CN107299324A - Spinelle/metal matrix composite materials and preparation method thereof - Google Patents

Spinelle/metal matrix composite materials and preparation method thereof Download PDF

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CN107299324A
CN107299324A CN201710426057.1A CN201710426057A CN107299324A CN 107299324 A CN107299324 A CN 107299324A CN 201710426057 A CN201710426057 A CN 201710426057A CN 107299324 A CN107299324 A CN 107299324A
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spinelle
composite materials
matrix composite
mncu
metal matrix
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赖永彪
郭平义
张宇
孙杭
郭云霞
邵勇
乔岩欣
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Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5853—Oxidation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention discloses a kind of spinelle/metal matrix composite materials and preparation method thereof, is that under inert gas shielding, MnCu alloy electrode materials are deposited on into metallic substrate surface with high energy differential of the arc alloying technology, and Cu is obtained after high-temperature oxydationyMn3‑yO4High temperature corrosion-resistant conductive coating, Cu concentration is controlled in 33at.% 47at.% in MnCu alloys, metallic matrix is ferritic stainless steel coating layer thickness in below 50um, even compact, it can be firmly combined with selected metal base, electric conductivity is strong and with excellent high-temperature oxidation resistance, can effectively prevent the external diffusion of Cr elements in metal base.

Description

Spinelle/metal matrix composite materials and preparation method thereof
Technical field
It is particularly to a kind of the present invention relates to SOFC metal connector surface protection coating By the alloy electrode material obtained by alloy melting, there is high temperature corrosion-resistant conductive with what high energy differential of the arc combination technique was prepared CuyMn3-yO4Spinelle coating.
Background technology
SOFC (Solid Oxide Fuel Cell, abbreviation SOFC) has that fuel tolerance is wide, energy Measure high conversion efficiency, all solid state, modularization assembling, no pollution the advantages of, can directly use hydrogen, carbon monoxide, natural gas, A variety of hydrocarbon fuels such as liquefied gas, coal gas and biogas.The application of SOFC is quite extensive, almost Cover all traditional electricity markets, including residence with, commercially use, industrial and government utility power plant etc., even Compact power, portable power source, electricity consumption and high quality power supply etc. from far-off regions, are alternatively arranged as ship power power supply, vehicular traffic The portable power sources such as electrical source of power.System and Miniature Power Unit market are wherein electrically incorporated with the commercial power source of static, industrial heat More have an optimistic view of.
With the development of SOFC technologies, SOFC operating temperature drops to 650 DEG C -800 DEG C from 1000 DEG C so that use metal Material substitution tradition perovskite ceramics manufacture connector is possibly realized.Compared with ceramic material, metal material has high electronics The advantages of electrical conductivity and thermal conductivity, low cost, easy processing and high mechanical strength, receive significant attention.Temperature is operated in intermediate temperature SOFC In the range of degree, metal material is still faced with high-temperature oxydation problem.Only surface forms Al2O3、SiO2Or Cr2O3The alloy of oxide-film Just possesses resistance to high temperature oxidation requirement.However, due to Al2O3And SiO2Electrical conductivity it is too low, therefore Al2O3And SiO2Film formation alloy is not Metallic interconnection materials are suitable as, Cr is only formed2O3The alloy of oxide-film is most expected as SOFC connection Body material.Using ferritic stainless steel metal base as SOFC connector materials be at present one of best selection, its possess compared with Good corrosion resistance, the thermal coefficient of expansion of matching and low cost and other advantages.But because during SOFC works, Cr is aoxidized The Cr formed afterwards2O3Or Cr2(OH)2It is diffused into negative electrode as a vapor and causes the existing picture of the poisoning of cathode, so that shortens SOFC service life.
In order to improve SOFC service life, selection deposits one layer on SOFC metal connector surface Protective coating, the coating can improve metal connector antioxygenic property can prevent Cr from volatilizing again.In recent years, it can be applied to SOFC Metal connector coating material is widely studied, and current coating material is broadly divided into following four classes material：Active element is aoxidized Thing, RE perovskite oxide, MAlCrYO High-temperature resistant alloy materials and high temperature corrosion-resistant conductive spinelle.The height for studying more Warm corrosion-resistant conductive spinelle coating has high electron conductivity and low ionic conductance, with adjacent fuel cell component phase Near thermal coefficient of expansion and chemical compatibility.
The content of the invention
