CN103184451B - A kind of preparation technology of anti-oxidant conductive spinel coating - Google Patents
A kind of preparation technology of anti-oxidant conductive spinel coating Download PDFInfo
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Abstract
The present invention relates to metal surface modification field, a kind of preparation technology of anti-oxidant conductive spinel coating is provided, step is as follows: carry out melting after Co metal-powder and Mn metal-powder being mixed, and is then annealed by melted CoMn alloy, cleans up as deposition of electrode material for subsequent use; By the depositing electrode of preparation, as the negative electrode in deposition process, metal, as body material, under protection of inert gas, carries out electric spark deposition in metallic surface, namely generates one deck CoMn alloy coat; The CoMn alloy coat of preparation is heated preoxidation in air atmosphere, CoMn spinel coating can be formed at CoMn alloyed layer.The present invention accurately can control alloy atom ratio, the electro-conductive material of electrode is molten infilters surface of workpiece, and form alloy layer, the coating prepared and matrix have the feature of metallurgical binding, bonding force is strong, and this coating formation Spinel can meet the protection needs of SOFC metal connector.
Description
Technical field
The present invention relates to metal surface modification field, especially metal connector surface protection technique in SOFC.
Background technology
The metallic interconnect materials of traditional Solid Oxide Fuel Cell (SOFC) generally selects Lanthanum Chromite as metallic interconnect materials, but its complicated process of preparation, and expensive, limit the commercial applications of SOFC.Along with the development of temperatureization in SOFC, metal becomes possibility as metallic interconnect materials.But, the selection of a particular job environment to metallic substance of SOFC is applied with strict restriction, because there is the problem such as anti-oxidant deficiency and chromium volatilization in metal connector in long service process, finally cause stack performance sharply to decline, this problem hinders Solid Oxide Fuel Cell commercial operation to a great extent.
In order to solve this key issue, simple, easy method applies high temperature corrosion-resistant conductive coating on metal connector surface.Researchist finds that the applicability of (Mn, Co) spinel oxide covering in SOFC is best, is also one of studied spinels coating system the most deep for this reason so far.Current preparation (Mn, Co)
3o
4spinel coating is generally by acquisitions such as colloidal sol slurry process, plasma spraying method, sol-gel method and electro-plating methods.Sol-gel method is generally difficult to the relation solving coat-thickness and cracking, wherein the spinel layer prepared of plated metal (alloy) coating postheat treatment is better to matrix coverage effect, but due to Co and Mn sedimentation potential difference comparatively large, be often difficult to the codeposition realizing CoMn alloy layer.So researchist utilizes a point pond electric plating method, be deposited on stainless steel base by continuous print metal Co and Mn layer and Ni metal and Mn, obtain CoMn spinel after thermooxidizing, this layer reduces Cr
2o
3the growth velocity of internal layer and surface film ASR value.But this experimental technique is difficult to the codeposition realizing CoMn, and this method is not easy the thickness controlling each element successive layers, be difficult at alloy layer the accurate control realizing Co/Mn ratio, also just accurately cannot control coating and change into CoMn spinel completely after thermooxidizing.
Summary of the invention
The technical problem to be solved in the present invention is: overcome metallic coating in prior art and be difficult to realize the accurate control of atomic ratio and coating and be combined deficiency loosely with matrix, provide a kind of preparation technology of anti-oxidant conductive spinel coating.
For solving the problems of the technologies described above the technical solution used in the present invention be: a kind of preparation technology of anti-oxidant conductive spinel coating, concrete steps are as follows:
(1) preparation of deposition of electrode material
Through row melting after adopting non-consumable arc melting technology Co metal-powder and Mn metal-powder to be mixed, then melted CoMn alloy is annealed, be then made into bar-shaped, clean up as deposition of electrode material for subsequent use;
(2) preparation of alloy coat
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 metal cleaned up as body material, under protection of inert gas, carry out electric spark deposition in metallic surface, namely generate one deck CoMn alloy coat;
(3) preoxidation of alloy coat
CoMn alloy coat prepared by step (2) is heated preoxidation in air atmosphere, CoMn spinel coating can be formed at CoMn alloyed layer.
The cleaning of the depositing electrode described in step (1) is that ultrasonic wave added oil removing cleans up in acetone soln, dries; 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.
Co metal-powder described in step (1) and the purity of Mn metal-powder > 99.9wt.%, both can to mix with arbitrary proportion as required.
