. Ganxian Branch Pledgor: GANZHOU HAILONG TUNGSTEN AND MOLYBDENUM Co.,Ltd. Registration number: Y2022980005545 |
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