CN112301402A - Novel magnesium alloy thermal barrier coating and preparation method thereof - Google Patents
Novel magnesium alloy thermal barrier coating and preparation method thereof Download PDFInfo
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- CN112301402A CN112301402A CN202011201622.2A CN202011201622A CN112301402A CN 112301402 A CN112301402 A CN 112301402A CN 202011201622 A CN202011201622 A CN 202011201622A CN 112301402 A CN112301402 A CN 112301402A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Abstract
The invention discloses a novel magnesium alloy thermal barrier coating and a preparation method thereof, wherein a layer of micro-arc oxidation layer with a loose and porous upper layer and a compact lower layer is generated in situ on a magnesium alloy matrix to serve as a bonding layer, and then an 8YSZ ceramic layer surface layer is prepared on the bonding layer by adopting an atmospheric plasma spraying technology, so that a brand-new YSZ/PEO/Mg thermal barrier coating system is prepared. The micro-arc oxidation layer and the substrate are metallurgically bonded, the bonding strength is high, and meanwhile, the micro-arc oxidation layer structure with loose and porous upper layer improves the contact area with the surface layer YSZ and forms a structure that YSZ is embedded into the upper layer of the micro-arc oxidation layer, so that the bonding strength between the surface layer and the bonding layer is improved. The method has the advantages of simple process flow, environmental protection and high automation degree, and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the field of surface modification of metal materials, and particularly relates to a novel magnesium alloy thermal barrier coating and a preparation method thereof.
Background
The magnesium alloy has abundant content in nature, the density of magnesium is the lowest in all structural metals, and meanwhile, the magnesium alloy has good specific strength, specific rigidity and good shock absorption and noise resistance, so the magnesium alloy has very wide application in the fields of aviation, aerospace, traffic and electronics. However, magnesium alloys have significantly limited applications due to their low melting point, active chemistry, poor heat resistance and poor corrosion resistance. Magnesium alloy is easy to react with humid air or water to produce MgO or Mg (OH) at normal temperature2Thereby, corrosion occurs. At high temperature, the magnesium alloy is easy to generate oxidation reaction to generate an MgO film, the PBR value of the MgO film is 0.81, so that larger tensile stress exists in the film, and the oxide film is not protective, thereby limiting the use of the magnesium alloy at high temperature.
Applying a thermal barrier coating can significantly improve the above problems. The thermal barrier coating is a heat-insulating functional coating, and a material with low thermal conductivity and higher melting point is usually coated on the surface of a metal substrate to form a barrier between a high-temperature medium and the metal substrate, so that the heat is prevented from being transmitted to the metal substrate, the temperature of the metal surface is reduced, and the function of protecting the substrate is achieved. The traditional thermal barrier coating is composed of MCrAlY (M ═ Ni, Co) bonding layer and Y2O3Partially stabilized ZrO2Ceramic coating (YSZ).
After the traditional thermal barrier coating is prepared on the surface of the magnesium alloy, the MCrAlY bonding layer and the magnesium alloy substrate are mainly combined mechanically, the bonding strength between the bonding layer and the substrate is low, the temperature of spraying flame flow of the atmospheric plasma spraying technology is high, and the activity of the magnesium alloy is active, so that the oxidation is easily generated on the interface of the bonding layer and the substrate, a loose magnesium oxide with high brittleness is formed, the bonding strength of the thermal barrier coating is obviously reduced, and the thermal barrier coating and the substrate fall off.
Therefore, the invention researches and develops a novel magnesium alloy thermal barrier coating structure system, a micro-arc oxidation layer is generated in situ on a magnesium alloy substrate to serve as a bonding layer, and meanwhile, after atmospheric plasma spraying of a surface layer YSZ, no oxidation area is generated on the interface between the substrate and the bonding layer, so that the bonding strength between the coating and the substrate is improved.
