CN102242374A - Production method of titanium-based boron-doping diamond coating electrode - Google Patents
Production method of titanium-based boron-doping diamond coating electrode Download PDFInfo
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Abstract
The invention relates to a production method of titanium-based boron-doping diamond coating electrode, the invention is characterized in that the method is realized by sputtering a transition layer on a substrate material and then depositing the boron-doping diamond coating by a CVD method. The electrode is composed of a substrate (1), a transition layer (2) and a diamond layer (3), and is characterized in that the substrate is titanium, the transition layer is niobium or tantalum through magnetron sputtering, and the boron-doping concentration used in the CVD technology is 6000 - 10000 ppm. The invention provides a production method of BDD electrode with long service life and high electrolytic efficiency, and has the advantages of low cost and high repeatability.
Description
Technical field
The present invention relates to a kind of preparation method of corrosion-resistant electrode, especially a kind of cost is relatively than the manufacture method of boron-doped diamond (BDD) coated electrode at the end, and is specifically a kind of with the preparation method of pure titanium as the base of the titanium cheaply b-doped diamond film electrode of base material.
Background technology
As everyone knows, boron-doped diamond (Boron doped diamond, be called for short BDD) have the characteristic of good electrical conductivity, wide electromotive force window, little background current, high electrochemical stability and many excellences such as anticorrosive, the BDD electrode has broad application prospects at sewage treatment area.
The BDD coating of processability excellence relates to the selection of base material, boron-doping mode, substrate pretreatment scheme, the multiple technologies such as control of CVD parameters Optimization and film-substrate cohesion.For industrial level BDD electrode, existing abroad proven technique and product are as Diachem BDD electrode etc.; Domestic also have extensive studies about the BDD electrode, but product all is in laboratory stage, and the industrial level BDD coated electrode technology of preparation big area and bonding properties and chemical property excellence becomes pressing for of industry member.
Titanium specific tenacity height, thermal expansivity is little, and titanium has good corrosion resistance, in the electrolytic process, the inertia oxide film of the strong adhesive force that the titanium anode surface can the densification of very fast generation one deck, even very fast passivation is also can very fast self-healing or regeneration again through mechanical wear.When carrying out sewage disposal with the BDD electrode, even electrode surface coating is damaged to some extent, the titanium substrate material of passivation also can not influence the integral working of electrode.
Using the substrate material of titanium as deposition boron-doped diamond electrode, mainly be the erosion resistance of using it, the characteristics of mechanical stability, but the subject matter that titanium base diamond coating exists is that film base binding performance is relatively poor, and this has restricted its application prospect.And the bonding properties of titanium and niobium or tantalum is good, and sedimentary diamond bonding properties is excellent relatively on niobium or tantalum simultaneously, but the price of niobium and tantalum will be far above titanium.The sputter transition layer on titanium that the present invention proposes prepares the superperformance that the BDD electrode has utilized titanium simultaneously, has solved the film base binding performance problem, has saved the cost of BDD electrode greatly.
Summary of the invention
The relatively poor caducous problem of bonding properties that the objective of the invention is b-doped diamond film and base material when utilizing titanium as electrode, invent a kind of by increasing the preparation method that transition layer improves the titanium base b-doped diamond film electrode of b-doped diamond film and titanium substrate material bonding force, it has made full use of titanium favorable mechanical performance, corrosion-resistant easy passivation and lower-cost characteristics; The magnetron sputtering technique maturation, bonding properties excellence between substrate and the transition layer; Utilize niobium or tantalum transition layer to improve the bonding properties of coating simultaneously.