CoMn alloy annealing conditions described in step (1) is vacuum annealing temperature is 900-1100 ° of C, and the time is 40-60h.
Rare gas element described in step (2) is argon gas, and flow is 5-30L/min.
The diameter of the depositing electrode described in step (1) is 2 ~ 4mm; 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: first the technology of preparing of cobalt-manganese spinel coating provided by the invention needs to smelt the CoMn alloy of required setting proportional components; using CoMn alloy as electrode, use electric spark deposition technology under the atmosphere of argon shield at metal material surface in-situ preparation cobalt manganese alloy layer.By controlling the amount of cobalt metal in smelting process and manganese metal, and smelting the ingot metal that through sufficient homogenizing annealing, accurately can control the Co:Mn atomic ratio in alloy layer.In the preparation process of protective coating provided by the invention, can by the CoMn alloy layer regulating the processing parameters such as electrode materials diameter, deposition voltage, deposition current, speed of rotation, depositing time to obtain different thickness.The present invention has widened the range of application of electric spark deposition technology, develop new way prepared by cobalt-manganese spinel coating, the electro-conductive material of electrode is molten infilters surface of workpiece, form alloy layer, the coating prepared and matrix have the feature of metallurgical binding, bonding force is strong, and effectively can reduce the Cr of matrix stainless steel surface after this coating formation Spinel
2o
3generating rate, stop the volatilization of Cr, meet the protection needs of SOFC metal connector.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 settled layer.
Specific embodiments:
The test button of preparation selected by coating can adopt size to be: the wide * of long * is high: 10*10*2mm.
Embodiment 1:
1): the preparation process of rotating and depositing electrode: take Co metal (purity is greater than 99.9wt.%) 25.88g and manganese metal (purity: be greater than 99.9wt.%) 24.12g, the ingot metal of 50g is smelted into after mixing, then ingot metal is put into tube furnace and carry out vacuum annealing, annealing temperature is 900 ° of C, time is 60h, make alloy interior tissue homogenization of composition, the Co:Mn atomic ratio of alloy is 1:1.Be made into the pole that diameter is approximately 4mm again, in acetone soln, ultrasonic wave added oil removing cleaning 3-5min, then uses deionized water rinsing, dries up for subsequent use.
2): be deposited test button preprocessing process: stainless steel sheet specimens is used 400-1200 respectively
#sand paper polish step by step, sample is put into the oil removing of acetone soln ultrasonic wave added cleaning 3 ~ 5min, then use deionized water rinsing, dry up for subsequent use.
3): the preparation process of CoMn spinel coating: adopt electric spark deposition equipment; select CoMn alloy bar as depositing electrode; choose suitable processing parameter; depositing device adopts one-way communication power supply; deposition voltage is 40V; frequency is 400Hz; pulsewidth is 400 μ s; pass to the argon gas of 5L/min as shielding gas; depositing electrode keeps the rotating speed that 4500r/min is fixing; deposit about 2min and can be deposited metallic surface and prepare the settled layer of one deck densification, deposit thickness is approximately 60 μm, and the Co:Mn atomic ratio in settled layer is approximately 1:1.By the test button prepared, put into tube furnace and can obtain the CoMn spinel protective coating of certain content, as Fig. 1 at 600 ° of C oxidation 10h in atmosphere: the XRD figure spectrum of embodiment 1 settled layer.
Embodiment 2:
1): the preparation process of rotating and depositing electrode: take Co metal (purity is greater than 99.9wt.%) 40.55g and manganese metal (purity: be greater than 99.9wt.%) 9.45g, smelt after mixing, then the ingot metal of smelting is put into tube furnace and carry out vacuum annealing, annealing temperature is 1100 ° of C, time is 40h, make alloy interior tissue homogenization of composition, the Co:Mn atomic ratio of alloy is 4:1.Be made into the pole that diameter is approximately 2mm again, in acetone soln, ultrasonic wave added oil removing cleaning 3-5min, then uses deionized water rinsing, dries up for subsequent use.
2): be deposited test button preprocessing process: stainless steel sheet specimens is used 400-1200 respectively
#sand paper polish step by step, sample is put into the oil removing of acetone soln ultrasonic wave added cleaning 3 ~ 5min, then use deionized water rinsing, dry up for subsequent use.
