CN112981368B - Improved CVD equipment and preparation method for realizing co-infiltration deposition of aluminum-silicon coating by using improved CVD equipment - Google Patents
Improved CVD equipment and preparation method for realizing co-infiltration deposition of aluminum-silicon coating by using improved CVD equipment Download PDFInfo
- Publication number
- CN112981368B CN112981368B CN202110147304.0A CN202110147304A CN112981368B CN 112981368 B CN112981368 B CN 112981368B CN 202110147304 A CN202110147304 A CN 202110147304A CN 112981368 B CN112981368 B CN 112981368B
- Authority
- CN
- China
- Prior art keywords
- valve
- reaction chamber
- deposition reaction
- pipeline
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
- C23C12/02—Diffusion in one step
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/42—Silicides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Abstract
The invention discloses an improved CVD device and a preparation method for realizing co-infiltration deposition of an aluminum-silicon coating by using the improved CVD device; the invention relates to an improved CVD device applied to preparation of an aluminum-silicon co-infiltration coating, which comprises a reaction gas supply unit, an improved CVD unit and a waste gas treatment unit. The deposition reaction chamber is internally provided with a first area and a second area which have different temperature environments. When the improved CVD equipment is used for carrying out the improved CVD process processing, the temperature field of the first area is used for carrying out chemical vapor deposition, and the temperature field of the second area is used for carrying out in-situ vacuum diffusion annealing. Co-infiltrating and depositing an aluminum-silicon coating on a hot-end part of a turbine engine by adopting the improved CVD equipment and matching with the improved CVD process, wherein the oxidation weight gain of the prepared co-infiltrated and deposited aluminum-silicon coating is 1.5mg/cm at 1150 ℃ for 100h2～3.5mg/cm2And the antioxidant capacity is high.
Description
Technical Field
The invention relates to the technical field of Chemical Vapor Deposition (CVD), in particular to a technical scheme for improving the traditional CVD equipment and a preparation method for realizing the co-infiltration deposition of an aluminum-silicon coating on a hot-end part of a turbine engine by applying the improved CVD equipment to carry out the improved CVD process.
Background
In order to improve the oxidation resistance and corrosion resistance of hot end parts of aeroengines, an aluminide coating is generally coated on the surface of the hot end parts, for example, when a turbine blade is in service at high temperature, Al or Cr in the coated aluminide coating can be selectively oxidized to form a continuous compact protective oxide film, so that the high-temperature oxidation resistance and corrosion resistance of a matrix are improved. However, the hot corrosion resistance of the existing single aluminized coating can not meet the use requirement of hot end parts of the aero-engine, and the aluminide coating needs to be modified. The addition of a proper amount of Si to a single aluminide coating can increase the binding force between the coating and a substrate, effectively improve the oxidation resistance and the hot corrosion resistance of the coating, and prolong the service life of the coating. Therefore, the preparation technology of the aluminide coating and the modification technology thereof are very important.
Currently, the preparation of aluminide coating mainly includes two modes of embedding method and Chemical Vapor Deposition (CVD). When the blade coating of the turbine engine is prepared by embedding aluminizing, because the cooling channel of the inner cavity of the blade is fine and the shape of the blade is complex, the coating effect is poor because the embedding permeating agent cannot be placed in the cooling channel of the inner cavity, and the coating is difficult to effectively protect. CVD is a process technique in which a reaction substance is chemically reacted in a gaseous state to generate a solid substance which is deposited on the surface of a heated solid substrate, thereby producing a solid material. Compared with the traditional preparation method, the CVD method has strong process controllability, is more suitable for preparing the aluminide coating on the surface of the blade with a complex structure, does not need to be cleaned after deposition, and has no penetrating agent residue on the surface. However, the preparation of the modified aluminide coating by the current CVD equipment requires multi-step deposition, is expensive, and cannot realize the direct preparation of the modified aluminide coating.
Disclosure of Invention
In order to realize the processing of the anti-oxidation coating on the hot end part of the turbine engine by adopting the CVD process, the invention designs an improved CVD device. The invention relates to an improved CVD device for preparing an aluminum-silicon co-infiltration coating applied to a hot end part of a turbine engine, which comprises a reaction gas supply unit, an improved CVD unit and an exhaust gas treatment unit. The deposition reaction chamber is internally provided with a first area and a second area which have different temperature environments.
