CN112708917A - Preparation method of micro-arc oxidation layer on surface of titanium alloy turbine blade - Google Patents
Preparation method of micro-arc oxidation layer on surface of titanium alloy turbine blade Download PDFInfo
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- CN112708917A CN112708917A CN202011536692.3A CN202011536692A CN112708917A CN 112708917 A CN112708917 A CN 112708917A CN 202011536692 A CN202011536692 A CN 202011536692A CN 112708917 A CN112708917 A CN 112708917A
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C25D11/026—Anodisation with spark discharge
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
The invention discloses a preparation method of a micro-arc oxidation layer on the surface of a titanium alloy turbine blade, which comprises the following steps of pretreating a titanium alloy sample; according to the selection principle of the titanium alloy micro-arc oxidation electrolyte, preparing a silicate micro-arc oxidation electrolyte, wherein the concentration of tantalum carbide particles in the electrolyte is 1-8 g/L; placing the pretreated aluminum alloy sample into the electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer with the diameter of 8-45 mu m on the surface of the pretreated aluminum alloy sample; according to the invention, after the titanium alloy turbine blade is pretreated, the titanium alloy turbine blade is put into silicate electrolyte containing nano-scale TaC powder, and micro-arc oxidation is carried out by matching with proper electrical parameters, so that the micro-arc oxidation layer doped with tantalum carbide can be prepared on the surface of the titanium alloy turbine blade.
Description
Technical Field
The invention belongs to the technical field of functional coatings on the surfaces of turbine blades, and particularly relates to a preparation method of a micro-arc oxidation layer on the surface of a titanium alloy turbine blade.
Background
Since the invention of the laite brother airplane, how to lighten the airframe without reducing the structural strength is one of the problems to be solved by the aviation industry. The Douglas aircraft and North American aviation in 1949 began using titanium alloys on DC-7 transport aircraft (engine compartment, insulation panels) and F-100 fighters, respectively, titanium, an alloy that combines the strength of steel with the light weight of aluminum, was dedicated by aircraft designers as an "aerial metal".
The titanium alloy has the characteristics of light weight (2/3 times of stainless steel), high strength (1.3 times of aluminum alloy, 1.6 times of magnesium alloy and 3.5 times of stainless steel), high heat-resistant strength (capable of working at the temperature of 450-500 ℃ for a long time), corrosion resistance (acid resistance, alkali resistance, atmospheric corrosion resistance and strong resistance to pitting corrosion and stress corrosion), and the like, and is not only tried to be used for non-bearing members such as a heat insulation board of a body of an airplane, an air guide cover and a tail cover, but also used for important bearing members such as a frame, a beam, a flap slide rail and the like. For example, the U.S. F-22 "bird of prey" fighter aircraft, titanium alloy structural components account for up to 41% by weight, much more than 24% of composite materials, 15% of aluminum alloys and 5% of steel, and have been applied to cabin unity bulkheads, fuselage sidewall panels, maneuvering brackets, horizontal tail back beams, hydraulic piping systems and fasteners (bolts, rivets), among others. Titanium alloy and titanium-based composite materials are also used in the matched F119 engine and the spray pipe and the like. The engine replaces the traditional steel component, and is more beneficial to improving the working efficiency.
In practical application, when the titanium alloy is used for replacing aluminum alloy with poor heat resistance and a steel structural member with larger weight at a high-temperature part of an airplane, a good weight reduction effect is realized, and the thrust-weight ratio of the thrust of an airplane engine to the gravity of the engine is favorably improved. And the titanium alloy has good corrosion resistance and low thermal expansion coefficient (9.41-10.03 multiplied by 10 < -6 >/DEG C), can provide better combination for structural members and fasteners, and meets the increasingly high requirements of the reliability and the service life of airplanes and engines. According to the concept of high performance and light weight, the titanium alloy is one of the currently extremely ideal aerospace materials.
During the high-speed operation of the aero-engine, the aero-engine blade generally has higher strength and corrosion resistance in the temperature range of 600-1000 ℃, and the titanium alloy can be subjected to the processes of surface integrity → cracking → peeling → severe peeling → total peeling along with the rise of temperature and the prolonging of oxidation time. Before the titanium alloy blade is used, a protective layer needs to be added for protection treatment.
The micro-arc oxidation is used as a surface ceramic treatment method, the ceramic layer and the substrate belong to metallurgical bonding, the bonding force is good, and the high-hardness ceramic layer can obviously improve the surface hardness, corrosion resistance, wear resistance and other properties of the titanium alloy. However, in order to improve the performances of the titanium alloy aircraft engine blade such as high temperature oxidation resistance, wear resistance and the like and achieve the aim of prolonging the service life of the aircraft engine, a better protective layer needs to be prepared.
