CN117626057A - Modified MCrAlY coating, preparation method thereof and single crystal superalloy - Google Patents
Modified MCrAlY coating, preparation method thereof and single crystal superalloy Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 265
- 239000011248 coating agent Substances 0.000 title claims abstract description 261
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 71
- 239000013078 crystal Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 14
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- 239000000758 substrate Substances 0.000 claims description 58
- 229910045601 alloy Inorganic materials 0.000 claims description 52
- 239000000956 alloy Substances 0.000 claims description 52
- 238000000151 deposition Methods 0.000 claims description 50
- 230000008021 deposition Effects 0.000 claims description 36
- 238000004544 sputter deposition Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000007733 ion plating Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
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- 239000000203 mixture Substances 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000009689 gas atomisation Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
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- 239000011261 inert gas Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 31
- 238000007254 oxidation reaction Methods 0.000 abstract description 31
- 230000007797 corrosion Effects 0.000 abstract description 25
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000004584 weight gain Effects 0.000 abstract description 12
- 235000019786 weight gain Nutrition 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
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- 238000000889 atomisation Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 101000912561 Bos taurus Fibrinogen gamma-B chain Proteins 0.000 description 4
- 238000004901 spalling Methods 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a modified MCrAlY coating, a preparation method thereof and a single crystal superalloy. The modified MCrAlY coating comprises the following chemical components in percentage by mass: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni. The modified MCrAlY coating has excellent high-temperature oxidation resistance, and the surface oxide layer has higher anti-stripping capability and higher strength. After the components of the modified MCrAlY coating are optimized, the volume weight gain is reduced by 50% after the modified MCrAlY coating is oxidized for 200 hours at 1140 ℃. Meanwhile, the modified MCrAlY coating has excellent hot corrosion resistance, and the weight of the modified MCrAlY coating is increased by 0.3mg/cm after hot corrosion for 200 hours at 900 DEG C 2 . The modified MCrAlY coating provided by the invention can be suitable for manufacturing high-temperature protection of long-life high-reliability hot-end high-temperature parts in the fields of aviation, aerospace, energy and the like.
Description
Technical Field
The invention relates to the technical field of high-temperature protective coating preparation, in particular to a modified MCrAlY coating, a preparation method thereof and a single crystal superalloy.
Background
The high-temperature alloy has excellent mechanical property and high-temperature creep resistance, so that the high-temperature alloy is widely applied to hot end piece materials in the aerospace industry. In order to continuously improve the working efficiency of the gas turbine engine, the air inlet temperature of the advanced gas turbine can reach 1600 ℃, and the working temperature of the blades can reach 1000-1200 ℃. Because the working temperature of the blade is highest and the stress is complex, the novel engine rotor blade adopts nickel-based single crystal superalloy with higher heat resistance temperature as a structural material. In order to protect these critical hot-end components and to extend the reliable service life of the hot-end components of the engine, it is generally necessary to coat the surfaces of the blades with a high-temperature protective coating to protect the base alloy from accelerated damage by high-temperature oxidation.
Compared with the traditional diffusion type coating, the MCrAlY coating has excellent environmental resistance and environmental adaptability, and the variation range of the composition and thickness of the coating can be adjusted according to the service environment and the matrix alloy, so that the interdiffusion behavior between the coating and the matrix is reduced, and the mechanical property damage of the coating to the matrix is reduced. Thus, the choice and control of the composition of the MCrAlY coating can greatly affect the performance of the coating and the substrate. At present, a large amount of active elements are added into the coating to carry out modification treatment, wherein Si element can improve the anti-stripping capability of the oxide film, the time for stripping the oxide film is prolonged, and meanwhile, the Si coating has better corrosion resistance. However, an excessive Si content increases the ratio between the volume of a single metal ion in the oxide film and the volume of each metal atom in the metal, and an excessive compressive stress is generated in the oxide film, which tends to cause cracking of the oxide film and a decrease in oxidation resistance of the coating. Therefore, how to provide an MCrAlY coating with excellent performance by reasonably blending the components of the coating is a problem to be solved based on consideration that Si may cause the stress of the oxide film of the coating to be aggravated while improving the anti-spalling capability of the oxide film, and the good and bad performances of other components are combined.
In summary, the existing MCrAlY coating has at least the following technical problems:
aiming at the existing MCrAlY coating, the problem that the stress of the oxide film of the coating is aggravated and the oxide film is broken easily while the anti-stripping capability of the oxide film on the coating is improved.
Disclosure of Invention
In view of the above, the invention provides a modified MCrAlY coating, a preparation method thereof and a single crystal superalloy, which can solve the problems of the prior art that the stress of an oxide film of the coating is aggravated and the oxide film is broken easily while the anti-stripping capability of the oxide film on the coating is improved.
In order to solve the problems, the invention provides a modified MCrAlY coating, which comprises the following chemical components in percentage by mass: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni.
The modified MCrAlY coating comprises the following chemical components in percentage by mass: 23 to 28 weight percent of Cr, 13 to 18 weight percent of Co, 8 to 12 weight percent of Al, 0.8 to 1.3 weight percent of Y, 0.06 to 0.12 weight percent of Si and the balance of Ni.
In the modified MCrAlY coating, the mass percentage of Si is a, and the sum of the mass percentages of Al and Cr is b; wherein a/b=1.5×10 -3 ～3×10 -3 。
The modified MCrAlY coating is deposited on the surface of the carrier;
forming a compact and pinning oxide film on the surface of the modified MCrAlY coating to improve the anti-stripping capability of the oxide film on the surface of the modified MCrAlY coating;
and/or the P-B ratio of the oxide film on the surface of the modified MCrAlY coating is 1.5-1.8;
and/or the modified MCrAlY coating contains 55-60% of beta phase and 40-45% of gamma' phase by volume fraction so as to improve the high-temperature strength.