In order to improve the high-temperature oxidation resistance of solid oxidized fuel cell metal connecting material and prevent chromaking under high temperature Thing volatilizees triggered poisoning of cathode phenomenon, it is an object of the invention to provide a kind of spinelle/stainless steel composite material, can be with Make up the shortcomings of metal connecting material high-temperature oxidation resistance is not enough.Wherein, CuyMn3-yO4The calorifics of spinel strucutre oxides and Electric property is excellent, and its electrical conductivity is about 100-200Scm at 800 DEG C-1, with the thermal expansion system close with metal alloy Number.In addition CuyMn3-yO4Spinelle has special crystal structure so that its 200 DEG C~1600 DEG C stability inferiors compared with Good, high-temperature oxidation resistance preferably, is suitably applied metal connector coating for surface protection, can reach raising solid oxidized fuel electricity The high-temperature oxidation resistance of pond metal connecting material and the dual purpose for preventing chromium compounds from volatilizing, with good application prospect.
It is another object of the present invention to provide a kind of high temperature corrosion-resistant conductive CuyMn3-yO4Spinelle/stainless steel composite wood The preparation method of material, first passes through vacuum Alloy melting technology and melts out MnCu alloy electrode materials, then with high energy differential of the arc alloy Technology is deposited onto metallic substrate surface, and Cu is obtained after high-temperature oxydationyMn3-yO4High temperature corrosion-resistant conductive coating.
In order to realize foregoing invention purpose, present invention employs following technical scheme：
High temperature corrosion-resistant conductive CuyMn3-yO4Spinelle/stainless steel composite material, is to be deposited on MnCu alloy electrode materials Metallic substrate surface, obtains Cu after high-temperature oxydationyMn3-yO4High temperature corrosion-resistant conductive coating.Coating layer thickness is 20~30um, uniform to cause Close, electric conductivity is strong and with excellent high-temperature oxidation resistance, can effectively prevent the volatilization of chromium compounds under high temperature.
Cu concentration is controlled in 33at.%-47at.% in MnCu alloys.
The metallic matrix is ferritic stainless steel, such as 430SS, 439SS, 436SS.
High temperature corrosion-resistant conductive CuyMn3-yO4The preparation method of spinelle/stainless steel composite material, including following four step：
Step one, metallic substrate surface is pre-processed：By metal base after polishing, cleaning, dry, sealing preserve；
Step 2, melting MnCu alloy materials：Mn is placed on material room bottom, and Cu is on upper strata；Diffusion pump electric furnace electrified regulation 1~ 2 hours, vacuum was 8~12Pa；After within vacuum 2Pa, heater switch is opened.
Step 3, will obtain MnCu alloys progress wire cutting processing, sand paper polishing and obtains cylinder alloy electrode material after melting Material；
Step 4, is deposited onto what is anticipated by obtained alloy electrode material using high energy differential of the arc alloy technology On metal base, high temperature pre-oxidation is then carried out, Cu is obtainedyMn3-yO4Composite coating, after oxidation gained coating layer thickness be 20~ 50um。
Alloy electrode deposition when parameter be：Voltage 176-208V, 1400~1600HZ of frequency, power 1200~ 1600W；50~60V of voltage, 1900~2100HZ of frequency, 300~400W of power (coating surface repairing ginsengs are adjusted after deposition Number), it is therefore an objective to carrying out repairing to gained coating surface makes its smooth.Whole deposition process is in order to prevent electrode material heavy Instantaneous oxidation during product process, is continually fed into argon gas as protective gas, 15~20L/min of flow.Prepared coating layer thickness In below 50um.
The high temperature pre-oxidation atmosphere and temperature field are oxidizing atmosphere, 750 DEG C~850 DEG C, oxidization time is 5~ 20h。
Beneficial effect:(1) alloy electrode material densification is deposited on Metal Substrate using high energy differential of the arc alloying technology technology On material, due to CuyMn3-yO4Composite coating has the thermal coefficient of expansion and chemical compatibility that match with metal connector, through high temperature Coating is firmly combined with metallic matrix after oxidation；(2) prepare coating layer thickness be 20~30um, with high electrical conductance and compared with Good high-temperature oxidation resistance, the poisoning of cathode phenomenon that can effectively prevent Cr elements from being triggered from matrix external diffusion.(3) using high Energy differential of the arc alloying technology can realize that the large area operation of coating, technique are simple efficient, with low cost, promote solid oxidation combustion Expect that the development and commercialization of battery play an important role with aspect.
Brief description of the drawings
Fig. 1 is gained Cu in embodiment 21.4Mn1.6O4The electron microscope of spinelle coating.
Embodiment
Illustrate technical scheme below with reference to specific embodiment：
Embodiment 1
Step (1) 430SS base materials through 400#-2000# silicon carbide papers polish, then cleaned with distilled water, acetone, dry or Drying, sealing preserve.
Step (2) uses WZS-20 double-chamber vacuum induction furnace melting MnCu alloys, wherein set Cu concentration as 33at.%.Specifically cross operating process as follows：Because Mn boiling point is relatively low, in order to prevent Mn volatilization, Mn is placed on material room bottom Layer, Cu is on upper strata.Mechanical pump and cold house's valve are opened, lobe pump is opened when absolutely empty degree reaches 250Pa surely.Later on hot cell Valve, when vacuum reaches 8Pa, to diffusion pump electric furnace electrified regulation about 1 hour.Gate valve is risen to hot cell feeding (rail is in high position), Enter car, drop rail, move back car, drop gate valve, heating.Cold house's valve is closed, when vacuum is reached within 2Pa, hot cell valve is closed, and open diffusion pump angle Valve, when reaching process requirements vacuum, opens heater switch.Start FP21 programs and perform key, final stage insulation terminates preceding ten Minute, close diffusion pump angle valve.Cold house's valve is finally driven, heater switch is closed.The alloy obtained after melting is subjected to wire cutting processing, Polished by sand paper and obtain being about 10mm, a diameter of 3mm cylinder alloy electrode material.