Disclosure of Invention
The invention aims to provide a novel magnesium alloy thermal barrier coating and a preparation method thereof, wherein the linear expansion coefficient of a micro-arc oxidation layer is between that of a magnesium alloy substrate and that of a surface layer ceramic layer, so that the preparation of the micro-arc oxidation layer effectively relieves the problem of coating falling caused by mismatching of thermal stress and the linear expansion coefficient between YSZ and Mg, and meanwhile, the micro-arc oxidation layer and the substrate are metallurgically bonded, so that the bonding strength between the substrate and a bonding layer is improved.
The technical scheme of the invention is as follows:
the novel magnesium alloy thermal barrier coating consists of a bonding layer and an 8YSZ ceramic surface layer, wherein the bonding layer is a magnesium alloy micro-arc oxidation layer.
The preferred scheme of the novel magnesium alloy thermal barrier coating is that the thickness of the bonding layer is 20-30 um, and the thickness of the 8YSZ ceramic surface layer is 90-110 um.
The preferable scheme of the novel magnesium alloy thermal barrier coating is that the magnesium alloy comprises the following components in percentage by weight: 14% of Gd, 2.3% of Zn, 1% of Zr and the balance of Mg.
A preparation method of a novel magnesium alloy thermal barrier coating comprises the following steps:
the method comprises the following steps: carrying out surface treatment on the magnesium alloy matrix to remove dirt on the surface of the magnesium alloy;
step two: carrying out micro-arc oxidation treatment on the magnesium alloy matrix so as to generate a micro-arc oxidation layer in situ on the magnesium alloy matrix as a bonding layer;
step three: after micro-arc oxidation is finished, washing the magnesium alloy with deionized water and drying;
step four: and after the sample is cleaned in the third step, carrying out sand blasting treatment on the magnesium alloy micro-arc oxidation layer, and then preparing the 8YSZ ceramic surface layer by adopting an atmosphere plasma spraying technology.
In the preparation method, the first step is specifically as follows: cutting a magnesium alloy sample with the size of 25mm multiplied by 12mm multiplied by 8mm by a linear cutting machine, polishing six surfaces of the sample by No. 400 abrasive paper, then cleaning the sample in an ultrasonic cleaner by absolute ethyl alcohol for 5-10 min, and drying the sample by a hair dryer to obtain the magnesium alloy after surface treatment.
In the preparation method, the second step is specifically as follows: the electrolyte for carrying out micro-arc oxidation treatment on the magnesium alloy is alkali silicate, the components of the electrolyte comprise sodium hydroxide, sodium silicate and potassium fluoride, and the concentrations of the three compounds are respectively as follows: 2g/L, 20g/L and 5g/L, and the solvent is water; in a constant current mode, wherein the current density is 2A/dm2The frequency is 1000Hz, the duty ratio is 50 percent, and the duration time of the oxidation process is 15 min; in the micro-arc oxidation process, the voltage gradually increases along with the increase of the thickness of the film layer, the voltage is controlled not to exceed the forward voltage of a power supply by 450V, and the temperature of the electrolyte is controlled at 20-40 ℃.
In the preparation method, the fourth step is specifically: after the sample is cleaned, carrying out sand blasting treatment on the micro-arc oxide layer by adopting 60-mesh white corundum sand, wherein the parameters of an atmospheric plasma spraying 8YSZ ceramic surface layer are as follows: spray current 900A, argon flow 80SLPM, helium flow 50SLPM, spray distance 80 mm.
Compared with the prior art, the method and the novel magnesium alloy thermal barrier coating structure system prepared by the method have the following advantages:
(1) the micro-arc oxidation layer consists of an outer MgO layer and an inner MgSiO layer3The linear expansion coefficients of the magnesium alloy substrate and the ceramic surface layer are between those of the magnesium alloy substrate and the ceramic surface layer, so that the preparation of the micro-arc oxidation layer effectively relieves the problem of coating peeling caused by mismatching of thermal stress and the linear expansion coefficient between YSZ and Mg;
(2) the micro-arc oxidation layer is generated in situ on the magnesium alloy substrate, and no potential difference exists between the coating and the substrate, so that electrochemical corrosion cannot occur;
(3) the micro-arc oxidation layer and the substrate are metallurgically bonded, so that the bonding strength between the substrate and the bonding layer is improved;
(4) the micro-arc oxidation layer is a loose and porous upper layer and a compact lower layer, and the loose and porous upper layer can improve the contact area with the ceramic layer surface layer, so that an embedded structure is formed, and the binding force between the micro-arc oxidation layer and the ceramic layer surface layer is improved. Meanwhile, the compact structure of the lower layer can also block the transmission of oxygen to the matrix, and the oxidation resistance of the matrix is improved.
