CN115404459B - Distributed boron-doped diamond/metal matrix composite material and preparation method and application thereof - Google Patents
Distributed boron-doped diamond/metal matrix composite material and preparation method and application thereof Download PDFInfo
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- CN115404459B CN115404459B CN202211088307.2A CN202211088307A CN115404459B CN 115404459 B CN115404459 B CN 115404459B CN 202211088307 A CN202211088307 A CN 202211088307A CN 115404459 B CN115404459 B CN 115404459B
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- boron
- doped diamond
- substrate
- matrix composite
- distributed
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 102
- 239000010432 diamond Substances 0.000 title claims abstract description 102
- 239000011156 metal matrix composite Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 23
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims description 54
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 33
- 229910052796 boron Inorganic materials 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002113 nanodiamond Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 238000004050 hot filament vapor deposition Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000557 Nafion® Polymers 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- -1 al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000835 electrochemical detection Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- INOIOAWTVPHTCJ-UHFFFAOYSA-N 6-acetamido-4-hydroxy-3-[[4-(2-sulfooxyethylsulfonyl)phenyl]diazenyl]naphthalene-2-sulfonic acid Chemical compound CC(=O)NC1=CC=C2C=C(C(N=NC3=CC=C(C=C3)S(=O)(=O)CCOS(O)(=O)=O)=C(O)C2=C1)S(O)(=O)=O INOIOAWTVPHTCJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
- B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
-
- 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a distributed boron-doped diamond/metal matrix composite material, a preparation method and application thereof, wherein the distributed boron-doped diamond/metal matrix composite material comprises a metal sheet and a plurality of boron-doped diamond electrode plates distributed on the surface of the metal sheet at intervals, and a lead oxide coating is arranged between the metal sheet and the boron-doped diamond electrode plates; the lead sub-oxide coating is fully coated on the surface of the metal sheet, or a plurality of lead sub-oxide coatings are arranged on the surface of the metal sheet at intervals; the invention provides a distributed boron-doped diamond/metal matrix composite for the first time, which is formed by combining a plurality of boron-doped diamond electrode plates, has good conductivity and larger electrochemical active area compared with single BDD, has better corrosion resistance effect and longer service life compared with single BDD.
Description
Technical Field
The invention relates to a distributed boron-doped diamond/metal matrix composite material, a preparation method and application thereof, belonging to the field of
Background
Diamond is a material with excellent physical and chemical properties, has the characteristics of high mechanical strength, excellent chemical stability and performance, no obvious change on the surface of an acting electrode under high-intensity current load, and the like, so that the diamond has wide prospect in the aspect of electrochemical application. The boron doped diamond electrode obtained by doping boron elements in the growth process of the diamond film, so that the prepared boron doped diamond film is changed into a semiconductor or a conductor with metal property, and the semiconductor or the conductor is deposited on the surface of certain electrode matrixes such as titanium sheets, silicon wafers, graphite and the like is an important point in the fields of sewage purification treatment, electrochemical biosensors and the like in recent years. Compared with the traditional electrode, the boron-doped diamond film electrode has the advantages of wide window, small background current, good electrochemical stability, good mechanical property, strong corrosion resistance, good conductivity and the like, and has good prospect in the field of electrochemical oxidation treatment of sewage.
The traditional single-layer electrode for growing boron-doped diamond on a titanium sheet or a silicon wafer often has the defects that the film is easy to fall off due to unmatched thermal expansion coefficients, and the conductivity of the silicon wafer is insufficient, so that the further development of the boron-doped diamond film electrode is limited.
Recent advances in electrochemical processes and the advent of new electrode materials and electrode structures have provided newer and more effective solutions for electrochemical research. The multilayer composite electrode material has better conductivity and longer electrode lifetime than a single layer electrode. Compared with the limited process production size of a single-layer electrode, the multi-layer composite electrode has larger size, and the multi-electrode combination obtains larger specific surface area, so that the electrochemical activity is stronger, the efficiency is higher, and the application range of the electrode is expanded while the excellent electrochemical performance is considered, so that the multi-layer composite electrode can be applied to more fields.
However, there is no report on the combination of multiple electrodes.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a long-life, high-conductivity and higher electrochemical activity distributed boron-doped diamond/metal matrix composite.
