CN103695902B - A kind of preparation method of rare earth modified spinel coating - Google Patents
A kind of preparation method of rare earth modified spinel coating Download PDFInfo
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Abstract
The invention belongs to metal surface modification field, refer in particular to a kind of preparation method of rare earth modified spinel coating.Concrete preparation process is as follows: by cobalt powder, manganese dioxide powder, lanthanum oxide powder mixes in proportion, hot pressing sintering method is adopted to make electrode materials, then adopt high energy differential of the arc alloying under protection of inert gas by deposit electrode material to stainless steel surface, prepare cobalt-based compound oxide coating, this coated material has good electroconductibility, coating is placed in further air or oxygen environment and heats preoxidation, the oxide coating of cobalt-manganese spinel and cobalt acid lanthanum compound can be prepared, cobalt-manganese spinel prepared by this technique and cobalt acid lanthanium complex oxide coating system, there is good high-temperature oxidation resistant and conductivity, overcome in the past spinel coating/metal interface in conjunction with insecure, coating density is low, the problem of thermal expansion coefficient difference, ferritic stainless steel linker surface oxidation-resistant can be met, the requirements such as conduction and anti-Cr volatilization.
Description
Technical field
The present invention relates to metal surface modification field, especially metal connector surface protection technique in SOFC, refer in particular to a kind of preparation method of rare earth modified spinel coating.
Background technology
Recent research finds, had the dielectric film of hyperoxia ionic conductivity by the thickness or employing reducing dielectric film, the service temperature of Solid Oxide Fuel Cell (SOFC) can be made to be down to 600-800 ° of C, and this makes metal become possibility as metallic interconnect materials.
At present in intermediate temperature solid oxide fuel cell, because ferritic stainless steel linker exists anti-oxidant deficiency in SOFC long service process, chromium volatilizees, the problems such as negative electrode poisons, stack performance is finally caused sharply to decline, this problem hinders Solid Oxide Fuel Cell commercial operation to a great extent, therefore the Functional Requirement of ferritic stainless steel metallic interconnect materials effects on surface coating is more harsh, not only need the thermal expansivity that coating has good high temperature oxidation resistance and mates with matrix phase, and require the face specific impedance that coating keeps lower in long service process, and can effectively stop negative electrode to poison.
In view of Co/Mn spinel all wants the good impact of performance in oxidation-resistance and suppression Cr volatilization, researchist takes first to obtain Co-Mn coating, carry out the Co-Mn spinel coating that thermooxidizing obtains heat growth again, this coating has good anti-Cr volatilization and conductivity, but the compactness of coating and to be improved with the bonding state of matrix, the Co-Mn coating of heat growth is often difficult to the test of bearing long-term stability in simulated SOFC environment, occurs peeling sometimes.
Summary of the invention
The technical problem to be solved in the present invention is:
(1) solve that spinel coating/metal interface is low in conjunction with insecure, easy stripping, coating density, the problem of thermal expansion coefficient difference; (2) high-quality Co-Mn spinel and LaCoO is provided
3composite oxide coating, ensures that coating has good high-temperature oxidation resistant and conductivity.
For solving the problems of the technologies described above the technical solution used in the present invention be: a kind of preparation technology of rare earth modified spinel coating, concrete steps are as follows:
(1) preparation of deposition of electrode material
Hot pressing sintering method is adopted to make Co+MnO
2+ La
2o
3depositing electrode: each group of raw material is mixed by a certain percentage, with mould under high pressure press forming, high temperature sintering obtains the depositing electrode of conduction;
(2) preparation of compound coating
Adopt high energy micro arc depositing device, by depositing electrode prepared by step (1), as the negative electrode in deposition process, to polish and the stainless steel cleaned up as body material, under protection of inert gas, carry out electric spark deposition in metallic surface, namely generate one deck compound coating;
(3) preoxidation of compound coating
Compound coating prepared by step (2) is heated preoxidation in air atmosphere, Co-Mn spinel+LaCoO can be formed on composite bed surface
3composite oxide coating.