The invention also provides a preparation method of the aluminum-silicon co-infiltration coating of the hot end part of the turbine engine by using the improved CVD process method, wherein when the improved CVD process is carried out by using improved CVD equipment, the chemical vapor deposition is carried out in a temperature field of one area, and the in-situ vacuum diffusion annealing is carried out in a temperature field of the second area. MiningThe improved CVD equipment is matched with the CVD process to co-infiltrate and deposit the aluminum-silicon coating on the hot end part of the turbine engine, and the prepared co-infiltrated and deposited aluminum-silicon coating has the oxidation weight gain of 1.5mg/cm at 1150 ℃ for 100h2～3.5mg/cm2And the antioxidant capacity is high.
The invention relates to a method for processing an aluminum-silicon co-infiltration coating of a hot-end part of a turbine engine by improving a CVD (chemical vapor deposition) process, which is characterized by comprising the following steps of:
selecting materials;
a siliconizing source placed in the siliconizing source container (1);
an aluminizing agent disposed in the crucible (64);
placing an IC21 substrate on the sample holder (63), and placing the sample holder 13 loaded with the IC21 substrate in a heating first area;
step two, treating the CVD process in a protective atmosphere environment;
vacuumizing, namely closing the AA valve (13), the BA valve (21) and the CB valve six (32), opening the BB valve (22), the CA valve (31) and the DA valve (42), starting a mechanical pump (41), and vacuumizing the deposition reaction chamber (6) and an air duct; up to 10 in the deposition reaction chamber (6)－2After the vacuum degree of Pa, closing the DA valve (42), closing the mechanical pump (41) and finishing vacuumizing;
filling protective atmosphere, opening a BA valve (21), starting a protective gas device (20), introducing high-purity nitrogen, opening a CB valve (32) after the furnace pressure is equal to or slightly greater than the atmospheric pressure, and finishing protective atmosphere filling after introducing gas for 5-15 min;
repeating the steps of vacuumizing and processing by filling protective atmosphere at least twice to ensure that the chemical vapor deposition process is in a high-purity nitrogen protection state;
step three, processing the required environment temperature by the CVD process;
heating a silicon source, and setting the frequency of the induction coil (15) to ensure that the temperature in the water bath 11 reaches 50-60 ℃, and keeping the temperature for 10 min;
heating the deposition reaction chamber (6), heating the deposition reaction chamber (6) by adopting a Mo-Si resistance heating rod, heating the temperature of one zone to 1180 ℃, and then preserving the heat; then heating the second area to 1000 ℃ and preserving heat;
the temperature rise rate of the first zone temperature is 5-10 ℃/min;
the temperature rise rate of the second zone temperature is 5-10 ℃/min;
step four, carrying out co-permeation deposition on the silicon-aluminum coating by using a CVD (chemical vapor deposition) process;
closing the BA valve (21), pushing the push rod (5), pushing the crucible (64) into the second zone for heating, opening the AA valve (13), starting the carrier gas device (10), starting to introduce silicon tetrachloride gas and high-purity nitrogen, and adjusting the carrier gas device (10) so as to fix the gas inlet flow to be 0.1-0.5L/min; adjusting the ventilation time according to the design thickness of the coating; after the ventilation time is up, closing the AA valve (13), the BB valve (22) and the CB valve (32), and pulling out the push rod (5) to enable the crucible (64) to be far away from the second area;
step five, in-situ vacuum diffusion annealing;
after the silicon-aluminum coating is deposited by the co-permeation, a mechanical pump (41) is opened, a DA valve (42) is opened, and residual reaction gas in a deposition reaction chamber (6) is pumped away; closing the CA valve (31), adjusting the heating temperature of the first zone to 1200 ℃, and carrying out in-situ vacuum diffusion annealing for 5-5 minutes;
step six, waste gas recovery treatment;
after the annealing is finished, opening a BA valve (21) and a BB valve (22), introducing high-purity nitrogen, and opening a CB valve (32) until the temperature of the deposition reaction chamber (6) is reduced to room temperature after the pressure of the deposition reaction chamber (6) reaches the atmospheric pressure; closing the BA valve (21) and the CA valve (32); and opening an end cover on the deposition reaction chamber (6) to take out a sample.