Step (3), obtained alloy electrode material is coated in the gold anticipated using high energy differential of the arc alloying technology Belong to base material on, after under 750 DEG C of air atmospheres pre-oxidize 5h obtain CuMn2O4Composite coating.Alloy electrode is in deposition, deposition ginseng Number is：Conditioning instrumentation parameter is voltage 50V, frequency 2100HZ, work(after voltage 208V, frequency 1600HZ, power 1200W, deposition Rate 300W, the purpose is to carry out repairing to gained coating surface to make its smooth.Whole deposition process is in order to prevent electrode material Expect the instantaneous oxidation in deposition process, be continually fed into argon gas as protective gas, flow is in 15L/min.
Gained composite coating thickness is 20~30um and even compact, and at 800 DEG C, its electrical conductivity is about 100- 200Scm-1, electric conductivity is relatively strong and has excellent high-temperature oxidation resistance, can effectively prevent the volatilization of chromium compounds under high temperature.
Embodiment 2
Step (1), 439SS base materials are polished through 400#-2000# silicon carbide papers, are then cleaned, dried with distilled water, acetone Or drying, sealing preserve.Step (2), using WZS-20 double-chamber vacuum induction furnace melting MnCu alloys, wherein setting Cu's is dense Spend for 35at.%.Specifically cross operating process as follows：Because Mn boiling point is relatively low, in order to prevent Mn volatilization, Mn is placed on material room Bottom, Cu is on upper strata；Mechanical pump and cold house's valve are opened, lobe pump is opened when absolutely empty degree reaches 250Pa surely；Later on hot cell Valve, when vacuum reaches 10Pa, to diffusion pump electric furnace electrified regulation about 1.5 hours；Lock is risen to hot cell feeding (rail is in high position) Valve, enters car, drops rail, moves back car, drops gate valve, heating；Cold house's valve is closed, when vacuum is reached within 2Pa, hot cell valve is closed, and open diffusion Pump angle valve, when reaching process requirements vacuum, opens heater switch；Start FP21 programs and perform key, final stage insulation terminates Preceding ten minutes, close diffusion pump angle valve；Cold house's valve is finally driven, heater switch is closed.The alloy obtained after melting is subjected to wire cutting Processing, polishes by sand paper and obtains being about 70mm, a diameter of 3.2mm cylinder alloy electrode material.
Obtained alloy electrode material is coated in the metal anticipated by step (3) using high energy differential of the arc alloying technology On base material, after under 750 DEG C of air atmospheres pre-oxidize 20h obtain Cu1.05Mn1.95O4Composite coating.
Alloy electrode is in deposition, and optimal deposition parameter is：After voltage 208V, frequency 1400HZ, power 1600W, deposition Conditioning instrumentation parameter is voltage 60V, frequency 2100HZ, power 400W, and the purpose is to carry out repairing to gained coating surface to make it It is smooth.Whole deposition process is continually fed into argon gas conduct to prevent instantaneous oxidation of the electrode material in deposition process Protective gas, flow 20L/min.
Prepared coating layer thickness is 15~35um, and even compact, and at 800 DEG C, its electrical conductivity is about 100- 200Scm-1, electric conductivity is relatively strong and has excellent high-temperature oxidation resistance, can effectively prevent the volatilization of chromium compounds under high temperature.
Embodiment 3
Step (1) 436SS base materials through 400#-2000# silicon carbide papers polish, then cleaned with distilled water, acetone, dry or Drying, sealing preserve.
Step (2) uses WZS-20 double-chamber vacuum induction furnace melting MnCu alloys, wherein set Cu concentration as 40at.%.Specifically cross operating process as follows：Because Mn boiling point is relatively low, in order to prevent Mn volatilization, Mn is placed on material room bottom Layer, Cu is on upper strata；Mechanical pump and cold house's valve are opened, lobe pump is opened when absolutely empty degree reaches 250Pa surely；Later on hot cell Valve, when vacuum reaches 12Pa, to diffusion pump electric furnace electrified regulation about 2 hours；Gate valve is risen to hot cell feeding (rail is in high position), Enter car, drop rail, move back car, drop gate valve, heating；Cold house's valve is closed, when vacuum is reached within 2Pa, hot cell valve is closed, and open diffusion pump angle Valve, when reaching process requirements vacuum, opens heater switch；Start FP21 programs and perform key, final stage insulation terminates preceding ten Minute, close diffusion pump angle valve；Cold house's valve is finally driven, heater switch is closed.Alloy will be obtained after melting and carries out wire cutting processing, warp Cross the cylinder alloy electrode material that sand paper polishing obtains being about 50mm, a diameter of 2.5mm.