Co metal-powder, MnO described in step (1)
2powder, La
2o
3powder mixes by a certain percentage and refers to: La
2o
3content is 23.59wt% ~ 50.23wt%, Co powder content is 36.24wt% ~ 51.28wt.%, MnO
2content is 13.41wt% ~ 27.59wt%.
Press forming in step (1) refers to: pressure is 4 ~ 5MPa, and the dwell time is 30-60s.
High temperature sintering condition described in step (1) is vacuum, and vacuum tightness is-0.1MPa, and sintering temperature is 1200 ° of C-1400 ° of C, and the time is 2h-4h.
The polishing of the metal matrix material described in step (2) is through 400-1200 by metal
#sand paper polish step by step, described cleaning in acetone soln ultrasonic oil removing clean up, dry.
Rare gas element described in step (2) is argon gas, and flow is 5-30L/min.
Electric spark deposition technique described in step (2) is one-way communication power supply for depositing power supply, and deposition voltage is 40-80V, and frequency is 400-600Hz, pulsewidth is 200-400 μ s, power is 300-3000W, and the speed of rotation of electrode is 1000r/min-4500r/min, and depositing time is 2-20min.
Pre oxidation described in step (3) is 600-800 ° of C; Oxidization time is 4-10h.
The invention has the beneficial effects as follows: the preparation technology that the invention provides a kind of rare earth modified spinel coating, probed into the modifying function of rare earth element to spinel coating, solve spinel coating deficiency in actual applications; The present invention has widened the range of application of electric spark deposition technology, develop new way prepared by cobalt-manganese spinel coating, meet the requirements such as ferritic stainless steel linker surface oxidation-resistant, conduction and anti-Cr volatilization, because the preparation method of this coating adopts high energy differential of the arc alloying means at metallic surface elder generation's metal refining compound coating and then carries out pre-oxidation treatment, prepare compound coating.This process also just determines, coating binding force this problem insecure can be solved, because the coating interface of deposition is metallurgical binding is that this technology decides, solve spinel coating/metal interface in conjunction with insecure, coating density is low, the problem of thermal expansion coefficient difference, improves coating high-temp solidity to corrosion and electroconductibility.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of coating in atmosphere after preoxidation, can find out that coating is Co-Mn spinel and LaCoO
3composite oxide coating.
specific embodiments:
The test button of preparation selected by coating can adopt size to be: long × wide × high: 10mm × 10mm × 2mm.
Be deposited test button preprocessing process: stainless steel sheet specimens is used 400-1200 respectively
#sand paper polish step by step, sample put into the oil removing of acetone soln ultrasonic wave added cleaning 3-5min, then use deionized water rinsing, dry up for subsequent use.
Embodiment 1:
1): the preparation process of rotating and depositing electrode: take Co metal-powder (purity is greater than 99.9wt.%) 0.83g, MnO
2powder (purity: be greater than 99.9wt.%) 0.31g, La
2o
3powder 1.15g, obtains electrode slice by hot pressing sintering method after mixing, and pressure is 4MPa, and the dwell time is 60s, and sintering condition is vacuum, and vacuum tightness is-0.1MPa, sintering temperature 1200 ° of C, time 4h.
2): the preparation process of rare earth modified spinel coating: adopt high energy differential of the arc alloying equipment, in the stainless steel specimen surface deposition that surface treatment is good, choose suitable processing parameter, depositing device adopts one-way communication power supply, deposition voltage is 40V, frequency is 400Hz, pulsewidth is 400 μ s, power is 300W, pass to the argon gas of 5L/min as shielding gas, depositing electrode keeps the rotating speed that 1000r/min is fixing, deposition 20min can be deposited metallic surface and preparing the settled layer of one deck densification, deposit thickness is approximately 60 μm, by the sample prepared, put into tube furnace and can obtain rare earth modified Co-Mn spinel+LaCoO at 600 ° of C oxidation 10h in atmosphere
3composite oxide coating, XRD figure spectrum is with embodiment 2.