The invention also provides a preparation method of the modified MCrAlY coating, which comprises the following steps:
the preparation method of the modified MCrAlY coating comprises the following steps:
preparing alloy powder: preparing a master alloy ingot, and preparing the master alloy ingot into alloy powder;
preparing a carrier containing a coating: pretreating a carrier, and depositing alloy powder on the pretreated carrier to obtain a carrier containing a coating;
in the preparation method of the modified MCrAlY coating, in the preparation of the alloy powder, the master alloy ingot is prepared into the alloy powder by adopting vacuum gas atomization treatment.
In the preparation method of the modified MCrAlY coating, the carrier containing the coating is prepared by the following steps: the pretreatment comprises electrochemical degreasing and activation treatment of the carrier in sequence;
preferably, the carrier is subjected to surface treatment prior to pretreatment, wherein the surface treatment comprises polishing, wet blasting and ultrasonic treatment which are sequentially carried out.
In the preparation method of the modified MCrAlY coating, the carrier containing the coating is prepared by the following steps: pre-sputtering and cleaning the pretreated carrier;
preferably, the parameters of the pre-sputter clean are controlled as follows:
carrying out air steaming treatment on the carrier and the furnace chamber for 10-15 min to obtain a deposition environment atmosphere; after the alloy powder is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 < -3 > to 8 multiplied by 10 < -3 > Pa, the temperature is raised to 100 ℃ to 120 ℃, inert gas is filled into the vacuum chamber, and the air pressure is maintained to be 0.23 Pa to 0.25Pa; pre-sputtering cleaning is carried out under the conditions of bias voltage of-600V to-800V, duty ratio of 25-30 percent and arc current of 55-65A, sputtering voltage is controlled to be-15V to-20V, and sputtering time is controlled to be 3-5 min.
In the preparation method of the modified MCrAlY coating, the carrier containing the coating is prepared by the following steps: depositing alloy powder on the pretreated carrier by adopting an arc ion plating deposition technology to obtain a carrier containing a coating;
preferably, parameters of the arc ion plating deposition technique are controlled as follows:
the target base distance is 220 mm-280 mm, the arc voltage is 20V-25V, the arc current is 70A-90A, the pulse bias voltage is-150 to-300V, the duty ratio is 20-40%, the deposition temperature is 150-300 ℃, the deposition time is 2h-5h, and the coating thickness is 40 μm-60 μm.
In the preparation method of the modified MCrAlY coating, the modified MCrAlY coating is prepared by the following steps: the heat treatment adopts vacuum heat treatment;
parameters of the vacuum heat treatment were controlled as follows:
adopting a vacuum gradient heat treatment mode, treating for 2-4 hours at the temperature of 650-800 ℃ and carrying out 2-4 hours at the temperature of 900-1000 ℃; the heating and cooling rates are controlled to be 1-3 ℃/min.
The invention also provides a material for preparing the modified MCrAlY coating, which comprises the following chemical components in percentage by mass: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni;
preferably, the mass percentage of Si is a, and the sum of the mass percentages of Al and Cr is b; wherein a/b=1.5×10 -3 ～3×10 -3 。
The invention also provides a single crystal superalloy, which comprises a single crystal superalloy substrate and a modified MCrAlY coating deposited on the single crystal superalloy substrate; wherein the modified MCrAlY coating is the modified MCrAlY coating;
preferably, the single crystal superalloy substrate is a single crystal superalloy blade.
Compared with the prior art, the modified MCrAlY coating and the preparation method thereof and the single crystal superalloy provided by the invention have at least the following beneficial effects.
In one aspect, the invention provides a modified MCrAlY coating, which comprises the following chemical components: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni. It should be noted that: the MCrAlY coating adopts trace Si element, and the Si element oxidizes film crystals along the coatingFormation of SiO with oxygen 2 Resulting in SiO 2 Exists at the surface of the MCrAlY coating and the grain boundary below the MCrAlY coating so that SiO 2 The surface of the MCrAlY coating is nailed in a pinning mode to form a compact and pinning oxide film, and the oxide film can be firmly pinned on the surface of the MCrAlY coating, so that the oxide film on the surface of the modified MCrAlY coating has excellent anti-stripping capability. Meanwhile, si element cooperates with Al and Cr elements to reduce the critical content value of oxidation of Al and Cr elements on the surface of the modified MCrAlY coating, and trace Si element can promote the surface of the coating to form Al 2 O 3 And Cr (V) 2 O 3 The oxide prevents the modified MCrAlY coating from internal oxidation, so that a stable oxide film is formed on the surface of the modified MCrAlY coating, and the coating has high-temperature oxidation resistance. The trace Si element enables the P-B ratio of the oxide film on the surface of the modified MCrAlY coating to be 1.5-1.8, enables the stress in the oxide film to be in a reasonable range value, enables the oxide film not to be easily broken, and further improves the high-temperature oxidation resistance of the modified MCrAlY coating.
Meanwhile, the microstructure and the growth mechanism of the oxide film can be changed by adding the Y element, and the plasticity and the spalling resistance of the oxide film are improved. Meanwhile, the Y element can utilize vacancy coarsening to eliminate holes at the interface of the coating and the oxide film, so that the binding force between the modified MCrAlY coating and the oxide film is improved. Further improving the anti-stripping capability of the oxide film.
On the other hand, the modified MCrAlY coating of the invention regulates the contents of Si, al and Cr: si/(al+cr) =1.5x10 -3 ～3×10 -3 . The oxidation film on the surface of the modified MCrAlY coating can also form a pinning shape during hot corrosion, so that the oxidation film is ensured to have excellent hot corrosion resistance, and experimental tests prove that the modified MCrAlY coating is subjected to hot corrosion for 200h at 900 ℃ and is increased by 0.3mg/cm 2 Is superior to the traditional MCrAlY coating.