Obtained alloy electrode material is coated in the metal anticipated by step (3) using high energy differential of the arc alloying technology On base material, after under 800 DEG C of air atmospheres pre-oxidize 10h obtain Cu1.2Mn1.8O4Composite coating.Alloy electrode is selected in deposition Optimal deposition parameter is：Conditioning instrumentation parameter is voltage 55V, frequency after voltage 200V, frequency 1600HZ, power 1200W, deposition 2000HZ, power 350W, the purpose is to carry out repairing to gained coating surface to make its smooth.Whole deposition process is in order to anti- Only instantaneous oxidation of the electrode material in deposition process, is continually fed into argon gas as protective gas, flow is in 20L/min.
Prepared coating layer thickness is 20~35um, and even compact, and at 800 DEG C, its electrical conductivity is about 100- 200Scm-1, electric conductivity is relatively strong and has excellent high-temperature oxidation resistance, can effectively prevent the volatilization of chromium compounds under high temperature.
Embodiment 4
Step (1), 430SS base materials are polished through 400#-2000# silicon carbide papers, are then cleaned, dried with distilled water, acetone Or drying, sealing preserve.
Step (2), using WZS-20 double-chamber vacuum induction furnace melting MnCu alloys, wherein set Cu concentration as 43at.%.Specifically cross operating process as follows：Because Mn boiling point is relatively low, in order to prevent Mn volatilization, Mn is placed on material room bottom Layer, Cu is on upper strata；Mechanical pump and cold house's valve are opened, lobe pump is opened when absolutely empty degree reaches 250Pa surely；Later on hot cell Valve, when vacuum reaches 10Pa, to diffusion pump electric furnace electrified regulation about 1.5 hours；Lock is risen to hot cell feeding (rail is in high position) Valve, enters car, drops rail, moves back car, drops gate valve, heating；Cold house's valve is closed, when vacuum is reached within 2Pa, hot cell valve is closed, and open diffusion Pump angle valve, when reaching process requirements vacuum, opens heater switch；Start FP21 programs and perform key, final stage insulation terminates Preceding ten minutes, close diffusion pump angle valve；Cold house's valve is finally driven, heater switch is closed.The alloy obtained after melting is subjected to wire cutting Processing, polishes by sand paper and obtains being about 40mm, a diameter of 3mm cylinder alloy electrode material.
Step (3), obtained alloy electrode material is coated in the gold anticipated using high energy differential of the arc alloying technology Belong to base material on, after under 800 DEG C of air atmospheres pre-oxidize 20h obtain Cu1.3Mn1.7O4Composite coating.
Alloy electrode is in deposition, and selected optimal deposition parameter is：Voltage 190V, frequency 1600HZ, power 1600W, sink Conditioning instrumentation parameter is voltage 60V, frequency 1900HZ, power 400W after product, and the purpose is to gained coating surface is repaired Make its smooth.Whole deposition process is continually fed into argon gas to prevent instantaneous oxidation of the electrode material in deposition process It is used as protective gas, flow 18L/min.
Prepared coating layer thickness is 30~40um, and even compact, and at 800 DEG C, its electrical conductivity is about 150- 225Scm-1, electric conductivity is relatively strong and has excellent high-temperature oxidation resistance, can effectively prevent the volatilization of chromium compounds under high temperature.
Embodiment 5
Step (1), 439SS base materials are polished through 400#-2000# silicon carbide papers, are then cleaned, dried with distilled water, acetone Or drying, sealing preserve.
Step (2) uses WZS-20 double-chamber vacuum induction furnace melting MnCu, alloy wherein set Cu concentration as 47at.%.Specifically cross operating process as follows：Because Mn boiling point is relatively low, in order to prevent Mn volatilization, Mn is placed on material room bottom Layer, Cu is on upper strata；Mechanical pump and cold house's valve are opened, lobe pump is opened when absolutely empty degree reaches 250Pa surely；Later on hot cell Valve, when vacuum reaches 12Pa, to diffusion pump electric furnace electrified regulation about 1.5 hours；Lock is risen to hot cell feeding (rail is in high position) Valve, enters car, drops rail, moves back car, drops gate valve, heating；Cold house's valve is closed, when vacuum is reached within 2Pa, hot cell valve is closed, and open diffusion Pump angle valve, when reaching process requirements vacuum, opens heater switch；Start FP21 programs and perform key, final stage insulation terminates Preceding ten minutes, close diffusion pump angle valve；Cold house's valve is finally driven, heater switch is closed.The alloy obtained after melting is subjected to wire cutting Processing, polishes by sand paper and obtains being about 30mm, a diameter of 2.8mm cylinder alloy electrode material.
Step (3), obtained alloy electrode material is coated in the gold anticipated using high energy differential of the arc alloying technology Belong to base material on, after under 850 DEG C of air atmospheres aoxidize 5h obtain Cu1.4Mn1.6O4Composite coating.
Alloy electrode is in deposition, and selected optimal deposition parameter is：Voltage 176V, frequency 1500HZ, power 1200W, sink Conditioning instrumentation parameter is voltage 50V, frequency 2100HZ, power 300W after product, and the purpose is to gained coating surface is repaired Make its smooth.Whole deposition process is continually fed into argon gas to prevent instantaneous oxidation of the electrode material in deposition process It is used as protective gas, flow 20L/min.
Prepared coating layer thickness is 35~45um, and even compact, and at 800 DEG C, its electrical conductivity is about 150- 225Scm-1, electric conductivity is relatively strong and has excellent high-temperature oxidation resistance, can effectively prevent the volatilization of chromium compounds under high temperature.
Embodiment 1-5 technique aggregations are as shown in table 1 below：
Table 1

