CN102653858B - Method for preparing MnCo spinel protecting film by magnetron sputtering and subsequent oxidation - Google Patents
Method for preparing MnCo spinel protecting film by magnetron sputtering and subsequent oxidation Download PDFInfo
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- CN102653858B CN102653858B CN201210168199XA CN201210168199A CN102653858B CN 102653858 B CN102653858 B CN 102653858B CN 201210168199X A CN201210168199X A CN 201210168199XA CN 201210168199 A CN201210168199 A CN 201210168199A CN 102653858 B CN102653858 B CN 102653858B
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Abstract
The invention provides a method for preparing a MnCo spinel protecting film by magnetron sputtering and subsequent oxidation. The method comprises the following steps of: step one, preparing a baseplate; step two, optimizing the process conditions of magnetron sputtering for preparing a Mn/Co film layer, setting background vacuum degree, heating temperature of the baseplate, glowing cleaning biasvoltage, sputtering air pressure, sputtering power and sputtering baseplate bias voltage, and sputtering the target material, wherein the sputtering baseplate bias voltage is the voltage at least changing one time from small to large, the sputtering of the target material is realized by multiple film composition treatment and a gradual adding element method, namely firstly coating a layer of Cr and then covering MnCo alloy, and the molar ratio of Mn to Co is less than 1:1; and step three, generating (Mn,Co)3O4 spinel through oxidation treatment. The method provided by the invention has the advantages that Mn/Co target materials of different proportions can be directly purchased, the traditional co-sputtering limitation is broken through, and meanwhile, the defect that the quality and the composition proportion of a film prepared by a water solution electroplating method are not easy to control is overcome; and the thickness of the film can be optimized, and the cost is reduced.
Description
Technical field
The present invention relates to prepare on the stainless steel method of coating structure, relate in particular to the method for preparing MnCo spinel protective membrane.
Background technology
The method that at present prepares the Mn/Co coating structure at stainless steel mainly contains the aqueous solution electrochemical plating such as direct current electrode position, pulse plating.Direct current electrode position refers to that the metal ion that is plated out in the plating bath is consumed in the solution gradually, deposits to matrix surface near cathode surface; Pulse plating is to make to electroplate the loop and periodically switch on and off, the electro-plating method of a certain waveform pulse that perhaps superposes again on fixing direct current; Magnetron sputtering method refers to that electronics under the effect of electric field E, bumps with ar atmo in flying to the substrate process, the Ar ion of generation accelerates to fly to cathode target under electric field action, and with high-energy bombardment target surface, target as sputter is arrived matrix surface.
The subject matter of direct current electrode position is that negative electrode and solution interface place can form thicker diffusion layer, the cathode surface concentration of metal ions is reduced produce concentration polarization, limit the speed of galvanic deposit, used large current density hydrogen embrittlement, pin hole, pit can occur, burn and foaming etc.The cost of pulse plating is higher, unsuitable large-scale commercial applications production.The method of electrochemistry plating Mn/Co is simple, but film quality and component proportions are wayward.In addition, all research does not consider that all the part Mn that matrix itself contains is diffused into film surface by the atomic diffusion effect in follow-up high-temperature oxidation process, so that rete Mn, Co mol ratio depart from initial value, and affect film performance; In addition, Initial Composition and the original depth of rete were not done optimization process yet.
Summary of the invention
In order to solve problem in the prior art, the invention provides the method that a kind of magnetron sputtering and subsequent oxidation prepare MnCo spinel protective membrane, it may further comprise the steps:
As a further improvement on the present invention, also comprise:
Under step 4, the prerequisite of Mn/Co mol ratio less than 1:1; be taken to few two kinds of different Mn/Co mol ratio experiments; and the thickness of Mn/Co rete is taken to few two kinds of different thickness; and different oxidization time; oxidated layer thickness and composition change in the middle of contrasting under the different oxidization times; time-based, thickness, composition rule are designed the protective membrane that permanent stability are good, the ASR value is low, original depth is the thinnest.
As a further improvement on the present invention; under the prerequisite of Mn/Co mol ratio less than 1:1; get three kinds of different Mn/Co mol ratio experiments; and the thickness of Mn/Co rete is got three kinds of different thickness; and three kinds of different oxidization times; oxidated layer thickness and composition change in the middle of contrasting under the different oxidization times, and time-based, thickness, composition rule are designed the protective membrane that permanent stability are good, the ASR value is low, original depth is the thinnest.
