CN101724301B - MCrAlY+AlSiY composite coating and preparation technique thereof - Google Patents
MCrAlY+AlSiY composite coating and preparation technique thereof Download PDFInfo
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- CN101724301B CN101724301B CN2008102280976A CN200810228097A CN101724301B CN 101724301 B CN101724301 B CN 101724301B CN 2008102280976 A CN2008102280976 A CN 2008102280976A CN 200810228097 A CN200810228097 A CN 200810228097A CN 101724301 B CN101724301 B CN 101724301B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 8
- 239000010410 layer Substances 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 238000009826 distribution Methods 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 238000009792 diffusion process Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 238000007733 ion plating Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 239000002344 surface layer Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
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- 238000003860 storage Methods 0.000 abstract description 3
- 229910000601 superalloy Inorganic materials 0.000 abstract description 2
- 239000011253 protective coating Substances 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910000943 NiAl Inorganic materials 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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Abstract
本发明涉及高温防护涂层技术，具体地说是一种MCrAlY+AlSiY复合涂层及制备方法。在常规MCrAlY涂层上沉积AlSiY涂层，再通过真空扩散退火的方法，形成外层富Al而内层富Cr的呈梯度分布的MCrAlY复合涂层，该复合涂层表层Al元素浓度为18～22wt％，内层Cr元素浓度为28～45wt％。本发明通过电弧离子镀沉积加真空扩散退火的方法，制备外层富Al、内层富Cr的呈梯度分布的MCrAlY复合涂层。与现有的常规MCrAlY高温防护涂层相比，本发明所涉及的这种MCrAlY+AlSiY复合涂层有效地提高了涂层表层中Al存储相含量和Si的含量，并在涂层内层形成了富Cr层，从而可以提高涂层抗高温氧化、抗热腐蚀性能，并能有效地延长涂层使用寿命。该复合涂层及其制备方法可应用于Ni基高温合金的防护。The invention relates to high-temperature protective coating technology, in particular to a MCrAlY+AlSiY composite coating and a preparation method. Deposit an AlSiY coating on the conventional MCrAlY coating, and then use vacuum diffusion annealing to form a MCrAlY composite coating with a gradient distribution in which the outer layer is rich in Al and the inner layer is rich in Cr. The Al element concentration in the surface layer of the composite coating is 18~ 22wt%, and the Cr element concentration in the inner layer is 28-45wt%. The invention adopts the method of arc ion plating deposition and vacuum diffusion annealing to prepare the gradient distribution MCrAlY composite coating which is rich in Al on the outer layer and rich in Cr on the inner layer. Compared with the existing conventional MCrAlY high-temperature protective coating, the MCrAlY+AlSiY composite coating involved in the present invention effectively increases the Al storage phase content and Si content in the coating surface layer, and forms in the coating inner layer The Cr-rich layer is formed, which can improve the high temperature oxidation resistance and hot corrosion resistance of the coating, and can effectively prolong the service life of the coating. The composite coating and its preparation method can be applied to the protection of Ni-based superalloys.
Description
Technical field
The present invention relates to the high-temperature protection coating technology, specifically a kind of MCrAlY+AlSiY composite coating and preparation method.
Background technology
MCrAlY (M=Ni; Co or Ni+Co) coating obtains good effect in the protection of nickel base superalloy; And composition and thickness can be controlled on request; Therefore satisfy the requirement of different applying working condition conditions, be widely used in the high temperature protection of gas turbine blades as high-temperature protection coating and thermal barrier coating bond coating.The document of related application is like 1. Chinese invention patent, and a kind of detonation flame spraying prepares the method for thermal barrier coating, application number 01133423.1; 2. Chinese invention patent, a kind of oxidation-inhibited thermal barrier coating and preparation method, application number 02133193.6; 3. Chinese invention patent, a kind of preparation method of heat shock resistance thermal barrier coating, application number 03133344.3; 4. Chinese invention patent, a kind of NiCoCrAlYSiB corrosion and heat resistant coating and preparation method thereof, application number 03111363.X; Or the like.
