CN106282962A - A kind of CVD prepares the preprocess method of large area BDD electrode - Google Patents
A kind of CVD prepares the preprocess method of large area BDD electrode Download PDFInfo
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- CN106282962A CN106282962A CN201610866336.5A CN201610866336A CN106282962A CN 106282962 A CN106282962 A CN 106282962A CN 201610866336 A CN201610866336 A CN 201610866336A CN 106282962 A CN106282962 A CN 106282962A
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- niobium
- titanium
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- ferrum
- hole
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
A kind of CVD prepares the preprocess method of large area BDD electrode.CVD is to prepare the universal method of diamond electrode, prepare large-area diamond electrode it is crucial that pretreatment, i.e. form hole a large amount of, uniform at substrate surface, in hole, plant diamond seeds a large amount of, uniform further.The alloy plating method of the present invention is the good method that substrate surface forms hole a large amount of, uniform.Using base material titanium or niobium as the chloride of negative electrode, titanium or niobium and the mixture of iron chloride as electroplate liquid, carry out electroplating processes, the Alloy Plating of titanium or niobium and ferrum is after cathode surface, and negative electrode takes out, with soak with hydrochloric acid, to dissolve the ferrum in alloy, after dissolution ferrum, cathode surface leaves uniform hole.
Description
Technical field
The present invention relates to the preparation method of diamond electrode.Relate to the use of chemical vapour deposition technique (CVD) and prepare large area
The preprocess method of boron-doped diamond electrode (BDD).
Background technology
Pure diamond is non-conductive, it is impossible to use as electrode.In diamond crystal, mix a certain proportion of boron element, then become
For good conductor.Boron-doped diamond electrode (BDD) is as anode for sewage disposal, and its performance is than the current titanio commonly used
Noble metal electrode (DSA electrode) is with the obvious advantage, and its oxygen evolution potential is high, and the efficiency of electrolysis is more than 5 times of titanium-based noble metal electrode,
And the good stability of diamond itself, electrode life is long.BDD electrode is reported in a large number for the premium properties of sewage disposal
Road, such as patent CN201210514062, CN201210514054, CN201210514000 disclosure.
The difficult point that BDD electrode is applied in sewage disposal is the index of large area BDD electrode.So-called large area, refers to face
Long-pending more than the electrode inside 100 square meters.The preparation of the BDD electrode of one square centimeters has been ripe technology, and large area BDD is electric
The preparation of pole is still difficult point.Chemical vapour deposition technique (CVD) is the universal method preparing diamond thin.CVD prepares big face
The technological difficulties of long-pending BDD have three: one, the pretreatment of base material, plant diamond seeds in substrate surface the most equably；Its
In two, CVD implementation process, being uniformly distributed of temperature field；Its three, in CVD implementation process, being uniformly distributed of temperature field.And first
Individual technological difficulties are crucial.
What the pretreatment of base material was reported has two kinds of methods, and one is surface chemistry etch, such as Korean Patent Laid
The fluorine etch of 10-2006-0051632 report.More trial is configuration chloroazotic acid, basis titanium or niobium is carried out surface rotten
Erosion；The second is mechanical grinding method, the more common application of this method.As Master's thesis numbering 1028705 13-S065 uses
Method, the preprocess method as disclosed in patent 200610023442.3.
Above two method has obvious defect, causes current large area BDD to fail at home to enter business application.Change
Learn etch, the concentration of control corrosion rate liquid, temperature, etching time can be passed through, but corrosive effect is difficult to control, it is difficult to ensure that rotten
, often there is macropore in the stability of erosion result, the diameter hole more than 10um, the bulk region of atresia the most often occurs.Machinery is beaten
Mill method, even if by controlling polishing time, the pressure of polishing, it is also difficult to ensure the homogeneity of each grinding depth and hole number.
In order to overcome CVD to prepare the unstability of pretreatment in large area BDD electrode process, the present invention provides a kind of new
Preprocess method.
Summary of the invention
It is an object of the invention to overcome CVD to prepare the unstability of pretreatment in large area BDD electrode process, propose one
Plant new preprocess method.Utilize the principle of plating, by substrate surface then with acid, ferrum is molten with the Alloy Plating of ferrum to titanium or niobium
Go out, to form uniform hole.By controlling the proportioning of electroplate liquid, the electrochemical parameter of plating, electroplating time, it is possible to achieve pre-
Process the stability of technique, obtain the pre-processed results of favorable reproducibility.This pretreating process standardization, is that CVD preparation is big
The essential condition of area B DD electrode.