As a further improvement on the present invention, step 1 specifically comprises oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning.
As a further improvement on the present invention, base vacuum degree: 1 * 10
-4Pa to 9 * 10
-4Pa, the base plate heating temperature: 200 ℃ to 500 ℃, aura cleans bias voltage: 500V-600V, sputtering pressure: 0.3 Pa-0.7Pa, Ar air pressure, sputter substrate bias: from-200V to 0V.
As a further improvement on the present invention, sputter substrate bias is three magnitudes of voltage that change from small to large.
As a further improvement on the present invention, the Mn/Co mol ratio is got less than 40/60 or pure Co, and preferred Mn/Co mol ratio gets 40/60 or 20/80 or pure Co.
As a further improvement on the present invention, the thickness span of Mn/Co rete is: 1000nm to 4000nm.
As a further improvement on the present invention, plate first one deck Cr, Cr herein, thickness play the effect that increases bonding force less than 50nm.
As a further improvement on the present invention, described sputtering power is 270W-320W
The invention has the beneficial effects as follows: adopt present method to prepare the Mn/Co mol ratio and form the good and fine and close (Mn of bonding force less than the rete of 1:1 through subsequent oxidation, Co) 3O4 spinel structure, can be good at stoping the volatilization of Cr in the stainless steel, improve the linker electric conductivity, with the SOFC(Solid Oxide Fuel Cell) the miscellaneous part matched coefficients of thermal expansion etc., potential practical value had aspect the Solid Oxide Fuel Cell metallic interconnect.
The present invention directly buys the Mn/Co target of different ratios, breaks through the limitation of traditional cosputtering, overcomes simultaneously the uppity defective of aqueous solution electrochemical plating film quality and component proportions;
Technique of the present invention is simple, and good reproducibility can be by regulating sputtering time and process parameter control thicknesses of layers;
The present invention prepares the rete densification, adopts dynamic biasing and the gradual change of multiple film layer element to process, and stress is little between rete, and is good with the substrate associativity;
Can obtain (Mn, Co) 3O4 spinel structure by subsequent oxidation, simply controlled, the commerce of being convenient to SOFC linker film material is used;
Thicknesses of layers can be optimized, Cost reduction.
Description of drawings
Fig. 1 is existing rete SEM figure;
Fig. 2 is to be that Mn/Co=40/60, thickness are the surface topography map SEM figure of 1500nm, oxidation 250h after the present invention improves;
Fig. 3 is that Mn/Co=20/80, thickness are the XRD figure spectrum of 3000nm, oxidation 250h;
Fig. 4 is that MnCo mol ratio 40/60 of the present invention, thickness are the SEM shape appearance figure of rete cross section behind 3600nm, the oxidation 500h;
Fig. 5 is that MnCo mol ratio 40/60 of the present invention, thickness are the SEM line sweep figure of rete cross section behind 3600nm, the oxidation 500h;
Fig. 6 is that different MnCo are than the ASR test result of rete.ASR: surface resistance is the resistance of unit surface, Area Specific Resistance.
Embodiment
The present invention is further described below in conjunction with description of drawings and embodiment.
The substrate that experiment is used is SUS430, massfraction wt%:Cr 16.5, and Mn 0.6, and Si 0.5, and C 0.1, Fe bal., wt%: weight percent, bal: all the other.SUS430: be the general steel grade with good corrosion resistance nature.Consider to contain part Mn in the stainless steel, can be diffused into film surface in the follow-up test process, and document shows that the best Mn/Co spinel ratio of performance is 1:1, therefore, the target of plated film selects the Mn/Co mol ratio less than 1:1.Three kinds of 40:60,20:80 and pure Co are used respectively in experiment, observe behind the different oxidization times that Mn, Co ratio and oxidated layer thickness change in the spinel rete, find out suitable Mn/Co target and suitable rete original depth.
The experiment concrete steps are as follows:
1) prepared substrate: oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning;
2) optimize magnetron sputtering and prepare Mn/Co rete processing condition:
Base vacuum degree: 1 * 10
-4Pa to 9 * 10
-4Pa;
Base plate heating temperature: select according to actual needs, for example 300 ℃, generally between 200 ℃ to 500 ℃, select;
Aura cleans bias voltage: 500V-600V;
Sputtering pressure: 0.3Pa to 0.7Pa, for example 0.5Pa, Ar air pressure;
Sputtering power: d.c. sputtering, 270W-320W;
Sputter substrate bias: change from small to large: for example: from-150V to-100V, arrive again-60V; Also can only change once, for example: from-150V to-100V, perhaps can change more than three times, from-150V to-100V, to-60V, arrive again-30V.The span of sputter substrate bias is generally :-200 V to 0 V.