3): the preparation process of CoMn spinel coating: adopt electric spark deposition equipment; select CoMn alloy bar as depositing electrode; choose suitable processing parameter; depositing device adopts one-way communication power supply; deposition voltage is 60V; frequency is 400Hz; pulsewidth is 200 μ s; pass to the argon gas of 30L/min as shielding gas; depositing electrode keeps the rotating speed that 1000r/min is fixing; deposit about 4min and can be deposited metallic surface and prepare the settled layer of one deck densification, deposit thickness is approximately 60 μm, and the Co:Mn atomic ratio in settled layer is approximately 4:1.By the test button prepared, put into tube furnace and can obtain CoMn spinel protective coating at 800 ° of C oxidation 4h in atmosphere.
Embodiment 3:
1): the preparation process of rotating and depositing electrode: take Co metal (purity is greater than 99.9wt.%) 25.88g and manganese metal (purity: be greater than 99.9wt.%) 24.12g, smelt after mixing, then the ingot metal of smelting is put into tube furnace and carry out vacuum annealing, annealing temperature is 1100 ° of C, time is 60h, make alloy interior tissue homogenization of composition, the Co:Mn atomic ratio of alloy is 1:1.Be made into the pole that diameter is approximately 2mm again, in acetone soln, ultrasonic wave added oil removing cleaning 3-5min, then uses deionized water rinsing, dries up for subsequent use.
2): be deposited test button preprocessing process: stainless steel sheet specimens is used 400-1200 respectively
#sand paper polish step by step, sample is put into the oil removing of acetone soln ultrasonic wave added cleaning 3 ~ 5min, then use deionized water rinsing, dry up for subsequent use.
3): the preparation process of CoMn spinel coating: adopt electric spark deposition equipment; select CoMn alloy bar as depositing electrode; choose suitable processing parameter; depositing device adopts one-way communication power supply; deposition voltage is 80V; frequency is 400Hz; pulsewidth is 200 μ s; pass to the argon gas of 10L/min as shielding gas; depositing electrode keeps the rotating speed that 3000r/min is fixing; deposit about 4min and can be deposited metallic surface and prepare the settled layer of one deck densification, deposit thickness is approximately 80 μm, and the Co:Mn atomic ratio in settled layer is approximately 1:1.By the test button prepared, putting into tube furnace in atmosphere can at the protective coating obtaining certain C oMn spinel at 800 ° of C oxidation 10h.
Embodiment 4:
1): the preparation process of rotating and depositing electrode: take Co metal (purity is greater than 99.9wt.%) 25.88g and manganese metal (purity: be greater than 99.9wt.%) 24.12g, smelt after mixing, then the ingot metal of smelting is put into tube furnace and carry out vacuum annealing, annealing temperature is 1100 ° of C, time is 60h, make alloy interior tissue homogenization of composition, the Co:Mn atomic ratio of alloy is 1:1.Be made into the pole that diameter is approximately 2mm again, in acetone soln, ultrasonic wave added oil removing cleaning 3-5min, then uses deionized water rinsing, dries up for subsequent use.
2): be deposited test button preprocessing process: stainless steel sheet specimens is used 400-1200 respectively
#sand paper polish step by step, sample is put into the oil removing of acetone soln ultrasonic wave added cleaning 3 ~ 5min, then use deionized water rinsing, dry up for subsequent use.
3): the preparation process of CoMn spinel coating: adopt electric spark deposition equipment; select CoMn alloy bar as depositing electrode; choose suitable processing parameter; depositing device adopts one-way communication power supply; deposition voltage is 60V; frequency is 600Hz; pulsewidth is 200 μ s; pass to the argon gas of 10L/min as shielding gas; depositing electrode keeps the rotating speed that 3000r/min is fixing; deposit about 4min and can be deposited metallic surface and prepare the settled layer of one deck densification, deposit thickness is approximately 90 μm, and the Co:Mn atomic ratio in settled layer is approximately 1:1.By the test button prepared, put into tube furnace and can obtain certain C oMn spinel protective coating at 800 ° of C oxidation 10h in atmosphere.
Embodiment 5:
1): the preparation process of rotating and depositing electrode: take Co metal (purity is greater than 99.9wt.%) 25.88g and manganese metal (purity: be greater than 99.9wt.%) 24.12g, smelt after mixing, then the ingot metal of smelting is put into tube furnace and carry out vacuum annealing, annealing temperature is 1100 ° of C, time is 60h, make alloy interior tissue homogenization of composition, the Co:Mn atomic ratio of alloy is 1:1.Be made into the pole that diameter is approximately 2mm again, in acetone soln, ultrasonic wave added oil removing cleaning 3-5min, then uses deionized water rinsing, dries up for subsequent use.