The base material titanium of the present invention or niobium.
Before plating, fully clean surface by ethanol or the third organic solvent of ketone, reach the purpose deoiled.
The plating of the present invention, anode selects titanio ruthenium iridium electrode, and negative electrode is that titanium or iridium are as base material.Between negative electrode and anode
Spacing 5 ~ 10mm.Electric current density 50 ~ 300 peaces/square meter.General electroplating time is 10 minutes.If it is intended to obtain thicker plating
Layer, can extend to 30 minutes.The thickness of coating is 2 ~ 20 microns, preferably 6 ~ 12 microns.The thickness of coating is by electroplating time
Control.In general, coating is the thickest more good.But coating is the thickest, it is unfavorable for pickling below, ferrum dissolution can be caused the completeest
Entirely.Coating is thin, is unfavorable for the surface grafting of diamond crystallites.Experiment shows, the thickness of coating of 5 ~ 12 microns is suitable.
Electric current density is the key factor affecting surface holes quantity with aperture.Electric current density is big, ferrum and titanium or niobium in alloy
Crystallite the least, after ferrum dissolution, aperture is little, and hole number is many.Electric current density is excessive, can cause electroplate liquid in electroplating process, especially
Being a gradient of cathode surface formation electroplate liquid proportioning, electrodeposited coating can be layered, and the iron content of every layer is different, causes ferrum dissolution
After, hole irregular.Research finds, electric current density 80 ~ 120 peace is suitable.
The proportioning of electroplate liquid is also to be crucial.Iron salt is that 1:3 ~ 30 iron salt contains with its molar ratio of proportioning of titanium salt or niobium salt
Amount height, in coating, ferrum crystallite is big, and after ferrum dissolution, Kong great, hole number is the fewest.The priority parameter that research and development find is 1:5 ~ 10.
After plating terminates, the ferrum in coating to be come out completely, at least steep 5 hours with the hydrochloric acid of heat.Concentration of hydrochloric acid is not
Less than 1%, temperature 50 ~ 60 degrees Celsius is suitable.
The way of the inspection complete dissolution of ferrum is, with new 1% soak with hydrochloric acid 10 minutes, bubbles out liquid and adds alkali and be adjusted to neutrality, observation
Iron salt whether is had to separate out.
Next step, by base material ultrasonic waves for cleaning, and plant the method for the diamond seeds ultrasound wave of 0.5um in base
The surface of material, can be used as CVD and prepares the base material of large area BDD electrode.
Accompanying drawing explanation
In conjunction with accompanying drawing 1, can the method for clearer description pretreatment disclosed in this invention.
Titanium or the base material of niobium, after over cleaning is deoiled, put in electroplanting device as negative electrode.Configure suitable electroplate liquid,
Plating a period of time, negative electrode is taken out.After overpickling dissolution ferrum, with ultrasound wave, diamond crystallites is planted in substrate surface,
CVD can be become and prepare the base material of large area BDD electrode.
Detailed description of the invention
Base material selects titanium or niobium, size 200mm*200mm, thickness 3mm.Cleanout fluid with 20% ethanol solution.The anode of plating
The DSA electrode of ruthenium iridium it is coated with for titanio.Two-stage spacing 10mm, electric current 4 ~ 12A.The configuration of electroplate liquid: iron chloride configuration concentration is
0.01mol/L, according to different requirements, adds quantitative titanium chloride or Columbium pentachloride..Iron salt and titanium salt or the mol ratio of mud salt
For 1:3 ~ 30. electroplating time 10 minutes.Concentration of hydrochloric acid 1%.With ultrasound wave, the diamond crystals of 0.5um is planted in base material table
Face, plants twice.
The mode of inspection is: put into by the base material of above-mentioned pretreatment in HFCVD device, prepares BDD electrode.By prepare
BDD electrode carries out life test, and the life-span is the most qualified higher than 100 hours.In test process, the life-span is more than 200 hours, is recorded as
>200.
HFCVD prepares the process of BDD electrode, first step evacuation, second step, heats up, heated filament carbonization, and the 3rd step is passed through hydrogen
The mixture of gas, methane and borine, ratio be the 98.3:1.2:0.5. diamond film time be 6 hours, the 4th step, cooling.
BDD tests way electrode life: using accelerated aging method, test in sulfuric acid solution, electric current rises to 40A, i.e. electricity
Current density is 10000 peaces/square meter, moves heat with heat exchanger in test process, and test liquid temperature is less than 40 degrees Celsius.