Embodiment 2:
1): the preparation process of rotating and depositing electrode: take Co metal-powder (purity is greater than 99.9wt.%) 0.83g, MnO
2powder (purity: be greater than 99.9wt.%) 0.31g, La
2o
3powder 1.15g, obtains electrode slice by hot pressing sintering method after mixing, and pressure is 5MPa, and the dwell time is 30s, and sintering condition is vacuum, and vacuum tightness is-0.1MPa, sintering temperature 1400 ° of C, time 2h.
2): the preparation process of rare earth modified spinel coating: adopt high energy differential of the arc alloying equipment, in the stainless steel specimen surface deposition that surface treatment is good, choose suitable processing parameter, depositing device adopts one-way communication power supply, deposition voltage is 80V, frequency is 600Hz, pulsewidth is 200 μ s, power is 3000W, pass to the argon gas of 10L/min as shielding gas, depositing electrode keeps the rotating speed that 4500r/min is fixing, deposition 2min can be deposited metallic surface and preparing the settled layer of one deck densification, deposit thickness is approximately 70 μm, by the sample prepared, put into tube furnace and can obtain rare earth modified Co-Mn spinel+LaCoO at 700 ° of C oxidation 8h in atmosphere
3composite oxide coating.
3) embodiment 3:
1): the preparation process of rotating and depositing electrode: take Co metal-powder (purity is greater than 99.9wt.%) 1.21g, MnO
2powder (purity: be greater than 99.9wt.%) 0.59g, La
2o
3powder 0.56g, obtains electrode slice by hot pressing sintering method after mixing, and pressure is 4MPa, and the dwell time is 60s, and sintering condition is vacuum, and vacuum tightness is-0.1MPa, sintering temperature 1200 ° of C, time 4h.
2): the preparation process of rare earth modified spinel coating: adopt high energy differential of the arc alloying equipment, in the stainless steel specimen surface deposition that surface treatment is good, choose suitable processing parameter, depositing device adopts one-way communication power supply, deposition voltage is 60V, frequency is 400Hz, pulsewidth is 400 μ s, power is 1500W, pass to the argon gas of 10L/min as shielding gas, depositing electrode keeps the rotating speed that 3000r/min is fixing, deposition 8min can be deposited metallic surface and preparing the settled layer of one deck densification, deposit thickness is approximately 60 μm, by the sample prepared, put into tube furnace and can obtain rare earth modified Co-Mn spinel+LaCoO at 600 ° of C oxidation 10h in atmosphere
3composite oxide coating, XRD figure spectrum is with embodiment 2.
Embodiment 4:
1): the preparation process of rotating and depositing electrode: take Co metal-powder (purity is greater than 99.9wt.%) 1.21g, MnO
2powder (purity: be greater than 99.9wt.%) 0.59g, La
2o
3powder 0.56g, obtains electrode slice by hot pressing sintering method after mixing, and pressure is 5MPa, and the dwell time is 30s, and sintering condition is vacuum, and vacuum tightness is-0.1MPa, sintering temperature 1400 ° of C, time 2h.
2): the preparation process of rare earth modified spinel coating: adopt high energy differential of the arc alloying equipment, in the stainless steel specimen surface deposition that surface treatment is good, choose suitable processing parameter, depositing device adopts one-way communication power supply, deposition voltage is 80V, frequency is 400Hz, pulsewidth is 400 μ s, power is 2000W, pass to the argon gas of 30L/min as shielding gas, depositing electrode keeps the rotating speed that 4500r/min is fixing, deposition 10min can be deposited metallic surface and preparing the settled layer of one deck densification, deposit thickness is approximately 80 μm, by the sample prepared, put into tube furnace and can obtain rare earth modified Co-Mn spinel+LaCoO at 800 ° of C oxidation 4h in atmosphere
3composite oxide coating, XRD figure spectrum is with embodiment 2.