Further, cr element can ensure that the coating has excellent high-temperature oxidation resistance, can improve the Type II hot corrosion resistance of the coating, and can reduce the formation of continuous Al 2 O 3 The minimum Al content required for the layer. At the same time, cr can also react with O element to form Cr 2 O 3 The film mainly plays a role in resisting hot corrosion. However, when the Cr content is high, the attaching capability of the oxide film and the coating is damaged, so that the invention adopts reasonable Cr element, and improves the high-temperature oxidation resistance and the hot corrosion resistance of the coating.
On the other hand, the addition of the trace Si element can avoid the formation of brittle phases inside the coating due to excessive Si element, thereby improving the strength of the modified MCrAlY coating. Meanwhile, the limited use of Si reduces the design and use cost of the coating.
On the other hand, co element is mainly used for relieving the interface stress between the modified MCrAlY coating and the high-temperature alloy matrix and improving the interface stability between the coating and the matrix. However, when the Co content is high, a Co-rich phase is formed, which is inconsistent with the potential of the coating, and the Co-rich phase is easy to become a micro-cathode area, so that the corrosion of the coating is accelerated. Therefore, the invention designs reasonable Co content, the Co element content is 10-20wt%, and the stability of the interface between the modified MCrAlY coating and the high-temperature alloy substrate can be effectively improved.
Furthermore, the invention carries out electrochemical degreasing and activation treatment on the carrier, and removes the oxide film on the surface of the carrier through pretreatment, thereby further improving the binding force of the MCrAlY coating and the superalloy substrate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. The drawings in the following description are merely exemplary and other implementations drawings may be derived from the drawings provided without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing a comparison of the cross-sectional tissue morphology of a modified MCrAlY coating of example 1 of the present invention and a MCrAlY coating of comparative example 1;
FIG. 2 is a graph comparing the oxidative weight gain curves of the modified MCrAlY coating of example 2 of the present invention with the MCrAlY coating of comparative example 1;
FIG. 3 is a schematic diagram showing the comparison of the morphology of the cross-sectional structures of the modified MCrAlY coating of example 3 and the MCrAlY coating of comparative example 1 after oxidation at 1000℃for 200 hours;
FIG. 4 is a graph showing the comparison of weight gain curves of the modified MCrAlY coating of example 4 of the present invention and the MCrAlY coating of comparative example 1 under the condition of hot corrosion at 900 ℃ for 200 hours;
FIG. 5 is a comparative graph of the weight gain of the modified MCrAlY coating of example 5, the modified MCrAlY coating of example 4, and the MCrAlY coating of comparative example 1 under conditions of hot corrosion at 900℃for 200 h.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
How to realize the MCrAlY coating with higher high-temperature oxidation resistance and strong spalling resistance of the surface oxide film needs to be further optimized.
The main scheme of the invention is as follows:
the invention provides a modified MCrAlY coating, which comprises the following chemical components in percentage by mass: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni.
Based on the above component proportions, the main inventive concept of the present invention is as follows: in the aspect of the components of the modified MCrAlY coating, the invention adopts trace Si element which forms stable SiO with oxygen along the grain boundary of the oxide film 2 The oxide film can be firmly pinned on the surface of the modified MCrAlY coating, so that the anti-stripping capability of the oxide film on the surface of the MCrAlY coating can be obviously improved, the cracking tendency of the oxide film is reduced, and the stripping time of the oxide film is prolonged. Meanwhile, the Si elements of the invention cooperateAl and Cr elements can reduce the critical content value of oxidation of Al and Cr elements on the surface of the modified MCrAlY coating, and the existence of trace Si elements can promote the surface of the coating to form Al 2 O 3 And Cr (V) 2 O 3 The oxide prevents the modified MCrAlY coating from being internally oxidized, so that a stable oxide film is formed on the surface of the modified MCrAlY coating. Based on the above, the P-B ratio of the oxide film on the surface of the modified MCrAlY coating is 1.5-1.8, so that the oxide film is not easy to crack. In conclusion, the Si content of the modified MCrAlY coating is selected to be 0.05-0.15 wt%. The anti-stripping capability of the oxide can be improved, the coating has better strength, and the stress of the oxide film of the coating is controlled within a reasonable range, so that the high-temperature oxidation resistance of the oxide film is improved.
On the other hand, the addition of the Y element can change the microstructure and the growth mechanism of the oxide film, and improve the plasticity and the spalling resistance of the oxide film. Meanwhile, the Y element can utilize vacancy coarsening to eliminate holes at the interface of the coating and the oxide film, so that the binding force between the coating and the oxide film is improved. Therefore, a certain amount of Y element is required to be added into the coating, and the Y content of the coating is 0.5-1.5 wt%.
Meanwhile, the Cr element adopted in the invention can ensure that the coating has excellent high-temperature oxidation resistance, can improve the Type II hot corrosion resistance of the coating, and can reduce the formation of continuous Al 2 O 3 The minimum Al content required for the layer. At the same time, cr can also react with O element to form Cr 2 O 3 The film mainly plays a role in resisting hot corrosion. However, when the Cr content in the coating is high, the adhesion between the oxide film on the surface of the coating and the coating is destroyed. Therefore, the invention needs to moderately control and improve the Cr content in the component design, and the Cr content is 20-30wt%.
The Co element is mainly used for relieving the interface stress between the coating and the matrix and improving the interface stability between the coating and the matrix. However, when the Co content is high, a Co-rich phase is formed, which is inconsistent with the potential of the coating, and the Co-rich phase is easy to become a micro-cathode area, so that the corrosion of the coating is accelerated. Therefore, the Co content of the modified MCrAlY coating is controlled to be 10-20wt%.