The second object of the invention is to provide a preparation method of the distributed boron-doped diamond/metal matrix composite material.
A third object of the present invention is to provide the use of a distributed boron doped diamond/metal matrix composite.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a distributed boron-doped diamond/metal matrix composite material, which comprises a metal sheet and a plurality of boron-doped diamond electrode plates distributed on the surface of the metal sheet at intervals, wherein a lead oxide coating is arranged between the metal sheet and the boron-doped diamond electrode plates.
The invention provides a distributed boron-doped diamond/metal matrix composite for the first time, which is formed by combining a plurality of boron-doped diamond electrode plates, has good conductivity and larger electrochemical active area compared with single BDD, has better corrosion resistance effect and longer service life compared with single BDD; and lead oxide coating with excellent conductivity is introduced between the metal sheet and the boron-doped diamond electrode sheet, so that the metal sheet and the boron-doped diamond electrode sheet are firmly sintered, welded and connected on the basis of ensuring conductivity.
In a preferred scheme, the lead sub-oxide coating is fully coated on the surface of the metal sheet, or a plurality of lead sub-oxide coatings are arranged on the surface of the metal sheet at intervals.
The inventor finds that when the lead sub-oxide coating is fully coated on the surface of the metal sheet and then a plurality of boron-doped diamond electrode plates are arranged on the lead sub-oxide coating, the lead sub-oxide can act together with BDD, so that the active area is larger, and when a plurality of lead sub-oxide coatings are arranged on the surface of the metal sheet at intervals and then a corresponding number of boron-doped diamond electrode plates are arranged on the surfaces of the lead sub-oxide coatings, the boron-doped diamond electrode plates can obtain higher oxidation potential.
Preferably, the thickness of the lead sub-oxide coating is 500nm-200 μm, preferably 50-150 μm, and the inventors have found that the thickness of the lead sub-oxide coating needs to be effectively controlled, and that excessive thickness and excessive thickness have an effect on the bonding force.
In a preferred scheme, the metal sheet is selected from one of a titanium-coated copper sheet, a tantalum-coated copper sheet, a titanium sheet, a niobium sheet, a tantalum sheet and a zirconium sheet.
Preferably, the structure of the metal sheet is selected from one of continuous plate-like, net-like, discontinuous frame, column-like, barrel-like, irregular solid-like, regular solid-like structures.
In a preferred scheme, the boron doped diamond electrode plates are arranged on the surface of the metal plate in an array arrangement mode.
The inventor finds that the boron-doped diamond electrode plates are arranged in various array modes according to the needs, so that the optimal electrode unit radiation range can be obtained, and the electrocatalytic active area and the current efficiency are higher.
In a preferred scheme, the boron-doped diamond electrode plate consists of a substrate and a boron-doped diamond film layer arranged on the surface of the substrate.
Further preferably, the substrate is selected from one of metallic nickel, niobium, tantalum, zirconium, copper, titanium, cobalt, tungsten, molybdenum, chromium, iron or one of alloys thereof; or the substrate is selected from the group consisting of ceramics Si, al 2 O 3 、ZrO 2 、SiC、Si 3 N 4 、BN、B 4 C、AlN、TiB 2 、TiN、WC、Cr 7 C 3 、Ti 2 GeC、Ti 2 AlC and Ti 2 AlN、Ti 3 SiC 2 、Ti 3 GeC 2 、Ti 3 AlC 2 、Ti 4 AlC 3 、BaPO 3 One of or a doped ceramic therein.
Further preferably, the substrate structure is at least one selected from the group consisting of a three-dimensional continuous network structure, a two-dimensional closed flat structure, a one-dimensional filament, a one-dimensional line, a one-dimensional rod, and a zero-dimensional particle.
Further preferably, the thickness of the boron doped diamond film layer is 5-20 μm.
Further preferably, the mass fraction of boron element in the boron-doped diamond film layer is 2-10 per mill.
In the invention, the shape of the boron doped diamond electrode sheet is not limited, and can be triangle, square, round, star or other regular or irregular shapes,
in the invention, the substrate can be welded with the boron doped diamond electrode plates with different shapes as leftover materials in production, and the materials can be reused.