The improved CVD equipment designed by the invention can manufacture the deposition reaction chamber (6) in a single piece according to the size of the hot end part of the turbine engine to be processed. The size of the circular ring joint of the cylindrical joint section and the external flange plate is kept. And sealing gaskets are adopted between the flanges for sealing. Meanwhile, the feeding and the discharging are completed through the opening and the closing of the flange plates.
Drawings
FIG. 1 is a flow chart of an improved CVD apparatus of the present invention.
FIG. 2 is a view showing the external structure of the improved deposition reaction chamber of the present invention.
FIG. 2A is an external block diagram of another perspective view of the improved deposition chamber of the present invention.
FIG. 2B is a block diagram of the internal layout of the improved deposition chamber of the present invention.
FIG. 2C is an exploded view of the improved deposition chamber of the present invention.
FIG. 3 is a graph of the performance of example 1 as processed by an improved CVD process using the improved CVD apparatus of the present invention; (a) the section SEM appearance of the prepared state of the coating with 30 percent of Al and 5 percent of Si and the element components of Al and Si are distributed along the section. Fig. 3 shows the cross-sectional structure and element distribution of the 30% Al-5% Si coating, with the Al element distributed in a gradient along the cross-section, with the highest content at the surface, 30 a.t%; the Si element is distributed more uniformly, and the content is 5a.t percent.
FIG. 4 is a graph of the oxidation weight gain of example 1 processed by the improved CVD apparatus of the present invention for an improved CVD process. In the figure, oxidation weight gain curves at 1150 ℃ before and after the substrate IC21 alloy is subjected to the co-infiltration of a 30% Al-5% Si coating, oxidation weight gain of the IC21 alloy is obviously reduced after the IC21 alloy is subjected to the co-infiltration of the AlSi coating, and oxidation weight gain is 57mg/cm at 1150 ℃ for 100h2Reduced to 2mg/cm2The oxidation resistance is obviously improved.
FIG. 5 is a graph of the performance of example 2 processed by an improved CVD process using the improved CVD apparatus of the present invention; (a) the sectional SEM appearance of the prepared state of the 35 percent Al-2 percent Si coating and (b) the elemental compositions of Al and Si are distributed along the section. Electron microscope scan and composition profile along the cross-section. Fig. 5 shows the cross-sectional structure and element distribution of the 35% Al-2% Si coating, with the Al element distributed in a gradient along the cross-section, with the highest content at the surface, 35 a.t%; the Si element is distributed more evenly, and the average content is 2a.t percent.
FIG. 6 is a graph of the oxidation weight gain of example 2 processed by the improved CVD apparatus of the present invention. (a) Oxidation weight gain curve at 1150 ℃ before and after 35% Al-2% Si coating co-infiltration of IC21 alloy; (b) oxidation weight gain curves for 35% Al-2% Si coating and 30% Al-5% Si coating. The graph shows the 1150 ℃ oxidation weight gain curves for a 35% Al-2% Si coating versus the 30% Al-5% Si coating of example 1. 35 percent of Al-2 percent of Si coating at 1150 ℃ and the oxidation weight gain of 100h is 1.8mg/cm22.2mg/cm of coating of less than 30% Al-5% Si2Of the compositionThe AlSi coating has better oxidation resistance.
FIG. 7 is a graph of example 3 performance for an improved CVD process using an improved CVD apparatus of the present invention; (a) the section SEM appearance of the prepared state of the 25 percent Al-3 percent Si coating and (b) the elemental compositions of Al and Si are distributed along the section. Electron microscope scan and composition profile along the cross-section. FIG. 7 is a cross-sectional structure and element distribution of a 25% Al-3% Si coating, wherein Al is distributed in a gradient manner along the cross section, and the content of Al is highest at the surface and is 25-30 a.t%; the Si element is distributed more evenly, and the average content is 3a.t percent.