Drawings
FIG. 1 is an SEM surface topography for YSZ/PEO/Mg as prepared;
FIG. 2 is a SEM cross-sectional profile of YSZ/PEO/Mg as prepared;
FIG. 3 is a SEM cross-sectional profile of YSZ/PEO/Mg as prepared;
Detailed Description
The present invention is further described in the following examples, which are intended to be illustrative of the best mode of carrying out the invention and are not intended to limit the scope of the invention in any way.
In this embodiment, the preparation method of the novel magnesium alloy thermal barrier coating system is as follows:
(1) cutting a magnesium alloy sample with the size of 25mm multiplied by 12mm multiplied by 8mm by a linear cutting machine, polishing six surfaces of the sample by No. 400 abrasive paper, then cleaning the sample in an ultrasonic cleaner by absolute ethyl alcohol for 5-10 min, and drying the sample by a hair dryer to obtain the magnesium alloy after surface treatment;
(2) the magnesium alloy is subjected to micro-arc oxidation treatment, the electrolyte is alkali silicate, the components of the electrolyte comprise sodium hydroxide, sodium silicate and potassium fluoride, and the concentrations of the three compounds are respectively as follows: 2g/L, 20g/L and 5g/L, and the solvent is water. Adopting a constant current mode, the current density is 2A/dm2The frequency is 1000Hz, the duty ratio is 50 percent, and the duration of the whole oxidation process is 15 min. In the micro-arc oxidation process, the voltage is gradually increased along with the increase of the thickness of the film layer, the control voltage is not required to exceed the forward voltage of a power supply by 450V, the temperature of the electrolyte is controlled to be 20-40 ℃, and therefore a 20-30 um micro-arc oxidation layer is generated in situ on the magnesium alloy substrate to serve as a bonding layer;
(3) after micro-arc oxidation is finished, washing the magnesium alloy with deionized water and drying;
(4) after the sample is cleaned, carrying out sand blasting treatment on the micro-arc oxide layer by adopting 60-mesh white corundum sand, wherein the atmospheric plasma spraying 8YSZ parameters are as follows: spraying current 900A, argon gas flow 80SLPM, helium gas flow 50SLPM, and spraying distance 80mm, thereby preparing a 90-110 um surface layer 8YSZ ceramic layer;
the sample prepared in example 1 was subjected to SEM surface morphology observation, and the result is shown in FIG. 1. At this time, the sample surface is formed of droplet-like ZrO2The particle composition, and the apparent microcrack and hole exist in the surface, this is because in the process of adopting atmospheric plasma spraying, 8YSZ ceramic powder is melted by plasma flame stream and forms the liquid droplet form, is sprayed to the lower magnesium alloy matrix surface of temperature fast afterwards, along with the pile-up of subsequent 8YSZ pottery, the liquid droplet solidifies rapidly when meeting the cold and forms the liquid droplet form surface, and 8YSZ ceramic powder in the cooling process, for releasing the internal thermal stress of coating and producing the microcrack and hole, the sample surface coating combines better, the sign that the coating drops off and peels off does not appear.
FIG. 2 is an SEM cross-sectional profile of YSZ/PEO/Mg as prepared. As can be seen from FIG. 2, the average thickness of the micro-arc oxidation layer is 25um, and the average thickness of the YSZ ceramic layer of the surface layer is 92 um. The micro-arc oxidation layer and the substrate are well combined, the loose porous structure on the upper layer of the micro-arc oxidation layer increases the contact area with the YSZ, and the structure that the YSZ is embedded into the micro-arc oxidation layer is formed, so that the bonding strength between the micro-arc oxidation layer and the surface layer is effectively improved, the design purpose is achieved, and meanwhile, no obvious defect exists at two groups of interfaces.