The invention relates to a preparation method of a distributed boron-doped diamond/metal matrix composite material, which comprises the following steps: and uniformly arranging the coating containing the lead sub-oxide on a metal sheet, then arranging the coating with the exposed surface of the substrate of the boron-doped diamond electrode sheet facing the lead sub-oxide on the metal sheet containing the coating containing the lead sub-oxide, drying and sintering to obtain the distributed boron-doped diamond/metal matrix composite material.
In a preferred scheme, the preparation method of the coating containing lead sub-oxide comprises the following steps: mixing absolute ethanol, water, lead oxide, sintering aid and binder, and stirring at 80-120deg.C for 30-90 min.
Further preferably, the mass ratio of the absolute ethyl alcohol to the water to the lead oxide is (1-3): 7-10): 8-11. In the actual operation process, the water is deionized water.
Further preferably, the sintering aid is selected from the group consisting of Al powder, ti powder, tiC powder 2 Powder, pbO 2 Powder, tiB 2 At least one of the powder, the addition amount of the sintering aid is lead oxide quality2wt.% to 10wt.% of the amount.
Further preferably, the binder is at least one selected from polyvinyl alcohol, polyethylene glycol and nafion, and the addition amount of the binder is 2-10 wt.% of the mass of lead suboxide.
In the actual operation process, when the lead sub-oxide coating is fully coated on the surface of the metal sheet, one or more modes of dipping, spin coating, roll coating, spraying and brushing can be adopted to uniformly set the coating containing lead sub-oxide on the metal sheet, and when a plurality of lead sub-oxide coatings are arranged on the surface of the metal sheet at intervals, a corresponding number of boron-doped diamond electrode plates are arranged on the surfaces of the lead sub-oxide coatings, one mode of spraying or brushing is adopted to uniformly set the coating containing lead sub-oxide on the metal sheet.
And then placing the coating with the exposed surface of the substrate of the boron-doped diamond electrode plate facing the lead sub-oxide-containing coating on a metal plate of the lead sub-oxide-containing coating, and fixing the boron-doped diamond electrode plate by adopting a clamp.
Preferably, the drying temperature is 60-90 ℃ and the drying time is 5-24h.
Preferably, the sintering process is as follows: heating to 300-450 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-3h, heating to 500-750 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-4 h, and controlling the vacuum degree to be 1000-6000pa and the flow rate of argon atmosphere to be 20-100sccm.
The inventors found that the electrode sheet, the lead oxide coating and the metal sheet can be well bonded by the above-described temperature rising process, but bonding is affected if the sintering process of the present invention is not performed.
In a preferred scheme, the acquisition process of the boron-doped diamond electrode plate comprises the following steps: firstly, etching a substrate, then planting nano diamond seed crystals on the surface of the etched substrate, and finally, adopting hot filament chemical vapor deposition to grow a boron doped diamond layer on the etching surface of the substrate.
The inventor finds that the etching treatment can remove the surface oxide film and the surface greasy dirt, increase the specific surface area of the substrate, strengthen the binding force and enable the electrode plate to be sintered and welded better.
Further preferably, when the substrate is ceramic, firstly ultrasonically cleaning the substrate, and then heating and etching the substrate in a water bath at 50-90 ℃ for 0.5-2 hours by using an alkali solution, wherein the mass fraction of alkali in the alkali solution is 5-20%, and the alkali is at least one selected from sodium hydroxide, potassium hydroxide and lithium hydroxide; when the substrate is metal, firstly carrying out ultrasonic cleaning on the substrate, and then carrying out heating etching treatment on the substrate by using oxalic acid solution at 70-100 ℃ for 1-3 hours, wherein the mass fraction of oxalic acid in the oxalic acid solution is 5% -15%.
Further preferably, the process of planting the nano diamond seed crystal on the surface of the substrate comprises the following steps: and vertically suspending and immersing the substrate into a suspension containing nano diamond seed crystals, carrying out ultrasonic vibration for more than or equal to 15min, and finally washing and drying by alcohol to obtain the nano diamond seed crystals, wherein the granularity of the nano diamond seed crystals is 5-20nm, and the mass concentration of the nano diamond seed crystals in the suspension is 1-5%.