Technical scheme of the present invention is:
A kind of preparation method of titanium base b-doped diamond film electrode is characterized in that it may further comprise the steps:
At first, be that the abrasive paper for metallograph of 40 microns (being W40) and 10 microns (being W10) was polished each 5-10 minute to the pure titanium plate surface as base material 1 respectively with granularity;
Secondly, will place alcohol ultrasonic cleaning 2-3 time, each 10 minutes, finish the sputter pre-treatment of blunt titanium plate through the pure titanium plate of polishing;
The 3rd, will place sputter equipment to carry out sputter through the pretreated blunt titanium plate of sputter, form sputter transition layer 2 on blunt titanium plate surface;
The 4th, having the blunt titanium plate of transition layer 2 to put into volumetric molar concentration sputter is that the hydrochloric acid soln of 5-10% carries out pickling, and the control pickling temperature is 70-90 ℃;
The 5th, the blunt titanium plate of pickling to be put into the alcohol suspension liquid of being prepared by 0.2～1 micron diamond powder carry out ultrasonic cleaning at least 30 minutes, the concentration of alcohol suspension liquid is 1g/100ml, so that carry out kind of a crystalline substance on sputter transition layer 2; Carry out ultrasonic cleaning 2-3 time with straight alcohol again after planting brilliant the end, each 2-4 minute, the alcohol ultrasonic cleaning dried up processing after finishing again, obtained process sputter transition layer 2 through pretreated pure titanium plate; The particle diameter of the diamond powder of the alcohol suspension liquid of configuration preferably is made up of the diamond powder of two different-grain diameters;
The 6th, utilize the CVD method on the pretreated sputter transition layer 2 of above-mentioned process, to deposit boron-doped diamond, on sputter transition layer 2, form the boron-doped diamond layer 3 that bonding strength meets the demands.
Described sputtering technology adopts the magnetically controlled DC sputtering technology, sputtering target material is niobium or tantalum, the magnetron sputtering parameter is: electric current 0.5～1.5A, voltage 100～140V, base vacuum 0.001～0.01Pa, working gas are argon gas, air pressure is 0.4～1.5Pa, the base material temperature is 400～600 ℃, sputter radius 65mm, target and matrix apart from 12-14cm.
The processing parameter of described CVD method deposition boron-doped diamond layer is: heated filament is to the distance 6 ~ 8mm of substrate, 2500 ~ 2700 ℃ of hot-wire temperatures, 700 ~ 900 ℃ of underlayer temperatures, carbon source concentration 0.5 ~ 2%, reaction pressure 2 ~ 3kPa; The boron-doping mode is solid, liquid or gas boron source doping, and doping content is 6000 ~ 10000ppm.
The thickness of described sputter transition layer 2 is 100 ~ 500nm, and the thickness of boron-doped diamond layer 3 is 5 ~ 10 μ m.
Beneficial effect of the present invention:
1) cost is lower, and is easy to operate.
2) mechanical property and film base binding performance excellence.
3) BDD electrode electro Chemical excellent performance.
4) saved the cost for preparing the BDD electrode greatly.
Description of drawings
Fig. 1 is the Raman spectrum picture with the BDD electrode of the inventive method preparation.
Fig. 2 is the electrode friction-wear test rear surface SEM image with BDD method preparation of the present invention.
Fig. 3 BDD of the present invention and the H of contrast DSA electrode at 0.5mol/L
2SO
4In cyclic voltammetric (CV) curve synoptic diagram.
Fig. 4 is the structural representation of BDD electrode of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
As shown in Figure 4.