The invention adopts Al element, which is the most main precipitation strengthening gamma' phase forming element in the high-temperature alloy. The coating can contain 55-60% of beta phase and 40-45% of gamma ' phase by volume fraction, and the gamma ' phase has higher high-temperature strength, so that the volume fraction of the gamma ' phase in the coating is further improved by controlling the Al content, and the high-temperature strength of the coating is further improved. At the same time, al reacts with the O element in the environment to form a dense alumina layer that can prevent further oxidation of the inner coating and substrate. Thus, the Al content of the inventive coating is 5-15 wt%.
Further, the modified MCrAlY coating comprises the following chemical components in percentage by mass: 23 to 28 weight percent of Cr, 13 to 18 weight percent of Co, 8 to 12 weight percent of Al, 0.8 to 1.3 weight percent of Y, 0.06 to 0.12 weight percent of Si and the balance of Ni.
Further, in the modified MCrAlY coating, the mass percentage of Si is a, and the sum of the mass percentages of Al and Cr is b; wherein a/b=1.5×10 -3 ～3×10 -3 。
The modified MCrAlY coating of the invention regulates the contents of Si, al and Cr: si/(al+cr) =1.5x10 -3 ～3×10 -3 . The oxidation film is ensured to have excellent hot corrosion resistance, and through experimental tests, the modified MCrAlY coating is subjected to hot corrosion for 200 hours at 900 ℃ and has 0.3mg/cm of weight gain 2 Is superior to the traditional MCrAlY coating.
Further, the modified MCrAlY coating is coated on the surface of the single crystal superalloy;
forming a compact and pinning oxide film on the surface of the modified MCrAlY coating to improve the anti-stripping capability of the oxide film on the surface of the modified MCrAlY coating;
and/or the P-B ratio of the oxide film on the surface of the modified MCrAlY coating is 1.5-1.8;
and/or the modified MCrAlY coating contains 55-60% of beta phase and 40-45% of gamma' phase by volume fraction so as to improve the high-temperature strength.
In the modified MCrAlY coating, as a trace amount of Si element is added, the Si element forms stable SiO with oxygen along the grain boundary of an oxide film 2 Can form an oxide film with a pinning shapeThe high-temperature oxidation resistant coating is firmly pinned on the surface of the MCrAlY coating to induce the internal oxidation of the coating to be converted into external oxidation, so that a more compact oxidation film with a pinning morphology is formed, and the coating has excellent high-temperature oxidation resistant performance. Al adopted in the invention is the most main forming element of precipitation strengthening gamma 'phase in the high-temperature alloy, and can ensure that the coating contains gamma' phase with the volume fraction of 30-40% and beta phase with the volume fraction of 55-60%, thereby ensuring the high-temperature strength of the coating. Meanwhile, the P-B ratio of the oxide film of the modified MCrAlY coating is increased to 1.5-1.8, so that the compressive stress of the modified MCrAlY coating is improved, and the weight gain is smaller than 1.0mg/cm after the oxidation for 200h at 1000 DEG C 2 。
The invention also provides a preparation method of the modified MCrAlY coating, which comprises the following steps:
preparing alloy powder: preparing a master alloy ingot, and preparing the master alloy ingot into alloy powder;
preparing a carrier containing a coating: pretreating a carrier, and depositing alloy powder on the pretreated carrier to obtain a carrier containing a coating;
preparing a modified MCrAlY coating: and (3) carrying out heat treatment on the carrier containing the coating to form a modified MCrAlY coating on the surface of the carrier.
Further, a master alloy ingot is prepared into alloy powder by adopting vacuum gas atomization treatment.
According to the invention, the master alloy ingot is prepared into alloy powder by adopting vacuum gas atomization treatment, so that the components of the prepared alloy powder are more uniform.
Further, the invention sequentially carries out electrochemical degreasing and activation treatment on the superalloy substrate.
Preferably, the superalloy substrate is subjected to a surface treatment prior to the pretreatment, the surface treatment comprising: sequentially polishing, wet sand blasting and ultrasonic treatment.
As a reasonable choice, the SiC sand paper of 150# and 240# and 400# and 600# and 800# is sequentially used on a pre-grinding machine to grind the superalloy substrate so as to remove an oxide film on the surface of the substrate, a sample is formed after the fresh surface of the superalloy substrate is ground, the sample is subjected to wet sand blasting treatment, and then the sample is sequentially subjected to ultrasonic treatment by using acetone and alcohol so as to remove oil stains and the like remained on the surface of the sample, so that the cleanliness of the surface of the sample is improved.
The invention adopts electrochemical degreasing and activation treatment, and the purpose of the electrochemical degreasing is to further remove dirt and grease: ensuring the surface cleanliness of the high-temperature alloy matrix; the roughening effect of the surface of the superalloy substrate is increased by the activation treatment, so that the binding force between the MCrAlY coating and the superalloy substrate is further increased.
Further, pre-sputtering cleaning is carried out on the pretreated carrier, and parameters of the pre-sputtering cleaning are controlled as follows:
carrying out air steaming treatment on the carrier and the furnace chamber for 10-15 min to obtain a stable deposition environment atmosphere; after the alloy powder is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 -3 ～8×10 -3 Pa, raising the temperature to 100-120 ℃, filling argon into the vacuum chamber and maintaining the air pressure to be 0.23-0.25 Pa; and then pre-sputtering cleaning is carried out under the conditions of bias voltage of-600V to-800V, duty ratio of 25-30% and arc current of 55-65A, sputtering voltage is controlled to be-15V to-20V, and sputtering is carried out for 3-5 min.