Further preferably, the process of growing the boron doped diamond layer on the etched surface of the substrate by hot filament chemical vapor deposition comprises the following steps: the mass flow ratio of the gas is as follows: methane: boron doped gas source = 100: (1-5): (0.1-2.5), the growth pressure is 2-5Kpa, the growth temperature is 600-950 ℃, the number of times of growth is 1-3, and the time of single growth is 5-24h.
The invention relates to an application of a distributed boron-doped diamond/metal matrix composite, which is applied to one of the fields of electrochemical synthesis, electrochemical sewage purification treatment, electrochemical detection and electrochemical biological sensors.
The invention relates to an application of a distributed boron-doped diamond/metal matrix composite, which is applied to electrochemical resource regeneration and recycling, wherein the distributed boron-doped diamond/metal matrix composite is used as an anode, at least one of permanganate, persulfate, hypochlorite, ozone and hydrogen peroxide is regenerated in the anode, at least one of gold, silver, aluminum, zinc, copper, chromium, nickel and palladium is recovered in the cathode, and an ion exchange membrane is arranged between the cathode and the anode.
Advantageous effects
1. Compared with the limited process production size of a single-layer electrode, the multi-layer composite electrode has larger size, and the multi-electrode combination obtains larger specific surface area, so that the electrochemical activity is stronger and the efficiency is higher.
2. The lead oxide has a ceramic phase and low preparation temperature, and the lead oxide is used as an intermediate layer coating, so that the phenomena that a film is easy to fall off due to unmatched thermal expansion coefficients, the conductivity deficiency of a silicon wafer is overcome, and the performances of conductivity, corrosion resistance and the like of the composite material are improved.
3. The lead sub-oxide high temperature sintering and the substrate are subjected to metallurgical reaction to form oxide substances, so that the bonding capability of the substrate to the boron-doped diamond film layer is improved, and the lead sub-oxide conductive intermediate layer plays a role of a bonding bridge between the substrate and the boron-doped diamond electrode plate.
Drawings
Fig. 1 is a schematic diagram of the distributed boron doped diamond/metal matrix composite material prepared in example 1, in which, from top to bottom: boron doped diamond electrode plate, lead oxide intermediate layer and metal sheet.
Fig. 2 is a schematic diagram of the distributed boron doped diamond/metal matrix composite according to example 2, wherein the schematic diagram is as follows, in order from top to bottom: boron doped diamond electrode plate, lead oxide intermediate layer and metal sheet.
Detailed Description
Example 1
Taking monocrystalline silicon ceramic as a substrate, firstly carrying out ultrasonic cleaning on the substrate, and carrying out water bath heating etching treatment on a silicon carbide substrate for 0.5h by using a sodium hydroxide solution with the mass fraction of 5%;
the method adopts hot filament chemical vapor deposition to grow the boron doped diamond layer, and comprises the following specific processes: the mass flow ratio of the gas is as follows: methane: boron doped gas source = 100:2:0.6, the growth pressure is 3Kpa, the growth temperature is 750 ℃, the growth times are 3 times, and the time of single growth is 12 hours; one surface of the boron-doped diamond electrode sheet is a bare substrate on one surface of the boron-doped diamond film layer;
and (3) stirring absolute ethyl alcohol, deionized water, lead oxide, al powder, a binder and polyvinyl alcohol at 100 ℃ for 60min to obtain the lead oxide conductive intermediate layer coating. Wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the lead suboxide is 2:8:11, the addition amount of the Al powder is 5wt.% of the mass fraction of the lead suboxide, and the addition amount of the polyvinyl alcohol is 7wt.% of the mass fraction of the lead suboxide.
Preparing a distributed boron-doped diamond/titanium-based composite electrode by adopting a thermal decomposition method, uniformly brushing the prepared lead sub-oxide conductive intermediate layer coating on a titanium sheet, and fixing the exposed substrate of the prepared boron-doped diamond electrode sheet facing the sub-oxide intermediate layer through a clamp; the mixture was moved to an oven and dried at 60℃for 12 hours, the coating thickness of the intermediate layer of the oxide being 100. Mu.m.
The prepared sample is sintered at a high temperature in a segmented way: the sintering temperature of the first section is 300 ℃, and the sintering time is 2 hours; the second stage sintering temperature is 500 ℃, the sintering time is 3 hours, the heating rate is 5 ℃/min, the vacuum degree is 3000pa, and the argon atmosphere flow is 70sccm; the sintered distributed boron-doped diamond/titanium-based composite electrode is firmly combined and has no falling-off phenomenon.