Disclosure of Invention
The invention aims to provide a preparation method of a micro-arc oxidation layer on the surface of a titanium alloy turbine blade so as to improve the wear resistance and hardness of the micro-arc oxidation layer on the surface of the titanium alloy turbine blade.
The invention adopts the following technical scheme: a preparation method of a micro-arc oxidation layer on the surface of a titanium alloy turbine blade comprises the following steps:
pretreating a titanium alloy sample;
according to the selection principle of the titanium alloy micro-arc oxidation electrolyte, preparing a silicate micro-arc oxidation electrolyte, wherein the concentration of tantalum carbide particles in the electrolyte is 1-8 g/L;
placing the pretreated aluminum alloy sample into the electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer with the diameter of 8-45 mu m on the surface of the pretreated aluminum alloy sample;
wherein, the micro-arc oxidation electric parameters are as follows: the voltage is 430-510V, the frequency is 400-1000 Hz, the duty ratio is 3-40%, and the power-on time is 10-30 min.
Further, the concentration of sodium silicate in the electrolyte is 25-30 g/L.
Further, the content of Ta in the micro-arc oxidation layer is 0.3-3.6 at.%.
Further, the electrolyte consists of 30g/L of sodium silicate, 2g/L of potassium fluoride, 2g/L of potassium hydroxide, 1g/L of sodium carboxymethyl cellulose, 2g/L of nano TaC powder and deionized water.
Further, the electrolyte consists of 30g/L of sodium silicate, 1g/L of potassium fluoride, 5g/L of sodium hydroxide, 1g/L of sodium dodecyl benzene sulfonate, 5g/L of nano TaC powder and deionized water.
Further, the electrolyte comprises 25g/L of sodium silicate, 8g/L of sodium metaaluminate, 10g/L of sodium tetraborate, 4g/L of potassium hydroxide, 2g/L of sodium carboxymethyl cellulose, 5g/L of nano-scale TaC powder and deionized water.
Further, the electrolyte consists of 30g/L of sodium silicate, 3g/L of sodium metaaluminate, 3g/L of potassium fluoride, 2g/L of sodium hydroxide, 2g/L of sodium carboxymethyl cellulose, 8g/L of nano-scale TaC powder and deionized water.
The invention has the beneficial effects that: according to the invention, after the titanium alloy turbine blade is pretreated, the titanium alloy turbine blade is put into silicate electrolyte containing nano-scale TaC powder, and micro-arc oxidation is carried out by matching with proper electrical parameters, so that the micro-arc oxidation layer doped with tantalum carbide can be prepared on the surface of the titanium alloy turbine blade.
Drawings
FIG. 1 is a schematic structural microscopic view of a titanium alloy surface ceramic layer prepared by the method of the present invention;
FIG. 2 is a micro-topography and EDS energy spectrum result chart of a TaC-particle-free micro-arc oxidation ceramic layer doped on the surface of a titanium alloy;
FIG. 3 is a microstructure diagram of a micro-arc oxidation ceramic layer on the surface of the TaC particle-doped titanium alloy in example 1 and an EDS energy spectrum result diagram;
FIG. 4 is an XPS survey of ceramic layers prepared on the surface of a titanium alloy turbine blade and an XPS high resolution map of Ta elements;
FIG. 5 is a graph showing the comparison result of the surface hardness of the micro-arc oxidation ceramic layer with or without TaC particles doped on the surface of the titanium alloy;
FIG. 6 is a comparison graph of the surface friction coefficient curves of the micro-arc oxidation ceramic layer with or without TaC particles doped on the surface of the titanium alloy.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a preparation method of a micro-arc oxidation layer on the surface of a titanium alloy turbine blade, which comprises the following steps:
pretreating a titanium alloy sample; according to the selection principle of the titanium alloy micro-arc oxidation electrolyte, preparing a silicate micro-arc oxidation electrolyte, wherein the concentration of tantalum carbide particles in the electrolyte is 1-8 g/L (more preferably 2-6 g/L); placing the pretreated aluminum alloy sample into an electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer with the diameter of 8-45 mu m on the surface of the pretreated aluminum alloy sample; wherein, the micro-arc oxidation electric parameters are as follows: the voltage is 430-510V, the frequency is 400-1000 Hz, the duty ratio is 3-40%, and the power-on time is 10-30 min.