FIG. 8 is a graph of the oxidation weight gain of example 3 processed by an improved CVD process using the improved CVD apparatus of the present invention. (a) Oxidation weight gain curve at 1150 ℃ before and after 25% Al-3% Si coating is co-infiltrated by IC21 alloy; (b) oxidation weight gain curves for 25% Al-3% Si coating, 35% Al-2% Si coating, and 30% Al-5% Si coating. The oxidation weight gain curve at 1150 ℃ for the 25% Al-3% Si coating in FIG. 8. The oxidation weight gain is 3.5mg/cm at 1150 ℃ for 100h2. The AlSi coating of the composition has better oxidation resistance than the coatings in examples 1 and 2 before 70 hours, and has sharply reduced oxidation resistance after the oxidation time is more than 70 hours, which is inferior to the coatings in examples 1 and 2.
| 1. |
11. Water bath pot | AA pipeline | |
| AA valve | AB lines | BA pipeline | |
| BA valve | BB valve | 3.CA pipeline | |
| CA valve | CB | DA pipeline | |
| 41. Mechanical | DA valve | 42 | 5. Push |
| 6. |
6A. front panel | 6A1. front group Mo-Si |
|
| 6B rear panel | 6B1 rear group Mo-Si |
6C. upper panel | |
| 6C1.FA via | 6C2.FB through |
6D right end cylinder joint | |
| |
601A. connecting |
601B. right countersunk head cavity | |
| FC through |
FD vias | FB flange | 602 |
| 602A. connecting |
602B. countersunk |
603, |
|
| 603A. connecting |
603B left end countersunk head cavity | 603c.fe via | |
| |
604A. connecting |
604B, countersunk ring segment | |
| 61.FA mullite end cap | FA array microwell | FB |
|
| 62A. |
63. |
64. Crucible pot | |
| 65.FA thermocouple | 66. |
10. |
|
| 20. |
30. Exhaust gas collecting device |
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
First, improved CVD apparatus
Generally, a CVD apparatus may generally consist of a gas source control component, a deposition reaction chamber, a deposition temperature control unit, a vacuum exhaust, and a pressure control component.
The invention designs an improved CVD system, which improves a deposition reaction chamber in a first aspect; the second aspect is an improvement to the silicon source line for carrier gas transport, referred to as the reactant gas supply unit.
Referring to fig. 1, the invention relates to an improved CVD system for producing an sial-co-coating for hot end parts of a turbine engine, comprising a reactant gas supply unit, an improved CVD unit and an exhaust gas treatment unit.
Reaction gas supply unit
In the invention, the reaction gas supply unit comprises a gas carrying device 10, a protective gas device 20, a siliconizing source container 1, a gas carrying channel and a protective channel.
The siliconizing source container 1 is connected to the BA line 2 via an AA line 12, and the siliconizing source container 1 is connected to the carrier gas device 10 via an AB line 14.A silicon source (silicon tetrachloride SiCl) is placed in the silicon-permeated source container 14) The siliconizing source container 1 is placed in a water bath 11, and the water bath 11 is heated by an induction coil 15. The power of the induction coil 15 is 100-350W/220V. An AA valve 13 is arranged on the AA pipeline 12.A BA pipe 2 is connected between the shielding gas device 20 and the FC through hole 601C on the right countersunk head cavity 601B of the FA flange 601. The BA line 2 is provided with a BA valve 21 and a BB valve 22. Between the BA valve 21 and the BB valve 22 is one end of the AA line 12.
In the invention, a reaction gas generating part is composed of a water bath 11, an induction coil 15 and a siliconizing source container 1. A water bath 11 provides heating for the siliconized source vessel 1.
In the present invention, the gas flow rate is controlled by the carrier gas device 10.
In the present invention, the shielding gas device 20 provides inert gas shielding for the prepared sample and provides cleaning gas for the modified CVD unit after the preparation is finished.
Improved CVD unit
In the invention, the improved CVD unit comprises a deposition reaction chamber 6, 4 flange plates (601, 602, 603 and 604), a mullite end cover, a sample holder 63, a crucible 64, an FA thermocouple 65 and an FB thermocouple 66.