A kind of preparation method of titanium base b-doped diamond film electrode, it may further comprise the steps:
At first, be that the diamond sand paper of 40 microns and 10 microns was polished each 5-10 minute to the pure titanium plate surface as base material 1 respectively with granularity;
Secondly, will place alcohol ultrasonic cleaning 2-3 time, each 10 minutes, finish the sputter pre-treatment of blunt titanium plate through the pure titanium plate of polishing;
The 3rd, will place sputter equipment to carry out sputter through the pretreated blunt titanium plate of sputter, forming thickness on blunt titanium plate surface is the sputter transition layer 2 of 100-500 nanometer; Adopt the magnetically controlled DC sputtering technology during sputter, sputtering target material is niobium or tantalum, the magnetron sputtering parameter is: electric current 0.5～1.5A, voltage 100～140V, base vacuum 0.001～0.01Pa, working gas are argon gas, air pressure is 0.4～1.5Pa, the base material temperature is 400～600 ℃, sputter radius 65mm, target and matrix apart from 12-14cm;
The 4th, having the blunt titanium plate of transition layer 2 to put into volumetric molar concentration sputter is that the hydrochloric acid soln of 5-10% carries out pickling, and the control pickling temperature is 70-90 ℃;
The 5th, the blunt titanium plate of pickling is put into two kinds of particle diameters by 0.2～1 micron of particle diameter (as 0.2 micron and 0.5 micron, 0.3 the micron and 0.6 micron, 0.4 carry out ultrasonic cleaning at least 30 minutes in the alcohol suspension liquid that diamond powder two kinds of particle diameters such as micron and 0.8 micron, 0.5 micron and 1 micron) is prepared, the concentration of alcohol suspension liquid is 1g/100ml, finishes kind of a brilliant process on sputter transition layer 2; Carry out ultrasonic cleaning 2-3 time with straight alcohol solution again after planting brilliant the end, each 2-4 minute, the alcohol ultrasonic cleaning dried up processing after finishing again, obtained process sputter transition layer 2 through pretreated pure titanium plate;
The 6th, utilize the CVD method on the pretreated sputter transition layer 2 of above-mentioned process, to deposit boron-doped diamond, the thickness that the formation bonding strength meets the demands on sputter transition layer 2 is at the boron-doped diamond layer 3 of 5-10 micron, as shown in Figure 4.The processing parameter of CVD method deposition boron-doped diamond layer is: heated filament is to the distance 6 ~ 8mm of substrate, 2500 ~ 2700 ℃ of hot-wire temperatures, 700 ~ 900 ℃ of underlayer temperatures, carbon source concentration 0.5 ~ 2%, reaction pressure 2 ~ 3kPa; The boron-doping mode is solid, liquid or gas boron source doping, and doping content is 6000 ~ 10000ppm.
The key of method of the present invention is by sputter transition layer on base material, realizes with CVD method deposition b-doped diamond film on this basis again.Wherein said sputtering technology adopts the magnetically controlled DC sputtering technology, and base material is pure titanium plate, and sputtering target material is niobium and tantalum, and the titanium plate grinds 5 ~ 10min respectively, alcohol ultrasonic cleaning 10min, 2 ~ 3 times with the sand paper of W40 and W10 before the sputter.The magnetron sputtering parameter is: substrate temperature is 400 ~ 600 ℃, electric current 0.5 ~ 1.5A, and voltage 100 ~ 140V, base vacuum 0.001 ~ 0.01Pa, working gas are argon gas, air pressure is 0.4 ~ 1.5Pa.
The transition layer pretreating scheme is before the described CVD method deposition BDD coating: 1. the titanium plate is put into 5 ~ 10MHCl solution, and the constant temperature water bath design temperature is at 70-90 ℃ of pickling 30min; 2. the titanium plate is planted crystalline substance more than putting into the alcohol suspension liquid ultrasonic cleaning 30min that is prepared by the diamond mixed powder of W0.5 and W0.2, uses alcohol ultrasonic cleaning 3min again, 2 ~ 3 times, dries up processing.
Described deposition BDD coating process is heated filament CVD(HFCVD) method, deposition parameter is that heated filament is to substrate distance 6 ~ 8mm, 2500 ~ 2700 ℃ of hot-wire temperatures, 700 ~ 900 ℃ of underlayer temperatures, carbon source concentration 0.5 ~ 2%, reaction pressure 2 ~ 3kPa.The boron-doping mode can be selected solid, liquids and gases boron source doping, and doping content is 6000 ~ 10000ppm.