Further, in step 3): specific parameters of the arc ion plating deposition technique are controlled as follows:
the target base distance is 220 mm-280 mm, the arc voltage is 20V-25V, the arc current is 70A-90A, the pulse bias voltage is-150 to-300V, the duty ratio is 20-40%, the deposition temperature is 150-300 ℃, the deposition time is 2h-5h, and the coating thickness is 40 μm-60 μm.
The bonding force between the high-temperature alloy matrix and the coating can be improved by adopting pre-sputtering cleaning; and the invention adopts the arc ion plating deposition technology, so as to further make the components of the coating more uniform.
Further, the heat treatment adopts vacuum heat treatment;
parameters of the vacuum heat treatment were controlled as follows:
adopting a vacuum gradient heat treatment mode, treating for 2-4 hours at the temperature of 650-800 ℃ and carrying out 2-4 hours at the temperature of 900-1000 ℃; the heating and cooling rates are controlled to be 1-3 ℃/min.
According to the invention, the deposited modified MCrAlY coating is subjected to gradient vacuum heat treatment, so that Si is uniformly present in the coating beta phase, and trace Si elements are adopted in combination with the coating, so that the uniform solid solution of the Si elements in the coating beta phase is ensured, the morphology of an oxidized film on the surface of the oxidized coating is obviously improved, and the high-temperature oxidation resistance of the coating is further improved.
The invention also provides a material for preparing the modified MCrAlY coating, which comprises the following chemical components in percentage by mass: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni;
preferably, the mass percentage of Si is a, and the sum of the mass percentages of Al and Cr is b; wherein a/b=1.5×10 -3 ～3×10 -3 。
The invention also provides a single crystal superalloy, which comprises a single crystal superalloy substrate and a modified MCrAlY coating deposited on the single crystal superalloy substrate; wherein the modified MCrAlY coating is the modified MCrAlY coating;
the single crystal superalloy substrate may be a single crystal superalloy blade. By adopting the single-crystal superalloy of the invention as a matrix, the blade forms the modified MCrAlY coating on the superalloy matrix, so that the blade has better high-temperature oxidation resistance and corrosion resistance, and the surface oxide film has higher anti-stripping capability, higher strength and excellent performance.
The modified MCrAlY coating, the preparation method thereof and the superalloy substrate according to the invention are described in further detail by specific examples and comparative examples.
Example 1
The modified MCrAlY coating prepared in the embodiment mainly comprises the following steps:
step 1): according to Cr:23%, co:17%, al:7%, Y:0.9%, si:0.08%, the balance being Ni, wherein Si/(Al+Cr) =2.7X10 -3 The method comprises the steps of carrying out a first treatment on the surface of the A master alloy ingot is prepared, and then alloy powder is prepared by a vacuum atomization method.
Step 2) sequentially polishing the single-crystal superalloy substrate by using SiC sand paper of No. 150, no. 240, no. 400, no. 600 and No. 800 on a pre-grinder, grinding the fresh surface of the single-crystal superalloy substrate to form a sample, carrying out wet sand blasting on the sample, and then sequentially carrying out ultrasonic treatment on the sample by using acetone and alcohol.
Step 3) firstly, carrying out 12min of air steaming treatment on the monocrystalline superalloy substrate and the furnace chamber to obtain a stable deposition environment atmosphere. After the sample is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 -3 Pa, increasing the temperature to 110 ℃, and filling argon into the vacuum chamber to maintain the air pressure to be 0.24Pa; then, pre-sputtering cleaning is carried out under the conditions of bias voltage of-700V, duty ratio of 25% and arc current of 60A, sputtering voltage is-18V, and sputtering is carried out for 4min.
Depositing an MCrAlY coating on a single crystal superalloy substrate: the target base distance is 260mm, the arc voltage is 25V, the arc current is 77A, the pulse bias voltage is-220V, the duty ratio is 30%, the deposition temperature is 230 ℃, the deposition time is 3h, and the coating thickness is 57 μm.
After the arc ion plating deposition, carrying out vacuum annealing treatment on the monocrystalline superalloy substrate containing the coating under the vacuum condition: vacuum gradient heat treatment is carried out at 700 ℃ for 4 hours and 950 ℃ for 3 hours, heating and cooling speeds are controlled at 1 ℃/min, and a modified MCrAlY coating is formed on the surface of the monocrystal superalloy substrate.
Example 2
Step 1): according to the following steps: cr:25%, co:16%, al:13%, Y:1.3%, si:0.11%, the balance being Ni, wherein Si/(Al+Cr) =2.9X10) -3 The method comprises the steps of carrying out a first treatment on the surface of the A master alloy ingot is prepared, and then alloy powder is prepared by a vacuum atomization method.
Step 2) sequentially polishing the single-crystal superalloy substrate by using SiC sand paper of No. 150, no. 240, no. 400, no. 600 and No. 800 on a pre-grinder, grinding the fresh surface of the single-crystal superalloy substrate to form a sample, carrying out wet sand blasting on the sample, and then sequentially carrying out ultrasonic treatment on the sample by using acetone and alcohol.
Step 3) firstly, carrying out 12mi on the monocrystalline superalloy substrate and a furnace chamberAnd (5) performing n-space steaming treatment to obtain a stable deposition environment atmosphere. After the sample is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 -3 Pa, increasing the temperature to 110 ℃, and filling argon into the vacuum chamber to maintain the air pressure to be 0.24Pa; then, pre-sputtering cleaning is carried out under the conditions of bias voltage of-700V, duty ratio of 25% and arc current of 60A, sputtering voltage is-18V, and sputtering is carried out for 4min.