Embodiment 5:
1): the preparation process of rotating and depositing electrode: take Co metal-powder (purity is greater than 99.9wt.%) 1.08g, MnO
2powder (purity: be greater than 99.9wt.%) 0.64g, La
2o
3powder 0.60g, obtains electrode slice by hot pressing sintering method after mixing, and pressure is 5MPa, and the dwell time is 30s, and sintering condition is vacuum, and vacuum tightness is-0.1MPa, sintering temperature 1300 ° of C, time 3h.
2): the preparation process of rare earth modified spinel coating: adopt high energy differential of the arc alloying equipment, in the stainless steel specimen surface deposition that surface treatment is good, choose suitable processing parameter, depositing device adopts one-way communication power supply, deposition voltage is 60V, frequency is 400Hz, pulsewidth is 400 μ s, power is 1500W, pass to the argon gas of 10L/min as shielding gas, depositing electrode keeps the rotating speed that 4500r/min is fixing, deposition 12min can be deposited metallic surface and preparing the settled layer of one deck densification, deposit thickness is approximately 70 μm, by the sample prepared, put into tube furnace and can obtain rare earth modified Co-Mn spinel+LaCoO at 700 ° of C oxidation 8h in atmosphere
3composite oxide coating, XRD figure spectrum is with embodiment 2.
Embodiment 6:
1): the preparation process of rotating and depositing electrode: take Co metal-powder (purity is greater than 99.9wt.%) 1.08g, MnO
2powder (purity: be greater than 99.9wt.%) 0.64g, La
2o
3powder 0.60g, obtains electrode slice by hot pressing sintering method after mixing, and pressure is 4MPa, and the dwell time is 60s, and sintering condition is vacuum, and vacuum tightness is-0.1MPa, sintering temperature 1400 ° of C, time 2h.
2): the preparation process of rare earth modified spinel coating: adopt high energy differential of the arc alloying equipment, in the stainless steel specimen surface deposition that surface treatment is good, choose suitable processing parameter, depositing device adopts one-way communication power supply, deposition voltage is 80V, frequency is 400Hz, pulsewidth is 400 μ s, power is 2000W, pass to the argon gas of 30L/min as shielding gas, depositing electrode keeps the rotating speed that 4500r/min is fixing, deposition 9min can be deposited metallic surface and preparing the settled layer of one deck densification, deposit thickness is approximately 80 μm, by the sample prepared, put into tube furnace and can obtain rare earth modified Co-Mn spinel+LaCoO at 500 ° of C oxidation 9h in atmosphere
3composite oxide coating, XRD figure spectrum is with embodiment 2.
Claims (7)
1. a preparation method for rare earth modified spinel coating, is characterized in that comprising the steps:
(1) preparation of deposition of electrode material
Hot pressing sintering method is adopted to make Co+MnO
2+ La
2o
3depositing electrode: by Co metal-powder, MnO
2powder and La
2o
3powder mixes by a certain percentage, and with mould under high pressure press forming, high temperature sintering obtains the depositing electrode of conduction;
(2) preparation of compound coating
Adopt high energy micro arc depositing device, by depositing electrode prepared by step (1), as the negative electrode in deposition process, to polish and the stainless steel cleaned up as body material, under protection of inert gas, carry out electric spark deposition in metallic surface, namely generate one deck compound coating;
(3) preoxidation of compound coating
Compound coating prepared by step (2) is heated preoxidation in air atmosphere, Co-Mn spinel+LaCoO can be formed on composite bed surface
3composite oxide coating; Described in step (1) by Co metal-powder, MnO
2powder, La
2o
3powder mixes by a certain percentage and refers to: La
2o
3content is 23.59wt% ~ 50.23wt%, Co powder content is 36.24wt% ~ 51.28wt%, MnO
2content is 13.41wt% ~ 27.59wt%.