Further, the concentration of sodium silicate in the electrolyte is 25-30 g/L, and more specifically, the content of Ta in the micro-arc oxidation layer is 0.3-3.6 at.%.
In the embodiment, the pretreatment comprises degreasing, grinding, polishing and water washing so that the titanium alloy satisfies the micro-arc oxidation condition no matter the blade.
In a traditional electrolyte system of sodium silicate and sodium metaaluminate, the content of TaC particles in the electrolyte and micro-arc oxidation electrical parameters (including voltage and oxidation time) are regulated and controlled, so that the controllable regulation (0.4-3.6 at.%) of the content of Ta in a micro-arc oxidation ceramic layer can be realized, and part of the TaC particles can be converted into Ta under the action of high temperature and high pressure of micro-arc oxidation reaction2O5But Ta2O5Still has higher melting point (1872 ℃ plus or minus 10 ℃) and meets the use temperature range (600 ℃ to 1000 ℃) of the prior titanium alloy turbine blade. Specifically, deionized water is selected as a solvent for the electrolyte, so that chloride ions are prevented from being contained in the solvent.
The micro-arc oxidation technology is a new technology for directly growing ceramic films on the surfaces of light metals in situ, and is a surface modification technology for obtaining metal oxide ceramic layers under the combined action of thermochemistry, plasma chemistry and electrochemistry by placing valve metals such as Al, Mg, Ti and the like or alloys thereof in an electrolyte aqueous solution as an anode and generating spark discharge spots on the surfaces of the materials by an electrochemical method.
As shown in fig. 1, which is a microscopic structural diagram of the ceramic layer on the surface of the titanium alloy prepared by the method of the present invention, the TaC particle has a high melting point (3800 ℃), high hardness, high conductivity (thermal) and stable chemical properties, and the introduction of the TaC particle into the micro-arc oxidation ceramic layer of the titanium alloy can block the micro-pores generated during the micro-arc oxidation process to a certain extent, and improve the hardness, corrosion resistance and wear resistance of the ceramic layer.
The ceramic layer with high performance, hardness and wear resistance, which is suitable for the surface of the titanium alloy aircraft engine blade, prepared by the invention, can prolong the service life of the titanium alloy aircraft engine blade. The method takes the titanium alloy material as a matrix, and prepares the TaC-doped titanium oxide (containing a small amount of aluminum oxide) ceramic layer in a sodium metaaluminate electrolyte system by regulating and controlling micro-arc oxidation electrical parameters, and the ceramic layer has excellent protective performance. By regulating and controlling the concentration and the particle size of TaC in the electrolyte, a relatively flat micro-arc oxidation ceramic layer with high hardness can be prepared on the surface of the titanium alloy; the wear resistance and hardness of the micro-arc oxidation ceramic layer containing the TaC are obviously higher than those of the traditional titanium alloy micro-arc oxidation ceramic layer, the protective performance of the ceramic layer on the titanium alloy is enhanced, and the micro-arc oxidation ceramic layer containing the TaC has good wear resistance and corrosion resistance.
Example 1:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film layer with a thickness of 9 μm on the surface of the titanium alloy turbine blade specifically includes the following steps:
step 1: the processed titanium alloy sample is subjected to oil and grease removing processes, then is ground by different water sand paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the titanium alloy micro-arc oxidation electrolyte, sodium silicate is taken as the main (30g/L), and potassium fluoride (2g/L), potassium hydroxide (2g/L), sodium carboxymethylcellulose (1g/L) and TaC nano-scale powder (2g/L) are added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, and the thickness of a micro-arc oxidation layer generated on the surface of the titanium alloy is 9 microns by adjusting the voltage to be 450V, the frequency to be 1000Hz, the duty ratio to be 6 percent and the electrifying time to be 10 min.
Through detection, the content of Ta in the micro-arc oxidation layer is 0.3 at.%.
Example 2:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film layer with a thickness of 12 μm on the surface of the titanium alloy specifically includes the following steps:
step 1: the processed titanium alloy sample is subjected to oil and grease removing processes, then is ground by different water sand paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: adding sodium silicate (30g/L), potassium fluoride (1g/L), sodium hydroxide (5g/L), sodium dodecyl benzene sulfonate (1g/L) and TaC nano-grade powder (5g/L) according to the titanium alloy micro-arc oxidation electrolyte.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, and the thickness of a micro-arc oxidation layer generated on the surface of the titanium alloy is 12 microns by adjusting the voltage to be 450V, the frequency to be 1000Hz, the duty ratio to be 6 percent and the electrifying time to be 10 min. After detection, the content of Ta in the micro-arc oxidation layer is 0.9 at.%.