Embodiment 1:
Sand paper with W40 and W10 grinds titanium plate 5 ~ 10min respectively, alcohol ultrasonic cleaning 10min, 2 times.Utilize the tantalum transition layer of magnetically controlled DC sputtering sputter 400nm on titanium, sputtering parameter is that substrate temperature is 400 ℃, electric current 1.2A, and voltage 110V, base vacuum 0.005Pa, working gas are argon gas, air pressure is 1.5Pa.The sample that sputter obtains is in 5mol/LHCl solution, the constant temperature water bath design temperature is at 70-90 ℃ of pickling 30min, carry out pre-treatment with ultrasonic cleaning 30min in the alcohol suspension liquid of the diamond mixed powder of W0.5 and W0.2 preparation again, plant brilliant, used the alcohol ultrasonic cleaning again 2-3 minute, each 2-4 minute.Deposit the BDD coating with the HFCVD method on transition layer, deposition parameter is that heated filament arrives substrate distance 6mm, 2600 ℃ of hot-wire temperatures, 800 ℃ of underlayer temperatures, carbon source concentration 1%, reaction pressure 2.4kPa.The boron-doping mode is selected solid boron source doping, and doping content is about 6000ppm, and the deposition certain hour can obtain certain thickness BDD coated electrode, and is higher through Raman spectrum analysis diamond composition, referring to Fig. 1.
The BDD coated electrode that obtains is carried out friction-wear test, and the coating after the test keeps good integrity, does not have significantly wearing and tearing or obscission, referring to Fig. 2, BDD electrode favorable mechanical performance and film base binding performance has been described.
With BDD coated electrode and the DSA electrode (Ti/IrO that obtains
2/ Ta
2O
5Oxide coating electrode) compares, place the H of 0.5mol/L
2SO
4Carry out the cyclic voltammetric test in the solution, obtain at H
2SO
4CV curve in the solution is referring to Fig. 3.The electromotive force window of electrode is 3.2V, and oxygen evolution potential is 2.3V, and background current is the mA rank, and the electromotive force window of DSA electrode is 2.1V, and oxygen evolution potential is 1.2V, has shown that prepared BDD electrode has good electrochemical.
The BDD coated electrode that obtains is carried out petroleum coking sewage disposal test as reacting anode, the long-pending 8cm of being of electrode face after encapsulating
2, negative electrode is the stainless steel steel disc, polar plate spacing 5mm adopts the magnetic agitation auxiliary treatment.The original COD of sewage is 8000mg/L, at 100mA/cm
2Under the current density, COD reduces to 800mg/L behind the constant-current electrolysis 120min, and degradation rate reaches 90%.It is intact to handle the rear electrode surface, and chemical property does not have considerable change, has shown electrode good whole stability.
Example 2.
Sand paper with W40 and W10 grinds titanium plate 5 ~ 10min respectively, alcohol ultrasonic cleaning 10min, 3 times.Utilize the niobium transition layer of magnetically controlled DC sputtering sputter 100nm on titanium, sputtering parameter is that substrate temperature is 600 ℃, electric current 0.5A, and voltage 100V, base vacuum 0.001Pa, working gas are argon gas, air pressure is 0.4Pa.The sample that sputter obtains is in 10mol/LHCl solution, the constant temperature water bath design temperature is at 70-90 ℃ of pickling 30min, carry out after kind of the brilliant pre-treatment again in spirituous solution ultrasonic cleaning 2-3 time with ultrasonic cleaning 30min in the alcohol suspension liquid of the diamond mixed powder of W0.5 and W0.2 preparation again, each 4 minutes.Deposit the BDD coating with the HFCVD method on transition layer, deposition parameter is that heated filament arrives substrate distance 8m, 2500 ℃ of hot-wire temperatures, 700 ℃ of underlayer temperatures, carbon source concentration 0.5%, reaction pressure 2kPa.The boron-doping mode is selected gas boron source doping, and doping content is about 10000ppm, and the deposition certain hour can obtain certain thickness BDD coated electrode, and is suitable with example 1 through Raman spectrum analysis diamond composition.
The BDD coated electrode that obtains is carried out friction-wear test, and the coating after the test keeps good integrity, does not have significantly wearing and tearing or obscission,, BDD electrode favorable mechanical performance and film base binding performance have been described.