Referring to FIGS. 2, 2A, 2B and 2C, the deposition chamber 6 is a corundum tube (Al)2O3). In the deposition reaction chamber 6The core is a cavity; a sample holder 63 and a crucible 64 are placed in the cavity. The sample holder 63 is mounted with a base. An aluminizing agent is placed in the crucible 64.
The front panel 6A of the deposition reaction chamber 6 is provided with a front set of Mo-Si resistance heating rods 6A1.
The rear panel 6B of the deposition reaction chamber 6 is provided with a rear set of Mo-Si resistance heating rods 6B1. The combination of the front group of Mo-Si resistance heating rods 6A1 and the rear group of Mo-Si resistance heating rods 6B1 realizes the convection heating of the internal environment of the cavity of the deposition reaction chamber 6, and is beneficial to the uniform deposition of the aluminum-silicon coating material on the substrate. The Mo-Si resistance heating rods arranged in an array mode are adopted, so that a single Mo-Si resistance heating rod can be heated respectively, temperature regulation of different areas in the cavity is achieved, different temperature environments of the different areas are achieved, and the cavity is at least provided with temperature fields of the first area and the second area.
The upper panel 6C of the deposition reaction chamber 6 is provided with FA via holes 6C1 and FB via holes 6C2. The FA through hole 6C1 is used for the sensitive end of the FA thermocouple 65 to pass through and is arranged in the second area. FB via 6C2 is for the sensitive end of FB thermocouple 66 to pass through and is located in one area.
The right end of the deposition reaction chamber 6 is provided with a right cylindrical joint 6D, and the right cylindrical joint 6D is sleeved on the countersunk ring section 602B of the FB flange 602.
The left end of the deposition reaction chamber 6 is a left end cylindrical joint which is sleeved on the countersunk ring section 604B of the FD flange 604.
One end of the FA flange plate 601 is a connecting plate 601A, and the other end of the FA flange plate 601 is a right countersunk head cavity 601B; an FA mullite end cover 61 is arranged in the right countersunk head cavity 601B; the right countersunk cavity 601B is provided with an FC through hole 601C, FD through hole 601D. The FC through hole 601C is used to mount the other end of the BA line 2, and one end of the BA line 2 is connected to the shielding gas device 20. The FD via hole 601D is used to mount the push rod 5. One end of the push rod 5 is sequentially threaded into the threaded hole in the side wall of the crucible 64 after passing through the through hole in the FD through hole 601D, FA mullite end cap 61. The push rod 5 is in threaded connection with the crucible 64. The position of the crucible 64 in the cavity of the deposition reaction chamber 6 is adjusted by the axial translation of the pusher rod 5 along the deposition reaction chamber 6.
One end of the FB flange 602 is a connection disc 602A, and the other end of the FB flange 602 is a countersunk circular ring section 602B; a connecting disc 602A of the FB flange plate 602 is fixed with a connecting disc 601A of the FA flange plate 601 through the matching of a screw and a nut; the countersunk ring section 602B of the FB flange 602 is sleeved on the right cylindrical joint 6D of the deposition reaction chamber 6.
One end of the FC flange plate 603 is a connecting disc 603A, and the other end of the FC flange plate 603 is a left countersunk cavity 603B; an FB mullite end cover 62 is arranged in the left countersunk head cavity 603B; the left countersunk cavity 603B is provided with an FE via 603C. The FE through hole 603C is used to mount the other end of the CA pipe 3, and one end of the CA pipe 3 is connected to the exhaust gas collection device 30.
One end of the FD flange 604 is a connecting disc 604A, and the other end of the FD flange 604 is a countersunk circular ring section 604B; the connecting disc 604A of the FD flange plate 604 and the connecting disc 603A of the FC flange plate 603 are fixed through the matching of screws and nuts; the countersunk ring section 604B of the FD flange 604 is sleeved on the left end cylindrical joint of the deposition reaction chamber 6.
Referring to fig. 2B and 2C, the FA mullite end cover 61 is provided with FA array micropores 61A and a through hole for the push rod 5 to pass through. The FA array micro-holes 61A facilitate uniform entry of the shielding gas into the inner cavity of the deposition reaction chamber 6.