2): be deposited test button preprocessing process: stainless steel sheet specimens is used 400-1200 respectively
#sand paper polish step by step, sample is put into the oil removing of acetone soln ultrasonic wave added cleaning 3 ~ 5min, then use deionized water rinsing, dry up for subsequent use.
3): the preparation process of CoMn spinel coating: adopt electric spark deposition equipment; select CoMn alloy bar as depositing electrode; choose suitable processing parameter; depositing device adopts one-way communication power supply; deposition voltage is 60V; frequency is 400Hz; pulsewidth is 200 μ s; pass to the argon gas of 10L/min as shielding gas; depositing electrode keeps the rotating speed that 3000r/min is fixing; deposit about 20min and can be deposited metallic surface and prepare the settled layer of one deck densification, deposit thickness is approximately 150 μm, and the Co:Mn atomic ratio in settled layer is approximately 1:1.By the test button prepared, put into tube furnace and can obtain certain C oMn spinel protective coating at 800oC oxidation 10h in atmosphere.
Embodiment 6:
1): the preparation process of rotating and depositing electrode: take Co metal-powder (purity is greater than 99.9wt.%) 25.88g and manganese metal-powder (purity: be greater than 99.9wt.%) 24.12g, smelt after mixing, then the ingot metal of smelting is put into tube furnace and carry out vacuum annealing, annealing temperature is 1100 ° of C, time is 60h, make alloy interior tissue homogenization of composition, the Co:Mn atomic ratio of alloy is 1:1.Be made into the pole that diameter is approximately 2mm again, in acetone soln, ultrasonic wave added oil removing cleaning 3-5min, then uses deionized water rinsing, dries up for subsequent use.
2): be deposited test button preprocessing process: stainless steel sheet specimens is used 400-1200 respectively
#sand paper polish step by step, sample is put into the oil removing of acetone soln ultrasonic wave added cleaning 3 ~ 5min, then use deionized water rinsing, dry up for subsequent use.
3): the preparation process of CoMn spinel coating: adopt electric spark deposition equipment; select CoMn alloy bar as depositing electrode; choose suitable processing parameter; depositing device adopts one-way communication power supply; deposition voltage is 60V; frequency is 400Hz; pulsewidth is 200 μ s; pass to the argon gas of 10L/min as shielding gas; depositing electrode keeps the rotating speed that 1000r/min is fixing; deposit about 4min and can be deposited metallic surface and prepare the settled layer of one deck densification, deposit thickness is approximately 20 μm, and the Co:Mn atomic ratio in settled layer is approximately 1:1.By the test button prepared, put into tube furnace and can obtain the CoMn spinel protective coating of certain content at 800 ° of C oxidation 10h in atmosphere.
Claims (5)
1. a preparation technology for anti-oxidant conductive spinel coating, is characterized in that: step is as follows,
(1) preparation of deposition of electrode material
Through row melting after adopting non-consumable arc melting technology Co metal-powder and Mn metal-powder to be mixed, then melted CoMn alloy is annealed, be then made into bar-shaped, clean up as deposition of electrode material for subsequent use;
(2) high energy micro arc depositing device is adopted; by depositing electrode prepared by step (1); as the negative electrode in deposition process; to polish and the metal cleaned up as body material; under protection of inert gas; carry out electric spark deposition in metallic surface, namely generate one deck CoMn alloy coat
Described depositing device adopts one-way communication power supply, deposition voltage is 40V or 60V, frequency is 400Hz, pulsewidth is 400 μ s or 200 μ s, pass to the argon gas of 5L/min or 30L/min as shielding gas, depositing electrode keeps the fixing rotating speed of 4500r/min or 1000r/min, deposition 2min or 4min;
(3) preoxidation of alloy coat
CoMn alloy coat prepared by step (2) is heated preoxidation in air atmosphere, CoMn spinel coating can be formed at CoMn alloyed layer.
2. the preparation technology of anti-oxidant conductive spinel coating according to claim 1, is characterized in that: the cleaning of the depositing electrode described in step (1) is that ultrasonic wave added oil removing cleans up in acetone soln, dries; The polishing of the metal matrix material described in step (2) is polished step by step by the sand paper of metal through 400-1200#, and described cleaning is that ultrasonic oil removing cleans up in acetone soln, dries.