With BDD coated electrode and the DSA electrode (Ti/IrO that obtains
2/ Ta
2O
5Oxide coating electrode) compares, place the H of 0.5mol/L
2SO
4Carry out the cyclic voltammetric test in the solution, obtain at H
2SO
4CV curve in the solution.The electromotive force window of electrode is 3.2V, and oxygen evolution potential is 2.3V, and background current is the mA rank, and the electromotive force window of DSA electrode is 2.1V, and oxygen evolution potential is 1.2V, has shown that prepared BDD electrode has good electrochemical.
The BDD coated electrode that obtains is carried out petroleum coking sewage disposal test as reacting anode, the long-pending 8cm of being of electrode face after encapsulating
2, negative electrode is the stainless steel steel disc, polar plate spacing 5mm adopts the magnetic agitation auxiliary treatment.The original COD of sewage is 8000mg/L, at 100mA/cm
2Under the current density, COD reduces to 800mg/L behind the constant-current electrolysis 120min, and degradation rate reaches 90%.It is intact to handle the rear electrode surface, and chemical property does not have considerable change, has shown electrode good whole stability.
Example 3.
Sand paper with W40 and W10 grinds titanium plate 5 ~ 10min respectively, alcohol ultrasonic cleaning 10min, 3 times.Utilize the tantalum transition layer of magnetically controlled DC sputtering sputter 500nm on titanium, sputtering parameter is that substrate temperature is 500 ℃, electric current 1.5A, and voltage 140V, base vacuum 0.01Pa, working gas are argon gas, air pressure is 1.5Pa.The sample that sputter obtains is in 10mol/LHCl solution, the constant temperature water bath design temperature is at 70-90 ℃ of pickling 30min, carry out after kind of the brilliant pre-treatment again in spirituous solution ultrasonic cleaning 2-3 time with ultrasonic cleaning 30min in the alcohol suspension liquid of the diamond mixed powder of W0.5 and W0.2 preparation again, each 3 minutes.Deposit the BDD coating with the HFCVD method on transition layer, deposition parameter is that heated filament arrives substrate distance 7m, 2700 ℃ of hot-wire temperatures, 900 ℃ of underlayer temperatures, carbon source concentration 2%, reaction pressure 3kPa.The boron-doping mode is selected the liquid boron source doping, and doping content is about 8000ppm, and the deposition certain hour can obtain certain thickness BDD coated electrode, and is suitable with example 1 through Raman spectrum analysis diamond composition.
The BDD coated electrode that obtains is carried out friction-wear test, and the coating after the test keeps good integrity, does not have significantly wearing and tearing or obscission,, BDD electrode favorable mechanical performance and film base binding performance have been described.
With BDD coated electrode and the DSA electrode (Ti/IrO that obtains
2/ Ta
2O
5Oxide coating electrode) compares, place the H of 0.5mol/L
2SO
4Carry out the cyclic voltammetric test in the solution, obtain at H
2SO
4CV curve in the solution.The electromotive force window of electrode is 3.2V, and oxygen evolution potential is 2.3V, and background current is the mA rank, and the electromotive force window of DSA electrode is 2.1V, and oxygen evolution potential is 1.2V, has shown that prepared BDD electrode has good electrochemical.
The BDD coated electrode that obtains is carried out petroleum coking sewage disposal test as reacting anode, the long-pending 8cm of being of electrode face after encapsulating
2, negative electrode is the stainless steel steel disc, polar plate spacing 5mm adopts the magnetic agitation auxiliary treatment.The original COD of sewage is 8000mg/L, at 100mA/cm
2Under the current density, COD reduces to 800mg/L behind the constant-current electrolysis 120min, and degradation rate reaches 90%.It is intact to handle the rear electrode surface, and chemical property does not have considerable change, has shown electrode good whole stability.
The part that the present invention does not relate to prior art that maybe can adopt all same as the prior art is realized.