Referring to fig. 2B and 2C, FB array micropores 62A are formed in the FB mullite end cap 62. The FB array micropores 62A facilitate the uniform collection of the reaction gas in the inner cavity of the deposition reaction chamber 6 by the exhaust gas collecting device 30.
In the present invention, the deposition reaction chamber 6 is divided into a first heating zone and a second heating zone.
In the present invention, the sample holder 63 is used to hold a sample substrate to be deposited.
In the present invention, the crucible 64 is used to hold the aluminizing agent.
In the present invention, the temperature environment of the cavity of the deposition reaction chamber 6 is provided using a front set of Mo-Si resistance heating rods 6A1 provided on the front panel 6A and a rear set of Mo-Si resistance heating rods 6B1 provided on the rear panel 6B. The power of the Mo-Si resistance heating rod is 150 kW/380V.
In the invention, the FA mullite end cover 61 and the FB mullite end cover 62 are obtained by processing mullite made of porous materials. The aim is to uniformly disperse the inlet air flow to obtain a stable air flow field in the deposition reaction chamber 6, thereby ensuring the uniformity of the co-permeation deposition silicon-aluminum coating.
Exhaust gas collection unit
In the present invention, the exhaust gas treatment unit includes an exhaust gas collecting device 30, a mechanical pump 41, and a gas collecting channel.
One end of the CA pipeline 3 is installed on the FE through hole 603C on the left end countersunk cavity 603B of the FC flange 603, the other end of the CA pipeline 3 is installed on the exhaust gas collection device 30, the CA valve 31 and the CB valve 32 are installed on the CA pipeline 3, one end of the DA pipeline 4 is installed between the CA valve 31 and the CB valve 32, and the mechanical pump 41 is installed at the other end of the DA pipeline 4. The DA pipeline 4 is provided with a DA valve 42.
In the present invention, the mechanical pump 41 is used to vacuumize the deposition chamber 6 and the pipeline, so as to reduce the oxygen content in the deposition chamber 6 and the pipeline.
In the present invention, the off-gas collecting means 30 is used to absorb a solution of polluting products generated during the manufacturing process.
Second part, CVD process using modified CVD equipment
Selecting materials;
a silicon-permeating source is arranged in the silicon-permeating source container 1.
An aluminizing agent placed in the crucible 64.
The sample holder 63 was loaded with the IC21 matrix and the sample holder 13 loaded with the IC21 matrix was placed in a heating zone.
In the present invention, the IC21 comprises, in terms of mass fraction, 7.6 to 8.3 wt% of Al, 1.5 to 2.5 wt% of Cr, 9.0 to 13.0 wt% of Mo, 0.5 to 1.5 wt% of Re, 2.4 to 4.0 wt% of Ta, 0.01 wt% of Y, and the balance Ni.
Step two, treating the CVD process in a protective atmosphere environment;
and (3) vacuumizing, closing the AA valve 13, the BA valve 21 and the CB valve six 32, opening the BB valve 22, the CA valve 31 and the DA valve 42, starting the mechanical pump 41, and vacuumizing the deposition reaction chamber 6 and the ventilation pipeline. A certain vacuum degree (10) is reached in the deposition reaction chamber 6－2Pa) is followed by closingThe DA valve 42 closes the mechanical pump 41, and the vacuum pumping is completed.
And (3) filling protective atmosphere, opening a BA valve 21, opening a protective gas device 20, introducing high-purity nitrogen, opening a CB valve 32 after the furnace pressure is equal to or slightly greater than the atmospheric pressure, and finishing the filling of the protective atmosphere after a period of time (5-15 min) of gas introduction.
The steps of vacuumizing and filling protective atmosphere are repeated at least twice to ensure that the chemical vapor deposition process is in a high-purity nitrogen protection state.
Step three, processing the required environment temperature by the CVD process;
heating the silicon source, and setting the frequency of the induction coil 15 to ensure that the temperature in the water bath 11 reaches 50-60 ℃, and keeping the temperature for 10 min.
Heating the deposition reaction chamber 6, heating the deposition reaction chamber 6 by adopting a Mo-Si resistance heating rod, heating the temperature of one zone to 1180 ℃, and then preserving the heat; then the temperature of the second area is heated to 1000 ℃ and then is kept.