Sputtering target material: multiple film layer becomes divisional processing, gradual added elements method: the Cr-Mn/Co alloy, plated first one deck Cr exactly before plating MnCo alloy;
Sputtering time: controlling diaphragm layer thickness;
3) oxide treatment generates (Mn, Co) 3O4 spinel: for example: 800 ℃, air;
4) optimize improvement:
At present the previous work of doing is optimized improvement, structure and the performance of rete are greatly improved.SEM is the abbreviation of scanning electron microscope, and Chinese is scanning electronic microscope.Fig. 2 is that Mn/Co=40/60, thickness are the surface topography map of 1500nm, oxidation 250h, can find out the more tiny densification of rete crystal grain after the improvement, and the surface is also more smooth, can well stop the diffusion of Cr; Fig. 3 is that Mn/Co=20/80, thickness are the XRD figure spectrum of 3000nm, oxidation 250h, and (curve 2) half-breadth is tall and big after improving, and oxide grain is little, and the MnCo2O4 peak-to-peak signal is strong simultaneously, is beneficial to reduce web plate ASR value; Fig. 4 and Fig. 5 are that MnCo mol ratio 40/60, thickness are SEM shape appearance figure and the line sweep figure of rete cross section behind 3600nm, the oxidation 500h, and cross-sectional view shows after the oxidation that rete is combined finely with matrix, does not have obvious crackle, hole; The line sweep element distributes and shows; film surface spinel Mn, Co ratio are diffused into surface by the atomic diffusion effect near Mn element in the 1:1(matrix in high-temperature oxidation process; so that rete Mn/Co mol ratio becomes 50:50 by 40:60); and film surface Cr content is almost nil, illustrates that the standby protective film of this legal system can fine inhibition negative electrode Cr intoxicating phenomenon.Fig. 6 is that different MnCo are than the ASR test result of rete, tendency can estimate that the MnCo mol ratio is that the ASR of 40/60,20/80 rete behind work 40000h is about 0.096 cm2, meets the SOFC web plate ASR of U.S. solid state energy sources conversion alliance (SECA) proposition less than the requirement of 0.1 cm2 from figure.
In addition, present work also compares composition variation in thickness after rete Initial Composition thickness and the oxidation, seeks Mn, Co, Cr, Fe diffusion mechanism and intermediate oxide layer growth rhythm, for rete optimization provides gross data.
Substrate applies the bias voltage of variation, and for example :-200V is to-50V.
Apply the energy that a suitable bias voltage not only can increase incident atoms to substrate, improve sedimentation rate, can also allow the rete in the growth constantly be subject to the bombardment of argon ion, removing may enter the gas of film surface, improves rete purity, and can remove the relatively poor deposited particles of sticking power, purify the surface, improve the sticking power of rete, reduce even elimination film surface drop, reduce the film surface roughness.
Beginning applies a little bias voltage to substrate during plated film, can improve the energy of deposited particles, makes it with faster speed bombardment substrate, improves the bonding force between itself and substrate; Afterwards gradually epitaxy of rete increases substrate bias to reduce the speed of particle, and the rete of avoiding having grown is subject to the bombardment of high speed deposition particle, causes the rete reverse sputtering, increases the film surface defective; But can not be too large, cause rete compactness poor.
Before plating MnCo alloy, at stainless steel deposition one deck Cr, thickness is less than 50nm first.
Advantage: adopt gradual added elements method, reduce the interface and the mechanical property jumping phenomenon occurs.The material of two kinds of different in kinds combines and can form an interface, and interfacial property has determined the bonding strength of two kinds of materials, processes bad meeting and has thermal stresses and other power, and the film phenomenon occurs falling.Between two kinds of materials, add chromium and play tackiness agent effect (contain 16.5% Cr in the substrate, Cr and substrate and MnCo rete associativity are all fine), make substrate and rete have good bonding force.
MnCo thicknesses of layers composition is optimized:
At present all not systematizes of research: the target component difference is very large, the thicknesses of layers variation, not considering that the high temperature Elements Diffusion can be diffused into the Mn in impact, the especially substrate of rete and intermediate oxidation composition of layer affects membranous layer ingredient in the rete, and then affects film performance.