Claims (5)
1. the preparation method of a titanium base b-doped diamond film electrode is characterized in that it may further comprise the steps:
At first, be that the abrasive paper for metallograph of W40 and W10 was polished each 5-10 minute to the pure titanium plate surface as base material (1) respectively with granularity;
Secondly, will place alcohol ultrasonic cleaning 2-3 time, each 10 minutes, finish the sputter pre-treatment of blunt titanium plate through the pure titanium plate that grinds;
The 3rd, will place sputter equipment to carry out sputter through the pretreated blunt titanium plate of sputter, form sputter transition layer (2) on blunt titanium plate surface;
The 4th, having the blunt titanium plate of transition layer (2) to put into volumetric molar concentration sputter is that the hydrochloric acid soln of 5-10% carries out pickling, and the control pickling temperature is 70-90 ℃;
The 5th, the blunt titanium plate of pickling to be put into the alcohol suspension liquid of being prepared by 0.2～1 micron diamond powder carry out ultrasonic cleaning at least 30 minutes, the concentration of alcohol suspension liquid is 1g/100ml, so that carry out kind of a crystalline substance on sputter transition layer (2); Carry out ultrasonic cleaning 2-3 time with straight alcohol again after planting brilliant the end, each 2-4 minute, the alcohol ultrasonic cleaning dried up processing after finishing again, obtained process sputter transition layer (2) through pretreated pure titanium plate;
The 6th, utilize the CVD method to go up the deposition boron-doped diamond at the pretreated sputter transition layer of above-mentioned process (2), go up at sputter transition layer (2) and form the boron-doped diamond layer (3) that bonding strength meets the demands.
2. method according to claim 1, it is characterized in that described sputtering technology adopts the magnetically controlled DC sputtering technology, sputtering target material is niobium or tantalum, and the magnetron sputtering parameter is: electric current 0.5～1.5A, voltage 100～140V, base vacuum 0.001～0.01Pa, working gas is an argon gas, and air pressure is 0.4～1.5Pa, and the base material temperature is 400～600 ℃, sputter radius 65mm, target and matrix apart from 12-14cm.
3. method according to claim 1, the processing parameter that it is characterized in that described CVD method deposition boron-doped diamond layer is: heated filament is to the distance 6 ~ 8mm of substrate, 2500 ~ 2700 ℃ of hot-wire temperatures, 700 ~ 900 ℃ of underlayer temperatures, carbon source concentration 0.5 ~ 2%, reaction pressure 2 ~ 3kPa; The boron-doping mode is solid, liquid or gas boron source doping, and doping content is 6000 ~ 10000ppm.
4. method according to claim 1, the thickness that it is characterized in that described sputter transition layer (2) is 100 ~ 500nm, the thickness of boron-doped diamond layer (3) is 5 ~ 10 μ m.
5. method according to claim 1 is characterized in that the formulated alcohol suspension liquid of diamond powder that described blunt titanium plate with pickling is put into by two kinds of different-grain diameters of 0.2～1 micron carries out ultrasonic cleaning at least 30 minutes.
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| CN106435518A (en) * | 2016-10-21 | 2017-02-22 | 中南大学 | High-specific-surface-area boron-doped diamond electrode and preparation method and application thereof |
| CN106637111B (en) * | 2016-10-21 | 2019-02-01 | 中南大学 | A kind of niobium base boron-doped diamond foam electrode and the preparation method and application thereof |
| US11603594B2 (en) | 2016-10-21 | 2023-03-14 | Nanjing Daimonte Technology Co., Ltd. | Boron doped diamond electrode and preparation method and applications thereof |
| CN107312958A (en) * | 2017-06-07 | 2017-11-03 | 北京科技大学 | A kind of diamond valve metal combination electrode material and preparation method thereof |
| CN109750291A (en) * | 2017-11-07 | 2019-05-14 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
| CN109722647A (en) * | 2018-12-29 | 2019-05-07 | 中国地质大学（北京） | A kind of BDD electrode and its purposes for monitoring Heavy Metals in Waters ion on-line |
| CN111705320A (en) * | 2020-05-08 | 2020-09-25 | 中国船舶重工集团公司第七二五研究所 | Auxiliary anode assembly for protecting cathode of icebreaker |
| CN113858036A (en) * | 2021-08-23 | 2021-12-31 | 四川纳涂科技有限公司 | Hard alloy grinding rod with diamond coating and preparation method thereof |
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Application publication date: 20111116 |