Depositing an MCrAlY coating on a single crystal superalloy substrate: the target base distance is 240mm, the arc voltage is 22V, the arc current is 80A, the pulse bias voltage is-260V, the duty ratio is 25%, the deposition temperature is 250 ℃, the deposition time is 2.5h, and the coating thickness is 50 μm.
After the arc ion plating deposition, carrying out vacuum annealing treatment on the monocrystalline superalloy substrate containing the coating under the vacuum condition: vacuum gradient heat treatment is carried out at 680 ℃ for 4 hours and 970 ℃ for 2 hours, the heating and cooling speeds are controlled at 1 ℃/min, and a modified MCrAlY coating is formed on the surface of the monocrystal superalloy substrate.
Example 3
Step 1): according to the following steps: cr:27%, co:12%, al:12%, Y:1.4%, si:0.08%, the balance being Ni, wherein Si/(Al+Cr) =2.1X10) -3 The method comprises the steps of carrying out a first treatment on the surface of the A master alloy ingot is prepared, and then alloy powder is prepared by a vacuum atomization method.
Step 2) sequentially polishing the single-crystal superalloy substrate by using SiC sand paper of No. 150, no. 240, no. 400, no. 600 and No. 800 on a pre-grinder, grinding the fresh surface of the single-crystal superalloy substrate to form a sample, carrying out wet sand blasting on the sample, and then sequentially carrying out ultrasonic treatment on the sample by using acetone and alcohol.
Step 3) firstly, carrying out 12min of air steaming treatment on the monocrystalline superalloy substrate and the furnace chamber to obtain a stable deposition environment atmosphere. After the sample is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 -3 Pa, increasing the temperature to 110 ℃, and filling argon into the vacuum chamber to maintain the air pressure to be 0.24Pa; then, pre-sputtering cleaning is carried out under the conditions of bias voltage of-700V, duty ratio of 25% and arc current of 60A, sputtering voltage is-18V, and sputtering is carried out for 4min.
Depositing an MCrAlY coating on a single crystal superalloy substrate: the target base distance is 240mm, the arc voltage is 25V, the arc current is 83A, the pulse bias voltage is-260V, the duty ratio is 24%, the deposition temperature is 180 ℃, the deposition time is 4h, and the coating thickness is 46 mu m.
After the arc ion plating deposition, carrying out vacuum annealing treatment on the monocrystalline superalloy substrate containing the coating under the vacuum condition: vacuum gradient heat treatment is carried out at 750 ℃ for 3 hours, and at 930 ℃ for 3 hours, the heating and cooling speeds are controlled at 1 ℃/min, and a modified MCrAlY coating is formed on the surface of the monocrystal superalloy substrate.
Example 4
Step 1): according to the following steps: cr:25%, co:18%, al:15%, Y:0.8%, si:0.12%, the balance being Ni, wherein Si/(Al+Cr) =3×10 -3 A master alloy ingot was prepared, and then powders of the same composition were prepared by a vacuum atomization method.
Step 2) sequentially polishing the single-crystal superalloy substrate by using SiC sand paper of No. 150, no. 240, no. 400, no. 600 and No. 800 on a pre-grinder, grinding the fresh surface of the single-crystal superalloy substrate to form a sample, carrying out wet sand blasting on the sample, and then sequentially carrying out ultrasonic treatment on the sample by using acetone and alcohol.
Step 3) firstly, carrying out 12min of air steaming treatment on the monocrystalline superalloy substrate and the furnace chamber to obtain a stable deposition environment atmosphere. After the sample is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 -3 Pa, increasing the temperature to 110 ℃, and filling argon into the vacuum chamber to maintain the air pressure to be 0.24Pa; then, pre-sputtering cleaning is carried out under the conditions of bias voltage of-700V, duty ratio of 25% and arc current of 60A, sputtering voltage is-18V, and sputtering is carried out for 4min.
Depositing an MCrAlY coating on a single crystal superalloy substrate: the target base distance is 270mm, the arc voltage is 22V, the arc current is 85A, the pulse bias voltage is-190V, the duty ratio is 22%, the deposition temperature is 280 ℃, the deposition time is 4h, and the coating thickness is 60 μm.
After the arc ion plating deposition, carrying out vacuum annealing treatment on the monocrystalline superalloy substrate containing the coating under the vacuum condition: vacuum gradient heat treatment is carried out at 800 ℃ for 2 hours, and at 950 ℃ for 2 hours, the heating and cooling speeds are controlled at 1 ℃/min, and a modified MCrAlY coating is formed on the surface of the monocrystal superalloy substrate.
Example 5
Step 1): according to the following steps: cr:25%, co:18%, al:15%, Y:0.8%, si:0.15% and the balance Ni, wherein Si/(Al+Cr) =3.75X10) -3 The method comprises the steps of carrying out a first treatment on the surface of the A master alloy ingot was prepared, and then powders of the same composition were prepared by a vacuum atomization method. Step 2) sequentially polishing the single-crystal superalloy substrate by using SiC sand paper of No. 150, no. 240, no. 400, no. 600 and No. 800 on a pre-grinder, grinding the fresh surface of the single-crystal superalloy substrate to form a sample, carrying out wet sand blasting on the sample, and then sequentially carrying out ultrasonic treatment on the sample by using acetone and alcohol.
Step 3) firstly, carrying out 12min of air steaming treatment on the monocrystalline superalloy substrate and the furnace chamber to obtain a stable deposition environment atmosphere. After the sample is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 -3 Pa, increasing the temperature to 110 ℃, and filling argon into the vacuum chamber to maintain the air pressure to be 0.24Pa; then, pre-sputtering cleaning is carried out under the conditions of bias voltage of-700V, duty ratio of 25% and arc current of 60A, sputtering voltage is-18V, and sputtering is carried out for 4min.