Claims (7)

1. spinelle/metal matrix composite materials, it is characterised in that be that MnCu alloy electrode materials are deposited on metal base table Face, obtains Cu after high-temperature oxydationyMn3-yO4High temperature corrosion-resistant conductive coating, coating layer thickness is in below 50um, even compact, electric conductivity Concentration that is strong and having Cu in excellent high-temperature oxidation resistance, MnCu alloys is controlled in 33at.%-47at.%.
2. spinelle/metal matrix composite materials described in claim 1, it is characterised in that metallic matrix is ferrite stainless Steel.
3. the preparation method of spinelle/metal matrix composite materials described in claim 1, it is characterised in that including following three Individual step：
Step one, metallic substrate surface is pre-processed：By metal base after polishing, cleaning, dry, sealing preserve；
Step 2, melting MnCu alloy materials, the concentration for obtaining Cu in MnCu alloys is controlled in 33~47at.%；After melting Obtain MnCu alloys to be cut, polished, obtain cylinder alloy electrode material；
Step 3, obtained alloy electrode material is deposited onto using the high energy differential of the arc alloy technology metal anticipated On base material, high temperature pre-oxidation is then carried out, Cu is obtainedyMn3-yO4Composite coating, after oxidation gained coating layer thickness be 20~ 50um。
4. the preparation method of spinelle/metal matrix composite materials described in claim 3, it is characterised in that Mn is placed on material Room bottom, Cu is placed on upper strata；Diffusion pump electric furnace electrified regulation 1~2 hour, vacuum is 8~12Pa；After within vacuum 2Pa, open Open heater switch.
5. the preparation method of spinelle/metal matrix composite materials described in claim 3, it is characterised in that in step 4, sinks Accumulating parameter is：176~208V of voltage, 1400~1600HZ of frequency, 1200~1600W of power；After deposition adjust voltage 50~ 60V, 1900~2100HZ of frequency, 300~400W of power；Whole deposition process is continually fed into inert gas, 15~20L/ of flow min。
6. the preparation method of spinelle/metal matrix composite materials described in claim 3, it is characterised in that high in step 4 The atmosphere of warm pre-oxidation is oxidizing atmosphere with temperature field, and 750 DEG C~850 DEG C, oxidization time is 5-20h.
7. the preparation method of spinelle/metal matrix composite materials described in claim 3, it is characterised in that in step 3, circle Post alloy electrode material a length of 30~100mm, a diameter of 2.5~3.2mm.
CN201710426057.1A 2017-06-08 2017-06-08 Spinelle/metal matrix composite materials and preparation method thereof Pending CN107299324A (en)