Packaging the prepared distributed boron-doped diamond/titanium-based composite electrode, and preparing 1L of electrolyte Na with initial concentration of 100mg/L by using a stainless steel electrode as a negative electrode 2 SO 4 Reactive orange X-GN simulated dye wastewater with the concentration of 0.1mol/L is put on a magnetic stirrer, the rotating speed is regulated to 200r/min, and the current density in the degradation process is kept to be 100mA/cm 2 And degrading for 2 hours, wherein the chromaticity removal rate of the dye reaches 98%, and basically degrading completely. The removal rate of the degraded TOC is 40% in 2 hours, the energy consumption is 46.379KJ, and the unit TOC removal energy consumption is 7.976KJ/KgTOC. The degradation effect is obviously better than that of a single boron-doped diamond electrode with the same area.
Example 2
Firstly, ultrasonically cleaning a substrate by taking zirconia ceramic as the substrate, and heating and etching the silicon carbide substrate by using a sodium hydroxide solution with the mass fraction of 5% in a water bath at 70 ℃ for 0.5h;
the method adopts hot filament chemical vapor deposition to grow the boron doped diamond layer, and comprises the following specific processes: the mass flow ratio of the gas is as follows: methane: boron doped gas source = 100:3:0.8, the growth pressure is 3Kpa, the growth temperature is 700 ℃, the growth times are 3 times, and the time of single growth is 20 hours; one surface of the boron-doped diamond electrode sheet is a bare substrate on one surface of the boron-doped diamond film layer;
and (3) stirring absolute ethyl alcohol, deionized water, lead oxide, al powder, a binder and polyvinyl alcohol at 100 ℃ for 60min to obtain the lead oxide conductive intermediate layer coating. Wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the lead suboxide is 2:7:10, the addition amount of the Al powder is 3wt.% of the mass fraction of the lead suboxide, and the addition amount of the polyvinyl alcohol is 5wt.% of the mass fraction of the lead suboxide.
Preparing a distributed boron-doped diamond/titanium-based composite electrode by adopting a thermal decomposition method, locally brushing the prepared lead sub-oxide conductive intermediate layer coating on a titanium sheet according to the distribution mode of boron-doped diamond, and fixing the prepared boron-doped diamond electrode sheet with the exposed substrate facing the sub-oxide intermediate layer through a clamp; the mixture was moved to an oven and dried at 60℃for 12 hours, the coating thickness of the intermediate layer of the oxide being 70. Mu.m.
The prepared sample is sintered at a high temperature in a segmented way: the sintering temperature of the first section is 300 ℃, and the sintering time is 2 hours; the second stage sintering temperature is 500 ℃, the sintering time is 3 hours, the heating rate is 5 ℃/min, the vacuum degree is 3000pa, and the argon atmosphere flow is 70sccm; the sintered distributed boron-doped diamond/titanium-based composite electrode is firmly combined and has no falling-off phenomenon.
Packaging the prepared distributed boron-doped diamond/titanium-based composite electrode, and preparing 1L of electrolyte Na with initial concentration of 100mg/L by using a stainless steel electrode as a negative electrode 2 SO 4 Reactive orange X-GN simulated dye wastewater with the concentration of 0.1mol/L is put on a magnetic stirrer, the rotating speed is regulated to 200r/min, and the current density in the degradation process is kept to be 100mA/cm 2 And degrading for 2 hours, wherein the chromaticity removal rate of the dye reaches 96%, and basically degrading completely. The removal rate of the degraded TOC is 37.650 percent, the energy consumption is 49.519KJ, and the unit TOC removal energy consumption is 8.03KJ/KgTOC. The degradation effect is obvious due to the single boron doped diamond electrode under the same area.