Depositing an MCrAlY coating on a single crystal superalloy substrate: the target base distance is 270mm, the arc voltage is 22V, the arc current is 85A, the pulse bias voltage is-190V, the duty ratio is 22%, the deposition temperature is 280 ℃, the deposition time is 4h, and the coating thickness is 60 μm.
After the arc ion plating deposition, carrying out vacuum annealing treatment on the monocrystalline superalloy substrate containing the coating under the vacuum condition: vacuum gradient heat treatment is carried out at 800 ℃ for 2 hours, and at 950 ℃ for 2 hours, the heating and cooling speeds are controlled at 1 ℃/min, and a modified MCrAlY coating is formed on the surface of the monocrystal superalloy substrate.
Comparative example 1
The present comparative example has an increased Si content compared to the above examples 1 to 5.
Step 1): according to the following steps: cr:27%, co:16%, al:13%, Y:1.6%, si:1.5% and the balance Ni, wherein Si/(Al+Cr) =37.5X10) -3 The method comprises the steps of carrying out a first treatment on the surface of the Preparing a master alloy ingot, and then atomizing the master alloy ingot by vacuumThe method prepares the powder with the same components.
Step 2) sequentially polishing the monocrystal superalloy substrate by using SiC sand paper of No. 150, no. 240, no. 400, no. 600 and No. 800 on a pre-grinder, grinding the fresh surface of the monocrystal superalloy substrate to form a sample, carrying out wet sand blasting on the sample, and then sequentially carrying out ultrasonic treatment on the sample by using acetone and alcohol;
step 3) firstly, carrying out 12min of air steaming treatment on the monocrystalline superalloy substrate and the furnace chamber to obtain a stable deposition environment atmosphere. After the sample is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 -3 Pa, increasing the temperature to 110 ℃, and filling argon into the vacuum chamber to maintain the air pressure to be 0.24Pa; then, pre-sputtering cleaning is carried out under the conditions of bias voltage of-700V, duty ratio of 25% and arc current of 60A, sputtering voltage is-18V, and sputtering is carried out for 4min.
Depositing an MCrAlY coating on a single crystal superalloy substrate: the target base distance is 250mm, the arc voltage is 25V, the arc current is 77A, the pulse bias voltage is-220V, the duty ratio is 30%, the deposition temperature is 230 ℃, the deposition time is 3h, and the coating thickness is 60 μm.
After the arc ion plating deposition, carrying out vacuum annealing treatment on the monocrystalline superalloy substrate containing the coating under the vacuum condition: vacuum gradient heat treatment is carried out at 800 ℃ for 6 hours, air cooling is carried out to room temperature, and a modified MCrAlY coating is formed on the surface of the monocrystalline superalloy substrate.
The chemical compositions of the modified MCrAlY coating of the invention and the conventional MCrAlY coating of comparative example 1 are shown in the following Table 1.
TABLE 1 list of chemical composition of the alloys of the invention (examples 1-4) and of conventional MCrAlY (wt.%)
The cross-sectional tissue morphology pairs of the conventional MCrAlY coatings of inventive example 1 and comparative example 1 are shown in FIG. 1. As can be seen from FIG. 1, the addition of trace Si element does not change the macroscopic structure of the as-deposited coating, both coatings are composed of beta phase and gamma' phase, and the thickness of the coating is about 50 μm, si element is mainly dissolved in the beta phase of the coating when the modified MCrAlY coating is in the preparation state, and the content of the beta phase in the coating is more and can reach 55-60%.
The oxidation weight gain curves of the traditional MCrAlY coatings of the invention example 2 and comparative example 1 are shown in FIG. 2, and it can be seen from FIG. 2 that the oxidation weight gain at 1000 ℃ for 200h is less than 1.0mg/cm 2 The high temperature oxidation resistance of the coating of the present invention is higher than that of the conventional coating of the comparative example.
The surface and section tissue morphology of the traditional MCrAlY coating of the embodiment 3 and the comparative example 1 after being oxidized for 100 hours at 1000 ℃ is shown in figure 3, and the oxide film of the modified MCrAlY coating of the invention is in a pinning shape and has excellent binding force with the coating as can be seen from figure 3. In comparative example 1, the oxide film was relatively flat, and the substrate adhesion was poor, and it was easy to fall off when thermally loaded.
As shown in FIG. 4, the 900 ℃ hot corrosion weight gain curve of the traditional MCrAlY coating of the embodiment 4 and the comparative example 1 shows that the coating has excellent hot corrosion resistance, and the 900 ℃ hot corrosion weight gain is 0.3mg/cm for 200 hours 2 Is superior to the traditional MCrAlY coating.
As shown in fig. 5, the MCrAlY coatings of example 5, example 4 and comparative example 1 according to the present invention showed a weight gain after 200 hours of hot corrosion at 900 ℃, and the performance of example 5 was better than that of comparative example 1, but slightly worse than that of example 4. Thus, a/b can be said to be 1.5X10 -3 ～3×10 -3 When the modified MCrAlY coating is in the range, the hot corrosion performance of the modified MCrAlY coating is more excellent.
In conclusion, the modified MCrAlY coating, the preparation method thereof and the single crystal superalloy adopt trace Si elements to cooperatively and reasonably control the content of Al, cr and other elements, so that the prepared modified MCrAlY coating has excellent high-temperature oxidation resistance, the anti-stripping capability of an oxide film on the surface of the modified MCrAlY coating is obviously improved, and the self strength of the modified MCrAlY coating is improved. Reducing the cracking tendency and the stripping of an oxide film on the surface of the modified MCrAlY coatingDrop ability. After the components of the modified MCrAlY coating are optimized, the oxidation resistance of the modified MCrAlY coating is obviously improved, and the volume weight gain is reduced by 50 percent after the modified MCrAlY coating is oxidized for 200 hours at 1140 ℃. Meanwhile, the modified MCrAlY coating has excellent hot corrosion resistance, and the weight of the modified MCrAlY coating is increased by 0.3mg/cm after hot corrosion for 200 hours at 900 DEG C 2 . The modified MCrAlY coating provided by the invention can be suitable for manufacturing high-temperature protection of long-life high-reliability hot-end high-temperature parts in the fields of aviation, aerospace, energy and the like.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (12)
1. The modified MCrAlY coating is characterized by comprising the following chemical components in percentage by mass: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni.