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Cited By (2)

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CN111593379A (en) * 2020-06-09 2020-08-28 南昌大学 Preparation of (Ni, Co, Cu) by electroplating method3O4Method for coating spinel and use thereof
CN117071014A (en) * 2023-10-12 2023-11-17 成都岷山绿氢能源有限公司 Preparation method of rare earth modified coating on surface of SOFC (solid oxide Fuel cell) metal connector

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CN101795782A (en) * 2007-08-02 2010-08-04 波士顿大学理事会 protective oxide coatings for sofc interconnections
CN103184451A (en) * 2013-03-28 2013-07-03 常州大学 Preparation technology of antioxidant and conductive spinel coating
CN104393315A (en) * 2014-10-09 2015-03-04 大连海事大学 Solid oxide fuel cell stainless steel bipolar connector and manufacturing method thereof
CN104878354A (en) * 2015-01-14 2015-09-02 东北大学 Coating for flat-plate intermediate-temperature solid oxide fuel cell metal connector

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CN111593379A (en) * 2020-06-09 2020-08-28 南昌大学 Preparation of (Ni, Co, Cu) by electroplating method3O4Method for coating spinel and use thereof
CN117071014A (en) * 2023-10-12 2023-11-17 成都岷山绿氢能源有限公司 Preparation method of rare earth modified coating on surface of SOFC (solid oxide Fuel cell) metal connector
CN117071014B (en) * 2023-10-12 2024-01-26 成都岷山绿氢能源有限公司 Preparation method of rare earth modified coating on surface of SOFC (solid oxide Fuel cell) metal connector

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Application publication date: 20171027