Research for many years shows; In the MCrAlY coating; Cr and Al are the elements that forms protective oxide film; For high temperature alloy and high-temperature protection coating parts, the element counterdiffusion of high-temperature oxydation, corrosion and coating and matrix causes Al, Cr element by lot of consumption for a long time, thereby coating system was lost efficacy.Therefore, can prolong coating service life effectively through the content that improves Al, Cr in the MCrAlY coating.But too high Al, Cr content can cause coating fragility to increase, and fusing point reduces, and are unfavorable for the coated component periodic duty that colds and heat succeed each other.Adopt the design of gradient composite coating to address these problems well.When Cr and Al Gradient distribution, can not produce very big influence to mechanical property.In addition, the design of Gradient distribution can also improve the interface and combine, and improves stress distribution.
Summary of the invention
In order to delay the degeneration of high-temperature protection coating, prolong the service life of coating, the object of the present invention is to provide the rich Al of a kind of skin and (MCrAlY+AlSiY) composite coating of the distribution gradient of the rich Cr of internal layer and preparation method thereof.
To achieve these goals, technical scheme of the present invention is:
A kind of MCrAlY+AlSiY composite coating; Depositing Al SiY coating on conventional MCrAlY coating; Form outer rich Al and the MCrAlY composite coating of the distribution gradient of the rich Cr of internal layer, this composite coating top layer Al concentration of element is 18～22wt%, and internal layer Cr concentration of element is 28～45wt%.
The present invention is depositing Al SiY coating on the conventional MCrAlY coating of arc ion plating (AIP, i.e. ArcIonPlating) method deposition, and the method that adopts vacuum diffusion annealing immediately prepares outer rich Al and the MCrAlY composite coating of the distribution gradient of the rich Cr of internal layer.
Said conventional MCrAlY coating alloy system composition (being the target alloying component) is Co:0～40, Cr:15～40, Al:6～16, Y:0.1～1, Si:0～2, B:0.01～0.03%, Ni: surplus by mass percentage.
The concrete preparation method of said MCrAlY+AlSiY composite coating is: 1) the conventional MCrAlY coating of arc ion plating (AIP) preparation; 2) depositing Al SiY coating on conventional MCrAlY coating basis; 3) vacuum diffusion annealing finally obtains outer rich Al and the MCrAlY composite coating of the distribution gradient of the rich Cr of internal layer.When adopting arc ion plating (aip) to deposit conventional MCrAlY coating, at first the vacuum chamber vacuum is evacuated to 2 * 10 in advance
-3～1 * 10
-2Pa feeds Ar gas, makes pressure in vacuum tank rise to 5 * 10
-2～3 * 10
-1Pa; Then sample is carried out preparatory sputter bombardment and clean, target-substrate distance is 230～250mm, pulsed bias is-800～-1000V, dutycycle 20～40%, time 2～5min; Deposit the MCrAlY coating again, target-substrate distance is 230～250mm, arc voltage 20～25V, arc current 50～70A, pulsed bias be-150～-300V, dutycycle 20～40%, 300～400 ℃ of depositing temperatures, coating layer thickness are 40～60 μ m.
During depositing Al SiY coating, by mass percentage, AlSiY nominal composition (being the target alloying component) is Si:7～14%, Y:0 < Y≤2%, Al: surplus on conventional MCrAlY coating basis; The conventional MCrAlY coating of deposition process parameters synsedimentary, the AlSiY coating layer thickness of deposition is 7～15 μ m.The above-mentioned MCrAlY+AlSiY composite coating that obtains is carried out vacuum heat: vacuum diffusion annealing; During vacuum diffusion annealing; Temperature is 950～1050 ℃, temperature retention time 3～5h, 5～8 ℃/>min of heating rate; Cool to room temperature with the furnace, obtain outer rich Al and the MCrAlY composite coating of the distribution gradient of the rich Cr of internal layer.
Before the deposition, need sample is carried out preliminary treatment, the base material sample is polished to Ra=0.4 μ m, adopt 60～220 order hollow glass ball wet abrasive blastings to handle, successively adopt metal detergent, deionized water, acetone ultrasonic cleaning 15min immediately, with drying after the alcohol rinsing.