The temperature rise rate of the first zone temperature is 5-10 ℃/min.
The temperature rise rate of the second zone temperature is 5-10 ℃/min.
Step four, carrying out co-permeation deposition on the silicon-aluminum coating by using a CVD (chemical vapor deposition) process;
closing the BA valve 21, pushing the push rod 5, pushing the crucible 64 into the second zone for heating, opening the AA valve 13, starting the carrier gas device 10, starting to introduce silicon tetrachloride gas and high-purity nitrogen, and adjusting the carrier gas device 10 so as to fix the gas inflow at a certain value (the gas inflow is 0.1-0.5L/min); adjusting the ventilation time according to the design thickness of the coating; after the aeration time is reached, the AA valve 13, the BB valve 22 and the CB valve 32 are closed, and the push rod 5 is pulled out to enable the crucible 64 to be far away from the two areas.
Step five, in-situ vacuum diffusion annealing;
after the silicon-aluminum coating is deposited by the co-permeation, a mechanical pump 41 is started, a DA valve 42 is opened, and residual reaction gas in the deposition reaction chamber 6 is pumped away; closing the CA valve 31, adjusting the heating temperature of the first zone to 1200 ℃, and carrying out in-situ vacuum diffusion annealing for 5-5 minutes;
step six, waste gas recovery treatment;
after the annealing is finished, opening the BA valve 21 and the BB valve 22, introducing high-purity nitrogen, and opening the CB valve 32 after the pressure of the deposition reaction chamber 6 reaches the atmospheric pressure until the deposition reaction chamber 6 is cooled to the room temperature; the BA valve 21 and CA valve 32 are closed. The end cap on the deposition reaction chamber 6 was opened to take out the sample.
Example 1 preparation of 30% Al-5% Si Coinfiltration coating
Selecting materials;
the silicon-permeating source arranged in the silicon-permeating source container 1 is silicon tetrachloride SiCl4。
The aluminising agent placed in crucible 64 was 80 w.t.% Al-20 w.t.% NaF. The aluminizing agent is powder with the granularity of 50-120 mu m.
An alloy of type IC21 was placed on the sample holder 63, and the sample holder 63 loaded with the IC21 alloy was placed in the heating zone.
Step two, treating the CVD process in a protective atmosphere environment;
and (3) vacuumizing, closing the AA valve 13, the BA valve 21 and the CB valve six 32, opening the BB valve 22, the CA valve 31 and the DA valve 42, starting the mechanical pump 41, and vacuumizing the deposition reaction chamber 6 and the ventilation pipeline. A certain vacuum degree (1X 10) is achieved in the deposition reaction chamber 6－2Pa), the DA valve 42 is closed, the mechanical pump 41 is closed, and the evacuation is completed.
And (3) filling protective atmosphere, opening a BA valve 21, opening a protective gas device 20, introducing high-purity nitrogen, opening a CB valve 32 after the furnace pressure is equal to or slightly greater than the atmospheric pressure, and finishing the filling of the protective atmosphere after a period of time (15min) of gas introduction.
The steps of vacuumizing and filling protective atmosphere are repeated at least twice to ensure that the chemical vapor deposition process is in a high-purity nitrogen protection state.
Step three, processing the required environment temperature by the CVD process;
heating silicon source, setting frequency of induction coil 15 to make temperature in water bath 11 reach 55 deg.C, and keeping constant temperature for 10 min.
Heating the deposition reaction chamber 6, heating the deposition reaction chamber 6 by adopting a Mo-Si resistance heating rod, heating the temperature of one zone to 1180 ℃, and then preserving the heat; then the temperature of the second area is heated to 1000 ℃ and then is kept.
The rate of temperature rise in the first zone temperature was 10 deg.C/min.
The temperature rise rate of the second zone temperature is 5 ℃/min.