Example 3:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film with a thickness of 22 μm on the surface of the titanium alloy specifically includes the following steps:
step 1: the processed titanium alloy sample is subjected to oil and grease removing processes, then is ground by different water sand paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the titanium alloy, sodium silicate is taken as the main electrolyte (25g/L), and micro-arc oxidation electrolyte of sodium metaaluminate (8g/L), sodium tetraborate (10g/L), potassium hydroxide (4g/L), sodium carboxymethylcellulose (2g/L) and TaC nano-scale powder (5g/L) is added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, and the thickness of the titanium alloy surface is 22 micrometers by adjusting the voltage to be 500V, the frequency to be 700Hz, the duty ratio to be 10 percent and the electrifying time to be 20 min. The detection shows that the content of Ta in the obtained micro-arc oxidation layer is 2.1 at.%.
Example 4:
in this embodiment, the preparation of the 23 μm thick TaC micro-arc oxidized ceramic film on the surface of the titanium alloy specifically includes the following steps:
step 1: the processed titanium alloy sample is subjected to oil and grease removing processes, then is ground by different water sand paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the titanium alloy, sodium silicate is taken as the main electrolyte (30g/L), and micro-arc oxidation electrolyte of sodium metaaluminate (3g/L), potassium fluoride (3g/L), sodium hydroxide (2g/L), sodium carboxymethylcellulose (2g/L) and TaC nano-scale powder (8g/L) is added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, a micro-arc oxidation layer with the thickness of 23 mu m is generated on the surface of the titanium alloy by adjusting the voltage of 500V, the frequency of 700Hz, the duty ratio of 30 percent and the electrifying time of 30min, and the content of Ta in the micro-arc oxidation layer is 3.2 at.%.
Example 5:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film with a thickness of 8 μm on the surface of the titanium alloy specifically includes the following steps:
step 1: the processed titanium alloy sample is subjected to oil and grease removing processes, then is ground by different water sand paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the titanium alloy, sodium silicate is taken as the main electrolyte (20g/L), and sodium hydroxide (2g/L), sodium carboxymethylcellulose (1g/L) and TaC nano-scale powder (1g/L) are added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, a micro-arc oxidation layer with the thickness of 8 mu m is generated on the surface of the titanium alloy by adjusting the voltage of 430V, the frequency of 400Hz, the duty ratio of 3 percent and the electrifying time of 10min, and the content of Ta in the micro-arc oxidation layer is 0.3at percent through detection.
Example 6:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film layer with a thickness of 45 μm on the surface of the titanium alloy specifically includes the following steps:
step 1: the processed titanium alloy sample is subjected to oil and grease removing processes, then is ground by different water sand paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the titanium alloy, sodium silicate is taken as the main electrolyte (40g/L), and micro-arc oxidation electrolyte of sodium hexametaphosphate (5g/L), sodium hydroxide (10g/L), sodium carboxymethylcellulose (3g/L) and TaC nano-scale powder (10g/L) is added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, a micro-arc oxidation layer with the thickness of 45 mu m is generated on the surface of the titanium alloy by adjusting the voltage of 510V, the frequency of 1000Hz, the duty ratio of 40% and the electrifying time of 30min, and the content of Ta in the micro-arc oxidation layer is 3.6 at.%.
The special micro-arc oxidation ceramic layer prepared by the invention not only overcomes the problems of the traditional anodic oxidation and magnetron sputtering combination difference, the thin film layer and the like, but also improves the performance of the traditional micro-arc oxidation ceramic layer at one time, and the film layer has great application prospect in the aspect of titanium alloy turbine blades of aircraft engines. Meanwhile, if an electrolytic solution system and electrical parameters are prepared, the corrosion potential is reduced by doping TaC particles, the corrosion resistance of the titanium alloy is improved, and the film is expected to make further breakthrough with the propeller blades of the marine submarine.