The present invention has the following advantages:
1. coating longer service life.Compare with existing conventional MCrAlY high-temperature protection coating; Owing to improved the content of Al source, coating top layer storage phase β-NiAl; In high-temperature oxidation process, can provide the Al source to support the generation and the reparation of surface layer oxide film, in the heat erosion process, can sacrifice the rich Al layer on top layer; Rely on the rich Cr layer opposing corrosion of internal layer, thereby prolong the service life of coating.
2. in the MCrAlY coating involved in the present invention, Al and Cr element have along the degree of depth and are outer rich Al and the characteristics of the Gradient distribution of the rich Cr of internal layer.
3. the present invention can be applicable to the protection of Ni based high-temperature alloy.
4. adopt the present invention can improve coating resistance to high temperature oxidation, hot corrosion resistance, and can prolong coating service life effectively.
Description of drawings
Fig. 1 (a)-(b) is the section S EM pattern of (MCrAlY+AlSiY) composite coating of (a) and anneal back (b) before 1050 ℃ of annealing.
Fig. 2 is the element mapping in cross section, (MCrAlY+AlSiY) composite coating annealing back.
Fig. 3 is the section S EM pattern of (MCrAlY+AlSiY) composite coating after 1000 ℃ of annealing.。
Fig. 4 is along white line Al among Fig. 3 and Cr concentration of element distribution map.
The specific embodiment
Through instance the present invention is done further explain below.
Embodiment 1
Base material adopts Ni based high-temperature alloy K465, and its nominal composition is (mass percent): 9.75%Co, 8.75%Cr, and 5.5%Al, 2.15%Ti, 1.85%Mo, 10.25%W, 1%Nb, Ni surplus, specimen size are Φ 15 * 1.5mm
2Adopt homemade MIP-8-800 type multi-arc ion plating equipment codeposition MCrAlY+AlSiY composite coating.MCrAlY target composition is (mass percent meter) as follows, Co:32; Cr:20; Al:8; Y:0.5; Si:1; B:0.03, Ni: surplus.Before the deposition sample is carried out preliminary treatment, be about to the base material sample and polish, adopt 200 order hollow glass ball wet abrasive blastings to handle, successively adopt metal detergent, deionized water, acetone ultrasonic cleaning 15min immediately, with dry for standby after the alcohol rinsing to Ra=0.4 μ m.Adopt MIP-8-800 type arc ion plating apparatus to deposit conventional MCrAlY coating, forvacuum to 7 * 10
-3Pa feeds Ar gas when bombardment and deposition, and vacuum is 2 * 10
-1Pa.When sample was carried out preparatory sputter bombardment and cleans, target-substrate distance was 240mm, and pulsed bias is-800V dutycycle 33%, scavenging period 5min; Arc voltage is 20V during deposition, and arc current 60～65A, pulsed bias be-250V, dutycycle 33%, and depositing temperature is 350 ℃, and sedimentation time is 300min, and the conventional MCrAlY coating layer thickness of acquisition is about 32 μ m.
Continuation is depositing Al SiY coating on conventional MCrAlY coating basis, and AlSiY target composition is (mass percent meter) as follows: Si:10; Y:1, Al: surplus.The conventional MCrAlY coating of depositing Al SiY coating process parameter synsedimentary, the AlSiY coating layer thickness of acquisition is about 8 μ m.The MCrAlY+AlSiY composite coating put into charge into the Ar gas shiled after quartz glass tube vacuumizes, 1050 ℃ of insulation 4h in Muffle furnace, heating rate is 5 ℃/min, cools to room temperature with the furnace.
The cross section pattern of coating is shown in Fig. 1 (a)-(b) before and after the diffusion annealing.Can know that by Fig. 1 (a)-(b) after the diffusion annealing, the about 25 μ m of MCrAlY+AlSiY composite coating skin depth are by the σ-NiCoCr and the Cr of β-NiAl and disperse distribution
3Si forms, and the about 15 μ m of interior layer thickness reach a small amount of β-NiAl mutually by rich Cr and form.
As shown in Figure 2, can be found out by the element mapping in cross section, MCrAlY+AlSiY composite coating annealing back: after the annealing, the MCrAlY+AlSiY composite coating has formed the Gradient distribution of outer rich Al, the rich Cr of internal layer.