FIG. 3 is an SEM cross-sectional profile of YSZ/PEO/Mg as prepared. The section morphology graph shows that when the sample of the micro-arc oxidation bonding layer is in a preparation state, the bonding layer is well combined with the matrix and the ceramic layer interface, and no obvious falling and separation tendency exists.
Claims (9)
1. The novel magnesium alloy thermal barrier coating is characterized by consisting of a bonding layer and an 8YSZ ceramic surface layer, wherein the bonding layer is a magnesium alloy micro-arc oxidation layer.
2. The novel magnesium alloy thermal barrier coating of claim 1, wherein the bond coat is 20-30 um thick and the 8YSZ ceramic topcoat is 90-110 um thick.
3. The novel magnesium alloy thermal barrier coating of claim 1 wherein the magnesium alloy composition comprises, in weight percent: 14% of Gd, 2.3% of Zn, 1% of Zr and the balance of Mg.
4. A preparation method of a novel magnesium alloy thermal barrier coating is characterized by comprising the following steps:
the method comprises the following steps: performing surface treatment on the magnesium alloy matrix to remove dirt on the surface of the magnesium alloy matrix;
step two: carrying out micro-arc oxidation treatment on the magnesium alloy matrix so as to generate a micro-arc oxidation layer in situ on the magnesium alloy matrix as a bonding layer;
step three: after micro-arc oxidation is finished, washing the magnesium alloy with deionized water and drying;
step four: and after the sample is cleaned in the third step, carrying out sand blasting treatment on the magnesium alloy micro-arc oxidation layer, and then preparing the 8YSZ ceramic surface layer by adopting an atmosphere plasma spraying technology.
5. The preparation method of the novel magnesium alloy thermal barrier coating as claimed in claim 4, wherein the first step is specifically: cutting a magnesium alloy sample with the size of 25mm multiplied by 12mm multiplied by 8mm by a linear cutting machine, polishing six surfaces of the sample by No. 400 abrasive paper, then cleaning the sample in an ultrasonic cleaner by absolute ethyl alcohol for 5-10 min, and drying the sample by a hair dryer to obtain the magnesium alloy after surface treatment.
6. The method for preparing the novel magnesium alloy thermal barrier coating according to claim 4, wherein in the second step, the magnesium alloy substrate is subjected to micro-arc oxidation treatment by using alkali silicate as an electrolyte; in a constant current mode, wherein the current density is 2A/dm2The frequency is 1000Hz, the duty ratio is 50 percent, and the duration time of the oxidation process is 15 min; in the micro-arc oxidation process, the voltage is gradually increased along with the increase of the thickness of the film layer, the voltage is controlled not to exceed the forward voltage of a power supply of 450V, and the temperature of the electrolyte is controlled to be 20～40℃。
7. The preparation method of the novel magnesium alloy thermal barrier coating according to claim 6, wherein the electrolyte comprises 2g/L of sodium hydroxide, 20g/L of sodium silicate and 5g/L of potassium fluoride, and the solvent is water.
8. The method for preparing a novel magnesium alloy thermal barrier coating according to claim 4, wherein the sand blasting in the fourth step is to perform sand blasting on a magnesium alloy micro-arc oxidation layer by using 60-mesh white corundum sand.
9. The preparation method of the novel magnesium alloy thermal barrier coating according to claim 4, wherein the parameters of the 8YSZ ceramic surface layer sprayed by the medium-atmosphere plasma in the fourth step are as follows: spray current 900A, argon flow 80SLPM, helium flow 50SLPM, spray distance 80 mm.
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| WO2004095532A2 (en) * | 2003-03-31 | 2004-11-04 | Tokyo Electron Limited | A barrier layer for a processing element and a method of forming the same |
| KR100798415B1 (en) * | 2006-09-27 | 2008-01-28 | 알마티(주) | Method of manufacturing protective layer of electrostatic chuck by coating hybrid ceramic |
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