Following table is test result
In terms of the result of upper table, it is highly effective that the preprocess method of the present invention prepares large area BDD electrode for CVD.
Claims (5)
1. using base material titanium or niobium as the chloride of negative electrode, titanium or niobium and the mixture of iron chloride as electroplate liquid, electroplate
Processing, the Alloy Plating of titanium or niobium and ferrum is after cathode surface, and negative electrode takes out, with soak with hydrochloric acid, to dissolve the ferrum in alloy, molten
After tapping a blast furnace, cathode surface leaves uniform hole, after planting the crystallite of diamond, can be used as CVD and prepares large area in hole
The base material of BDD electrode.
2. electroplating technology as claimed in claim 1, the thickness of cathodic coating is 2 ~ 20 microns, preferably 6 ~ 12 microns.
3. electroplating technology as claimed in claim 1, the ratio of iron salt and titanium salt or niobium salt is for controlling the hole of substrate surface
Size, its molar ratio is 1:3 ~ 30, preferably 1:5 ~ 10.
4. electroplating technology as claimed in claim 1, electric current density 50 ~ 300 peaces/square meter, preferably 80 ~ 120 peaces/square meter.
5. the method for claim 1, hydrochloric acid invades the temperature of bubble at 50 ~ 60 degrees Celsius, and concentration of hydrochloric acid is not less than 1%, soaks
Time is not less than 5 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610866336.5A CN106282962A (en) | 2016-09-30 | 2016-09-30 | A kind of CVD prepares the preprocess method of large area BDD electrode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110230044A (en) * | 2019-07-12 | 2019-09-13 | 中国工程物理研究院激光聚变研究中心 | It is the method that counterfeit template prepares porous boron-doped diamond electrode with nano-diamond powder |
| CN111115762A (en) * | 2019-12-25 | 2020-05-08 | 河南省功能金刚石研究院有限公司 | Novel foam nickel electrode and preparation method thereof |
Citations (5)
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|---|---|---|---|---|
| CN1007737B (en) * | 1988-04-16 | 1990-04-25 | 华东师范大学 | Active cathode with porous nickel plating and preparation thereof |
| KR20050065643A (en) * | 2002-11-13 | 2005-06-29 | 세타곤 인코포레이티드 | Medical devices having porous layers and methods for making same |
| WO2015056981A1 (en) * | 2013-10-16 | 2015-04-23 | 부산대학교 산학협력단 | Method for manufacturing nanoporous metals using osmium or rhenium dissolution, and nanoporous metal thereof |
| KR101561966B1 (en) * | 2015-03-26 | 2015-10-20 | 부산대학교 산학협력단 | A fabrication method of nano porous metal |
| CN105063400A (en) * | 2015-09-16 | 2015-11-18 | 哈尔滨工业大学 | Preparation method for nanometer porous titanium |
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2016
- 2016-09-30 CN CN201610866336.5A patent/CN106282962A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1007737B (en) * | 1988-04-16 | 1990-04-25 | 华东师范大学 | Active cathode with porous nickel plating and preparation thereof |
| KR20050065643A (en) * | 2002-11-13 | 2005-06-29 | 세타곤 인코포레이티드 | Medical devices having porous layers and methods for making same |
| WO2015056981A1 (en) * | 2013-10-16 | 2015-04-23 | 부산대학교 산학협력단 | Method for manufacturing nanoporous metals using osmium or rhenium dissolution, and nanoporous metal thereof |
| KR101561966B1 (en) * | 2015-03-26 | 2015-10-20 | 부산대학교 산학협력단 | A fabrication method of nano porous metal |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110230044A (en) * | 2019-07-12 | 2019-09-13 | 中国工程物理研究院激光聚变研究中心 | It is the method that counterfeit template prepares porous boron-doped diamond electrode with nano-diamond powder |
| CN110230044B (en) * | 2019-07-12 | 2021-07-27 | 中国工程物理研究院激光聚变研究中心 | Method for preparing porous boron-doped diamond electrode by using nano diamond powder as pseudo template |
| CN111115762A (en) * | 2019-12-25 | 2020-05-08 | 河南省功能金刚石研究院有限公司 | Novel foam nickel electrode and preparation method thereof |
| CN111115762B (en) * | 2019-12-25 | 2022-06-03 | 河南省功能金刚石研究院有限公司 | Foamed nickel electrode and preparation method thereof |
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Application publication date: 20170104 |