Example 3
The electricity prepared in example 1The anode is used for degrading the PCB copper etching waste liquid, the prepared distributed boron-doped diamond and metal-based composite electrode is used as an anode, copper is used as a cathode, a cation exchange membrane is arranged between the anode and the cathode, and gauze is covered outside the cation exchange membrane and used for filtering particle impurities in the waste liquid; the conditions of the electrolysis parameters are as follows: current 60A, voltage 23V, current density 200A/m2, electrode spacing 50mm, cathode/anode electrode area ratio 2; SO in etching waste liquid 4 2- The concentration of copper ions is 232g/L, the concentration of copper ions is 180g/L, and the etching speed is 10.0 mu m/min; the etching waste liquid is electrolyzed until the copper ion content is reduced to about 40g/L, and obvious red copper simple substance precipitation on the cathode can be seen; detection S 2 O 8 2- The current efficiency of the system for generating persulfate through anodic oxidation is calculated to be about 80% under the output condition, S 2 O 8 2- The regeneration and copper recovery effects are obvious.
Comparative example 1
Otherwise, the conditions were the same as in example 1, except that no intermediate lead sub-oxide coating was provided for direct sintering, BDD was hardly bonded to the titanium substrate, and was significantly dropped.
Comparative example 2
Other conditions are the same as those of the embodiment 1, only titanium oxide is selected as the middle conductive coating, the bonding force between the boron doped diamond electrode and the metal substrate after sintering is not strong, the boron doped diamond electrode is easy to peel off after being stressed, and the degradation effect is far less than that of the embodiment 1.
Comparative example 3
Other conditions are the same as those of the embodiment 2, the heating rate is too high in high-temperature sintering and is 20 ℃/min, lead oxide formed by sintering is poor in cohesiveness, the binding force between the boron-doped diamond and a metal substrate is not strong, the boron-doped diamond is easy to fall off, and the degradation effect is far less than that of the embodiment 2.
Claims (7)
1. A distributed boron doped diamond/metal matrix composite, characterized by: the distributed boron-doped diamond/metal matrix composite material comprises a metal sheet and a plurality of boron-doped diamond electrode plates which are distributed on the surface of the metal sheet at intervals, wherein a lead oxide coating is arranged between the metal sheet and the boron-doped diamond electrode plates;
the metal sheet is selected from one of a titanium-coated copper sheet, a tantalum-coated copper sheet, a titanium sheet, a niobium sheet, a tantalum sheet and a zirconium sheet;
the boron-doped diamond electrode plates are arranged on the surface of the metal plate in an array arrangement mode;
the lead sub-oxide coating is fully coated on the surface of the metal sheet, or a plurality of lead sub-oxide coatings are arranged on the surface of the metal sheet at intervals; the thickness of the lead oxide coating is 500nm-200 mu m;
the boron-doped diamond electrode plate consists of a substrate and a boron-doped diamond film layer arranged on the surface of the substrate;
the substrate is selected from one of metal nickel, niobium, tantalum, zirconium, copper, titanium, cobalt, tungsten, molybdenum, chromium and iron or one of alloys thereof; or the substrate is selected from Si, al 2 O 3 、ZrO 2 、SiC、Si 3 N 4 、BN、B 4 C、AlN、TiB 2 、TiN、WC、Cr 7 C 3 、Ti 2 GeC、Ti 2 AlC and Ti 2 AlN、Ti 3 SiC 2 、Ti 3 GeC 2 、Ti 3 AlC 2 、Ti 4 AlC 3 、BaPO 3 One or more of the doped ceramics;
the preparation method of the distributed boron-doped diamond/metal matrix composite material comprises the following steps: uniformly arranging a coating containing lead sub-oxide on a metal sheet, then placing the coating with the exposed surface of the substrate of the boron-doped diamond electrode sheet facing the lead sub-oxide on the metal sheet of the coating containing lead sub-oxide, drying and sintering to obtain the distributed boron-doped diamond/metal matrix composite material;
the preparation method of the coating containing lead oxide comprises the following steps: mixing absolute ethanol, water, lead oxide, sintering aid and binder, and stirring at 80-120deg.C for 30-90 min;
wherein the mass ratio of the absolute ethyl alcohol to the water to the lead oxide is (1-3): 7-10): 8-11;
the sintering aid is selected from Al powder, ti powder and TiC 2 Powder, pbO 2 Powder, tiB 2 At least one of the powders, wherein the addition amount of the sintering aid is 2 wt-10 wt% of the mass of the lead oxide;
the binder is at least one of polyvinyl alcohol, polyethylene glycol and nafion, and the addition amount of the binder is 2 wt-10 wt% of the mass of the lead oxide;
the sintering process comprises the following steps: heating to 300-450 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-3h, heating to 500-750 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-4 h, controlling the vacuum degree to be 1000-6000Pa, and controlling the flow of argon atmosphere to be 20-100sccm.