3. the preparation technology of anti-oxidant conductive spinel coating according to claim 1, it is characterized in that: the Co metal-powder described in step (1) and the purity of Mn metal-powder > 99.9wt.%, both atomic ratios are 1:1.
4. the preparation technology of anti-oxidant conductive spinel coating according to claim 1, is characterized in that: the CoMn alloy annealing conditions described in step (1) is vacuum annealing temperature is 900-1100 DEG C, and the time is 40-60h.
5. the preparation technology of anti-oxidant conductive spinel coating according to 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422090B (en) * | 2013-07-26 | 2016-08-10 | 江苏科技大学 | High temperature corrosion-resistant conductive ceramic coating material for SOFC metal connector and preparation method thereof |
| CN103695902B (en) * | 2013-12-02 | 2016-02-24 | 常州大学 | A kind of preparation method of rare earth modified spinel coating |
| CN104694930B (en) * | 2015-03-20 | 2017-03-08 | 哈尔滨工业大学 | A kind of electric spark deposition is combined the method preparing thermal barrier coating with micro-arc oxidation process |
| CN105132870B (en) * | 2015-08-13 | 2018-04-13 | 江苏科技大学 | A kind of composite oxide coating with high-temperature electric conduction performance and preparation method thereof |
| CN105839155A (en) * | 2016-06-07 | 2016-08-10 | 沈阳飞机工业（集团）有限公司 | Method for preparing MnCo2O4 spinel coating by electrodeposition method |
| CN107299324A (en) * | 2017-06-08 | 2017-10-27 | 江苏科技大学 | Spinelle/metal matrix composite materials and preparation method thereof |
| CN108486567B (en) * | 2018-04-03 | 2020-01-03 | 江西省科学院应用物理研究所 | Preparation method of nano-particle reinforced wear-resistant coating for blade tip of single crystal turbine blade |
| CN109267114B (en) * | 2018-10-22 | 2020-08-21 | 中国科学院金属研究所 | Preparation method of cobalt-manganese spinel coating |
| CN114318248A (en) * | 2021-12-17 | 2022-04-12 | 国家能源集团新能源有限责任公司 | Preparation method and application of manganese-cobalt spinel coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560338A (en) * | 2010-12-09 | 2012-07-11 | 中国科学院金属研究所 | Metal ceramic coating and preparation method thereof |
| CN102925892A (en) * | 2012-11-23 | 2013-02-13 | 北京科技大学 | Electric spark deposition method for molten zinc corrosion resistant Ti-Al-Nb coating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10025108A1 (en) * | 2000-05-20 | 2001-11-29 | Forschungszentrum Juelich Gmbh | High temperature material |
| EP2276094B1 (en) * | 2008-04-24 | 2014-04-16 | Osaka Gas Co., Ltd. | Cell for solid oxide fuel battery |
-
2013
- 2013-03-28 CN CN201310106664.1A patent/CN103184451B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560338A (en) * | 2010-12-09 | 2012-07-11 | 中国科学院金属研究所 | Metal ceramic coating and preparation method thereof |
| CN102925892A (en) * | 2012-11-23 | 2013-02-13 | 北京科技大学 | Electric spark deposition method for molten zinc corrosion resistant Ti-Al-Nb coating |
Non-Patent Citations (4)
| Title |
|---|
| Advanced PVD protective coatings for SOFC interconnects;Paul Gannon, et al.;《International Journal of Hydrogen Energy》;20080219;第33卷;第3991-4000页 * |
| Effect of Mn-Co spinel coating for Fe-Cr ferritic alloys ZMG232L and 232J3 for solid oxide fuel cell interconnects on oxidation behavior and Cr-evaporation;Toshihiro Uehara, et al.;《Journal of Power Sources》;20101124;第196卷;第7251-7256页 * |
| High-temperature oxidation process analysis of MnCo2O4 coating on Fe-21Cr alloy;Yuchao Fang, et al.;《International Journal of Hydrogen Energy》;20110303;第36卷;第5611-5616页 * |
| SOFC金属连接体Mn/Co保护膜层的制备及其性能研究;王安祺;《万方数据知识服务平台》;20130320;第19页第3段至第20页第4段，第52页第3段 * |
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