Embodiment 2
Be with embodiment 1 difference:
Base material adopts directional solidification Ni based high-temperature alloy DZ125, and its nominal composition is (mass percent meter): 10%Co, 9%Cr, 7%W, 5%Al, 2.5%Ti, 3.5%Ta, C trace, Ni surplus.Specimen size is 15 * 10 * 1.5mm
3The coating deposition parameter is with embodiment 1.The MCrAlY+AlSiY composite coating put into charge into the Ar gas shiled after quartz glass tube vacuumizes, 1000 ℃ of insulation 5h in Muffle furnace, heating rate is 6 ℃/min, cools to room temperature with the furnace.
The cross section pattern of coating is as shown in Figure 3 before and after the diffusion annealing, can be known by Fig. 3, after the diffusion annealing; The about 15 μ m of MCrAlY+AlSiY composite coating skin depth are made up of the about 20wt% of Al content β-NiAl and σ-NiCoCr; The about 10wt% of Cr content, the about 22 μ m of interior layer thickness are by rich Cr phase composition; The about 6wt% of Al content, the about 30wt% of Cr content.
Fig. 4 is that therefrom can find out: along depth direction, Al content has Gradient distribution characteristic from high to low along the Al, the Cr distribution diagram of element that are coated with layer cross section, and the Cr element has Gradient distribution characteristic from low to high.
Embodiment result shows, the present invention adds the method for vacuum diffusion annealing through electric arc ion-plating deposition, prepares the MCrAlY composite coating of the distribution gradient of outer rich Al, the rich Cr of internal layer.Compare with existing conventional MCrAlY high-temperature protection coating; This MCrAlY+AlSiY composite coating involved in the present invention has improved the content of storage phase content of Al in the coating top layer and Si effectively; And formed rich Cr layer at the coating internal layer; Thereby can improve coating resistance to high temperature oxidation, hot corrosion resistance, and can prolong coating service life effectively.This composite coating and preparation method thereof can be applicable to the protection of Ni based high-temperature alloy.
Claims (6)
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| CN102400099B (en) * | 2011-11-04 | 2013-06-12 | 四川大学 | Technology for preparing nuclear fission reactor fuel clad surface CrAlSiN gradient coating |
| CN104372390A (en) * | 2014-12-08 | 2015-02-25 | 广东电网有限责任公司电力科学研究院 | Novel process for manufacturing MCrAlY thermal barrier coatings |
| CN104760349B (en) * | 2015-02-04 | 2016-10-19 | 南京航空航天大学 | High-temperature oxidation-resistant and heat-corrosion-resistant Al-Cr coating on the surface of a titanium-aluminum alloy and its preparation method |
| CN109234674A (en) * | 2018-11-14 | 2019-01-18 | 中国航发动力股份有限公司 | A kind of turbo blade MCrAlY coating physics restorative procedure |
| CN112663001B (en) * | 2020-12-14 | 2022-07-01 | 中国兵器工业第五九研究所 | A kind of titanium alloy blade protective coating and preparation method thereof |
| CN114075665B (en) * | 2021-11-18 | 2024-03-15 | 常州大学 | NiSiAlY coating on surface of titanium alloy and preparation method thereof |
| CN114196918A (en) * | 2021-12-02 | 2022-03-18 | 浙江浙能技术研究院有限公司 | Power station high-temperature bolt protective coating and preparation method thereof |
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| CN1665959A (en) * | 2002-07-09 | 2005-09-07 | 西门子公司 | High oxidation resistance parts |
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| CN1665959A (en) * | 2002-07-09 | 2005-09-07 | 西门子公司 | High oxidation resistance parts |
Non-Patent Citations (2)
| Title |
|---|
| 刘旭.NiCoCrAlY(Si)梯度涂层对Ni_3Al基单晶合金IC6SX抗氧化性能的影响.《材料工程》.2008,(第5期), * |
| 戴文君.后处理对多弧离子镀NiCoCrAlY涂层高温氧化性能的影响.《腐蚀科学与防护技术》.2007,第27卷(第2期), * |
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