By the oxidation of three kinds of compositions, three kinds of thickness and 0 ~ 1000h, contrast under the different oxidization times in the middle of oxidated layer thickness and composition change, seek Mn, Co, Cr, Fe diffusion mechanism and intermediate oxide layer growth rhythm.Time-based, thickness, composition rule are designed optimum protective membrane (permanent stability are good, the ASR value is low, original depth is the thinnest).
Advantage:
1, solves the blindness of for a long time MnCo spinel protective membrane being studied;
2, obtain Mn, Co, Cr, Fe diffusion mechanism, for follow-up optimization design provides theoretical foundation; 3, optimize thickness, reduce the Film preparation cost;
4, with MnCo rete (composition thickness) stdn, lay the first stone for realizing as early as possible the commercialization of SOFC metallic interconnect.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that implementation of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a magnetron sputtering and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that, it may further comprise the steps:
Step 1, prepared substrate;
Step 2, optimization magnetron sputtering prepare Mn/Co rete processing condition, base vacuum degree, base plate heating temperature, aura cleaning bias voltage, sputtering pressure, sputtering power, sputter substrate bias are set, and described sputter substrate bias is the voltage that changes at least from small to large once; Sputtering target material: multiple film layer becomes divisional processing, gradual added elements method: plate first one deck Cr, plate the MnCo alloy again, the Mn/Co mol ratio is less than 1:1;
Step 3, oxide treatment generate (Mn, Co) 3O4 spinel.
2. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that, also comprise:
Step 4, be taken to few two kinds of different Mn/Co mol ratios experiments; and the thickness of Mn/Co rete is taken to few two kinds of different thickness; and different oxidization time; oxidated layer thickness and composition change in the middle of contrasting under the different oxidization times; time-based, thickness, composition rule are designed the protective membrane that permanent stability are good, the ASR value is low, original depth is the thinnest.
3. magnetron sputtering according to claim 2 and subsequent oxidation prepare the method for MnCo spinel protective membrane; it is characterized in that; under the prerequisite of Mn/Co mol ratio less than 1:1; get three kinds of different Mn/Co mol ratio experiments; and the thickness of Mn/Co rete is got three kinds of different thickness; and three kinds of different oxidization times; oxidated layer thickness and composition change in the middle of contrasting under the different oxidization times; time-based, thickness, composition rule are designed the protective membrane that permanent stability are good, the ASR value is low, original depth is the thinnest.
4. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that: step 1 specifically comprises oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning.
5. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that: base vacuum degree: 1 * 10
-4Pa to 9 * 10
-4Pa, the base plate heating temperature: 200 ℃ to 500 ℃, aura cleans bias voltage: 500V-600V, sputtering pressure: 0.3 Pa-0.7Pa, Ar air pressure, sputter substrate bias: from-200V to 0V.
6. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that: the sputter substrate bias is three magnitudes of voltage that change from small to large.
7. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that: the Mn/Co mol ratio is got less than 40/60 or pure Co.
8. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that: the thickness span of Mn/Co rete is: 1000nm to 4000nm.
9. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that: plate first one deck Cr, and Cr herein, thickness is less than 50nm.
10. magnetron sputtering according to claim 1 and subsequent oxidation prepare the method for MnCo spinel protective membrane, it is characterized in that: described sputtering power is 270W-320W.
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| CN103103592B (en) * | 2013-01-22 | 2015-07-22 | 昆明理工大学 | A method for preparing (Mn, co)3O4spinel coating |
| CN103695902B (en) * | 2013-12-02 | 2016-02-24 | 常州大学 | A kind of preparation method of rare earth modified spinel coating |
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| CN105239050B (en) * | 2015-11-12 | 2018-09-07 | 哈尔滨工业大学 | A kind of preparation method of solid oxide fuel cell stainless steel connector spinel oxide protective coating |
| CN106571476B (en) * | 2016-11-14 | 2020-08-25 | 江苏科技大学 | Coating material for high-temperature fuel cell metal connector and preparation method thereof |
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| CN110184570B (en) * | 2019-06-04 | 2021-11-23 | 哈尔滨工业大学（深圳） | Preparation method of solid oxide fuel cell connector protective film |
| CN112018417A (en) * | 2020-07-16 | 2020-12-01 | 哈尔滨工业大学（深圳） | Method for preparing electrolyte layer or electrolyte barrier layer of solid oxide fuel cell |
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