2. the preparation method of a kind of rare earth modified spinel coating as claimed in claim 1, it is characterized in that: the press forming in step (1) refers to: pressure is 4 ~ 5MPa, the dwell time is 30-60s.
3. the preparation method of a kind of rare earth modified spinel coating as claimed in claim 1, it is characterized in that: the high temperature sintering condition described in step (1) is vacuum, vacuum tightness is-0.1MPa, and sintering temperature is 1200 DEG C-1400 DEG C, and the time is 2h-4h.
4. the preparation method of a kind of rare earth modified spinel coating as claimed in claim 1, is characterized in that: the polishing of the metal matrix material described in step (2) is through 400-1200 by metal
#sand paper polish step by step, described cleaning in acetone soln ultrasonic oil removing clean up, dry.
5. the preparation method of a kind of rare earth modified spinel coating as claimed in claim 1, it is characterized in that: the rare gas element described in step (2) is argon gas, flow is 5-30L/min.
6. the preparation method of a kind of rare earth modified spinel coating as claimed in claim 1, it is characterized in that: the electric spark deposition technique described in step (2) is one-way communication power supply for depositing power supply, deposition voltage is 40-80V, frequency is 400-600Hz, pulsewidth is 200-400 μ s, power is 300-3000W, and the speed of rotation of electrode is 1000r/min-4500r/min, and depositing time is 2-20min.
7. the preparation method of a kind of rare earth modified spinel coating as claimed in claim 1, is characterized in that: the Pre oxidation described in step (3) is 600-800 DEG C; Oxidization time is 4-10h.
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| CN106835206B (en) * | 2017-01-03 | 2018-10-02 | 北京科技大学 | A kind of preparation method and application of Lanthanum Chromite base inert anode |
| CN109321785B (en) * | 2018-12-12 | 2021-03-23 | 常州大学 | Method for preparing cobalt-based coating on surface of cobalt-based alloy |
| CN111690926B (en) * | 2020-06-24 | 2022-01-18 | 哈尔滨工业大学 | Method for preparing compact Mn-Co spinel protective layer of stainless steel connector by hot-pressing sintering method |
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| CN101670999A (en) * | 2009-09-27 | 2010-03-17 | 中国科学院上海硅酸盐研究所 | Mn-Co-doped spinel composite nanometer material and low-temperature sintering method thereof |
| CN102653858A (en) * | 2012-05-28 | 2012-09-05 | 哈尔滨工业大学深圳研究生院 | Method for preparing MnCo spinel protecting film by magnetron sputtering and subsequent oxidation |
| CN103184402A (en) * | 2013-03-28 | 2013-07-03 | 常州大学 | Preparation method for rare-earth modified metal ceramic coating |
| CN103184451A (en) * | 2013-03-28 | 2013-07-03 | 常州大学 | Preparation technology of antioxidant and conductive spinel coating |
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| JPH05271852A (en) * | 1992-03-30 | 1993-10-19 | Sumitomo Metal Ind Ltd | Production of rare earth magnet alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101670999A (en) * | 2009-09-27 | 2010-03-17 | 中国科学院上海硅酸盐研究所 | Mn-Co-doped spinel composite nanometer material and low-temperature sintering method thereof |
| CN102653858A (en) * | 2012-05-28 | 2012-09-05 | 哈尔滨工业大学深圳研究生院 | Method for preparing MnCo spinel protecting film by magnetron sputtering and subsequent oxidation |
| CN103184402A (en) * | 2013-03-28 | 2013-07-03 | 常州大学 | Preparation method for rare-earth modified metal ceramic coating |
| CN103184451A (en) * | 2013-03-28 | 2013-07-03 | 常州大学 | Preparation technology of antioxidant and conductive spinel coating |
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