2. A distributed boron doped diamond/metal matrix composite according to claim 1, wherein: the thickness of the boron-doped diamond film layer is 5-20 mu m;
the mass fraction of boron element in the boron-doped diamond film layer is 2-10 per mill.
3. A distributed boron doped diamond/metal matrix composite according to claim 1, wherein: the drying temperature is 60-90 ℃ and the drying time is 5-24h.
4. The method for preparing the distributed boron-doped diamond/metal matrix composite according to claim 1, wherein the method comprises the following steps: the acquisition process of the boron-doped diamond electrode slice comprises the following steps: firstly, etching a substrate, then planting nano diamond seed crystals on the surface of the etched substrate, and finally, adopting hot filament chemical vapor deposition to grow a boron doped diamond layer on the etching surface of the substrate.
5. A distributed boron doped diamond/metal matrix composite according to claim 1, wherein: when the substrate is ceramic, firstly ultrasonically cleaning the substrate, and then heating and etching the substrate in a water bath at 50-90 ℃ for 0.5-2 hours by using an alkali solution, wherein the mass fraction of alkali in the alkali solution is 5% -20%, and the alkali is at least one selected from sodium hydroxide, potassium hydroxide and lithium hydroxide; when the substrate is metal, firstly carrying out ultrasonic cleaning on the substrate, and then carrying out heating etching treatment on the substrate in a water bath at 70-100 ℃ for 1-3 hours by using oxalic acid solution, wherein the mass fraction of oxalic acid in the oxalic acid solution is 5% -15%;
the process of planting the nano diamond seed crystals on the surface of the substrate comprises the following steps: vertically suspending and immersing a substrate into a suspension containing nano diamond seed crystals, carrying out ultrasonic vibration for more than or equal to 15min, and finally washing and drying by alcohol to obtain the nano diamond seed crystals, wherein the granularity of the nano diamond seed crystals is 5-20nm, and the mass concentration of the nano diamond seed crystals in the suspension is 1-5%;
the process of growing boron doped diamond layer on the etched surface of the substrate by hot filament chemical vapor deposition comprises the following steps: the mass flow ratio of the gas is as follows: methane: boron doped gas source = 100: (1-5): (0.1-2.5), the growth pressure is 2-5KPa, the growth temperature is 600-950 ℃, the number of times of growth is 1-3, and the time of single growth is 5-24h.
6. Use of a distributed boron doped diamond/metal matrix composite according to any one of claims 1 to 3, wherein: the distributed boron-doped diamond/metal matrix composite is applied to one of the fields of electrochemical synthesis, electrochemical sewage purification treatment, electrochemical detection and electrochemical biological sensors.
7. Use of a distributed boron doped diamond/metal matrix composite according to any one of claims 1 to 3, wherein: the distributed boron-doped diamond/metal matrix composite is applied to electrochemical resource regeneration and recycling, wherein the distributed boron-doped diamond/metal matrix composite is used as an anode, at least one of permanganate, persulfate, hypochlorite, ozone and hydrogen peroxide is regenerated in the resources of the anode, at least one of gold, silver, aluminum, zinc, copper, chromium, nickel and palladium is recovered in the cathode, and an ion exchange membrane is arranged between the cathode and the anode.
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| 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 |
| CN111676462A (en) * | 2020-05-11 | 2020-09-18 | 中南大学 | High-specific-surface-area patterned boron-doped diamond electrode and preparation method and application thereof |
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| JP5971521B2 (en) * | 2012-08-23 | 2016-08-17 | 住友電気工業株式会社 | Metal manufacturing method |
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| CN1815672A (en) * | 2005-02-05 | 2006-08-09 | 三星Sdi株式会社 | Plasma display device and method producing same |
| CN104233216A (en) * | 2014-10-09 | 2014-12-24 | 南京航空航天大学 | Preparation method of titanium-based boron-doped diamond electrode provided with nano-structure array on surface |
| CN106637111A (en) * | 2016-10-21 | 2017-05-10 | 中南大学 | Niobium-base boron doped diamond foam electrode and preparing method and application thereof |
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