In the invention, FIG. 2 is a micro-topography of a TaC-particle-free micro-arc oxidation ceramic layer doped on the surface of a titanium alloy and an EDS energy spectrum result diagram; fig. 3 is a microstructure diagram of the micro-arc oxidation ceramic layer on the surface of the TaC particle-doped titanium alloy in example 1 and an EDS energy spectrum result diagram, and it can be seen that the atomic percentage content of Ta in the micro-arc oxidation layer prepared in this example is 0.3. FIG. 4 is an XPS survey of ceramic layers prepared on the surfaces of the titanium alloys of examples 1 to 3 and an XPS high resolution plot of Ta elements, and peak fitting of Ta shows that Ta exists in the form of various compounds, indicating that introduced TaC exists inside the micro-arc oxidized ceramic layer; FIG. 5 is a graph showing the hardness comparison between the surface hardness of a micro-arc oxidized ceramic layer doped with TaC particles on the surface of a titanium alloy, wherein the hardness of the micro-arc oxidized ceramic layer doped with MAO particles is 378HV, the hardness of the micro-arc oxidized ceramic layer doped with MAO + TaC-1 is 558HV in example 1, and the hardness of the micro-arc oxidized ceramic layer doped with TaC particles is 623HV in example 2, thereby demonstrating that the hardness of the micro-arc oxidized ceramic layer doped with TaC is improved. FIG. 6 is a comparison graph of the surface friction coefficient curves of the micro-arc oxidation ceramic layers doped with TaC particles on the titanium alloy surfaces, and it can be seen from the graph that the highest TC4 titanium alloy has the largest friction coefficient, the middle TC4 titanium alloy has a friction coefficient smaller than that of the TC4 titanium alloy after the micro-arc oxidation, and TC4+ MAO + TaC is the friction coefficient of the micro-arc oxidation ceramic layers doped with TaC, which is smaller than that of the micro-arc oxidation ceramic layers not doped with TaC.
Claims (7)
1. The preparation method of the micro-arc oxidation layer on the surface of the titanium alloy turbine blade is characterized by comprising the following steps of:
pretreating a titanium alloy sample;
according to the selection principle of the titanium alloy micro-arc oxidation electrolyte, preparing a silicate micro-arc oxidation electrolyte, wherein the concentration of tantalum carbide particles in the electrolyte is 1-8 g/L;
placing the pretreated aluminum alloy sample into the electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer with the diameter of 8-45 mu m on the surface of the pretreated aluminum alloy sample;
wherein, the micro-arc oxidation electric parameters are as follows: the voltage is 430-510V, the frequency is 400-1000 Hz, the duty ratio is 3-40%, and the power-on time is 10-30 min.
2. The method for preparing the micro-arc oxidation layer on the surface of the titanium alloy turbine blade according to claim 1, wherein the concentration of the sodium silicate in the electrolyte is 25-30 g/L.
3. The method for preparing the micro-arc oxidation layer on the surface of the titanium alloy turbine blade according to claim 2, wherein the content of Ta in the micro-arc oxidation layer is 0.3 to 3.6 at.%.
4. The method for preparing the micro-arc oxidation layer on the surface of the titanium alloy turbine blade as claimed in claim 2 or 3, wherein the electrolyte comprises 30g/L of sodium silicate, 2g/L of potassium fluoride, 2g/L of potassium hydroxide, 1g/L of sodium carboxymethyl cellulose, 2g/L of nano-scale TaC powder and deionized water.
5. The method for preparing the micro-arc oxidation layer on the surface of the titanium alloy turbine blade as claimed in claim 2 or 3, wherein the electrolyte comprises 30g/L of sodium silicate, 1g/L of potassium fluoride, 5g/L of sodium hydroxide, 1g/L of sodium dodecyl benzene sulfonate, 5g/L of nano-scale TaC powder and deionized water.
6. The method for preparing the micro-arc oxidation layer on the surface of the titanium alloy turbine blade as claimed in claim 2 or 3, wherein the electrolyte comprises 25g/L sodium silicate, 8g/L sodium metaaluminate, 10g/L sodium tetraborate, 4g/L potassium hydroxide, 2g/L sodium carboxymethyl cellulose, 5g/L nano TaC powder and deionized water.
7. The method for preparing the micro-arc oxidation layer on the surface of the titanium alloy turbine blade as claimed in claim 2 or 3, wherein the electrolyte comprises 30g/L of sodium silicate, 3g/L of sodium metaaluminate, 3g/L of potassium fluoride, 2g/L of sodium hydroxide, 2g/L of sodium carboxymethyl cellulose, 8g/L of nano-scale TaC powder and deionized water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114107881A (en) * | 2021-11-15 | 2022-03-01 | 湖南弘辉科技有限公司 | High-speed fan blade machining process |
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| CN1623013A (en) * | 2002-03-27 | 2005-06-01 | 岛屿涂层有限公司 | Process and device for forming ceramic coatings on metals and alloys, and coatings produced by this process |
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| CN114107881A (en) * | 2021-11-15 | 2022-03-01 | 湖南弘辉科技有限公司 | High-speed fan blade machining process |
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