2. A modified MCrAlY coating according to claim 1, characterized in that the chemical composition of the modified MCrAlY coating in mass percent is as follows: 23 to 28 weight percent of Cr, 13 to 18 weight percent of Co, 8 to 12 weight percent of Al, 0.8 to 1.3 weight percent of Y, 0.06 to 0.12 weight percent of Si and the balance of Ni.
3. A modified MCrAlY coating according to claim 2, wherein in the modified MCrAlY coating, the mass percentage of Si is a and the sum of the mass percentages of Al and Cr is b; wherein a/b=1.5×10 -3 ～3×10 -3 。
4. A modified MCrAlY coating according to any of claims 1-3, wherein in case the modified MCrAlY coating is deposited on the surface of a support;
the surface of the modified MCrAlY coating forms a compact oxide film with a pinning morphology so as to improve the anti-stripping capability of the oxide film on the surface of the modified MCrAlY coating;
and/or the P-B ratio of the oxide film on the surface of the modified MCrAlY coating is 1.5-1.8;
and/or the modified MCrAlY coating contains 55-60% of beta phase and 40-45% of gamma' phase by volume fraction so as to improve the high-temperature strength of the modified MCrAlY coating.
5. A method for preparing a modified MCrAlY coating according to any of claims 1 to 4, comprising the steps of:
preparing alloy powder: preparing a master alloy ingot, and preparing the master alloy ingot into alloy powder;
preparing a carrier containing a coating: pretreating a carrier, and depositing alloy powder on the pretreated carrier to obtain a carrier containing a coating;
preparing a modified MCrAlY coating: and (3) carrying out heat treatment on the carrier containing the coating to form a modified MCrAlY coating on the surface of the carrier.
6. The method for producing a modified MCrAlY coating according to claim 5, wherein in producing the alloy powder, a master alloy ingot is produced into the alloy powder by vacuum gas atomization.
7. The method for preparing a modified MCrAlY coating according to claim 6, wherein in preparing the support comprising the coating: the pretreatment comprises electrochemical degreasing and activation treatment of the carrier in sequence;
preferably, the carrier is subjected to surface treatment prior to pretreatment, wherein the surface treatment comprises polishing, wet blasting and ultrasonic treatment which are sequentially carried out.
8. The method for preparing a modified MCrAlY coating according to claim 5, wherein in preparing the support comprising the coating: pre-sputtering and cleaning the pretreated carrier;
preferably, the parameters of the pre-sputter clean are controlled as follows:
carrying out air steaming treatment on the carrier and the furnace chamber for 10-15 min to obtain a deposition environment atmosphere; after the alloy powder is loaded into the furnace, the furnace chamber is vacuumized to 7 multiplied by 10 < -3 > to 8 multiplied by 10 < -3 > Pa, the temperature is raised to 100 ℃ to 120 ℃, inert gas is filled into the vacuum chamber, and the air pressure is maintained to be 0.23 Pa to 0.25Pa; pre-sputtering cleaning is carried out under the conditions of bias voltage of-600V to-800V, duty ratio of 25-30 percent and arc current of 55-65A, sputtering voltage is controlled to be-15V to-20V, and sputtering time is controlled to be 3-5 min.
9. The method for preparing a modified MCrAlY coating according to claim 5, wherein in preparing the support comprising the coating: depositing alloy powder on the pretreated carrier by adopting an arc ion plating deposition technology to obtain a carrier containing a coating;
preferably, parameters of the arc ion plating deposition technique are controlled as follows:
the target base distance is 220 mm-280 mm, the arc voltage is 20V-25V, the arc current is 70A-90A, the pulse bias voltage is-150 to-300V, the duty ratio is 20-40%, the deposition temperature is 150-300 ℃, the deposition time is 2h-5h, and the coating thickness is 40 μm-60 μm.
10. The method for preparing a modified MCrAlY coating according to claim 5, wherein in preparing the modified MCrAlY coating: the heat treatment adopts vacuum heat treatment;
parameters of the vacuum heat treatment were controlled as follows:
adopting a vacuum gradient heat treatment mode, treating for 2-4 hours at the temperature of 650-800 ℃ and carrying out 2-4 hours at the temperature of 900-1000 ℃; the heating and cooling rates are controlled to be 1-3 ℃/min.
11. The material for preparing the modified MCrAlY coating is characterized by comprising the following chemical components in percentage by mass: 20 to 30 weight percent of Cr, 10 to 20 weight percent of Co, 5 to 15 weight percent of Al, 0.5 to 1.5 weight percent of Y, 0.05 to 0.15 weight percent of Si and the balance of Ni;
preferably, the mass percentage of Si is a, the Al andthe sum of the mass percentages of Cr is b; wherein a/b=1.5×10 -3 ～3×10 -3 。
12. A single crystal superalloy characterized in that the single crystal superalloy comprises a single crystal superalloy substrate and a modified MCrAlY coating deposited on the single crystal superalloy substrate; wherein the modified MCrAlY coating is the modified MCrAlY coating of any one of claims 1-4;
preferably, the single crystal superalloy substrate is a single crystal superalloy blade.
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