Step four, carrying out co-permeation deposition on the silicon-aluminum coating by using a CVD (chemical vapor deposition) process;
closing the BA valve 21, pushing the push rod 5, pushing the crucible 64 into the second zone for heating, opening the AA valve 13, starting the carrier gas device 10, starting to introduce silicon tetrachloride gas and high-purity nitrogen, and adjusting the carrier gas device 10 so as to fix the gas inflow at a certain value (the gas inflow is 0.5L/min); adjusting the ventilation time according to the design thickness of the coating; after the aeration time is reached, the AA valve 13, the BB valve 22 and the CB valve 32 are closed, and the push rod 5 is pulled out to enable the crucible 64 to be far away from the two areas.
Step five, in-situ vacuum diffusion annealing;
after the silicon-aluminum coating is deposited by the co-permeation, a mechanical pump 41 is started, a DA valve 42 is opened, and residual reaction gas in the deposition reaction chamber 6 is pumped away; closing the CA valve 31, adjusting the heating temperature of the first zone to 1200 ℃, and carrying out in-situ vacuum diffusion annealing for 15 minutes;
step six, waste gas recovery treatment;
after the annealing is finished, opening the BA valve 21 and the BB valve 22, introducing high-purity nitrogen, and opening the CB valve 32 after the pressure of the deposition reaction chamber 6 reaches the atmospheric pressure until the deposition reaction chamber 6 is cooled to the room temperature; the BA valve 21 and CA valve 32 are closed. The end cap on the deposition reaction chamber 6 is opened to take out the sample.
Step seven, performance test;
the surface cross-sectional morphology of the sample was observed using a field emission scanning electron microscope (Zeiss Supra 55) and the composition change in the thickness direction was analyzed. The constant-temperature oxidation experimental method comprises the following steps: the sample was put into Al with a lid2O3The crucible is put into a resistance furnace at 1150 ℃ together for cooling-heating circulation oxidation. The cycle of the cold and heat circulation is that the temperature is kept at 1150 ℃ for 50min and then the air cooling is carried out for 10min to the room temperature. The crucible was removed and cooled to room temperature every 10h, after which the samples were weighed for recording the change in oxidative weight gain of the samples.
Fig. 3 shows the cross-sectional structure and element distribution of the 30% Al-5% Si coating, with the Al element distributed in a gradient along the cross-section, with the highest content at the surface, 30 w.t.%; the Si element is distributed more uniformly, and the content is 5 w.t.%.
FIG. 4 is an oxidation weight gain curve at 1150 ℃ before and after the alloying of the IC21 alloy with 30% Al-5% Si coating, the oxidation weight gain of the IC21 alloy after the alloying of the AlSi coating is obviously reduced, the oxidation weight gain is 57mg/cm at 1150 ℃ for 100h2Reduced to 2mg/cm2The oxidation resistance is obviously improved.
Example 2 preparation of 35% Al-2% Si Coinfiltration coating
Selecting materials;
the silicon-permeating source arranged in the silicon-permeating source container 1 is silicon tetrachloride SiCl4。
The aluminising agent placed in crucible 64 was 80 w.t.% Al-20 w.t.% NaF. The aluminizing agent is powder with the granularity of 50-120 mu m.
An alloy of type IC21 was placed on the sample holder 63, and the sample holder 13 loaded with IC21 was placed in the heating zone.
Step two, treating the CVD process in a protective atmosphere environment;
and (3) vacuumizing, closing the AA valve 13, the BA valve 21 and the CB valve six 32, opening the BB valve 22, the CA valve 31 and the DA valve 42, starting the mechanical pump 41, and vacuumizing the deposition reaction chamber 6 and the ventilation pipeline. A certain vacuum degree (1X 10) is achieved in the deposition reaction chamber 6－2Pa), the DA valve 42 is closed, the mechanical pump 41 is closed, and the evacuation is completed.
And (3) filling protective atmosphere, opening a BA valve 21, opening a protective gas device 20, introducing high-purity nitrogen, opening a CB valve 32 after the furnace pressure is equal to or slightly greater than the atmospheric pressure, and finishing the filling of the protective atmosphere after a period of time (15min) of gas introduction.
The steps of vacuumizing and filling protective atmosphere are repeated at least twice to ensure that the chemical vapor deposition process is in a high-purity nitrogen protection state.
Step three, processing the required environment temperature by the CVD process;
heating silicon source, setting frequency of induction coil 15 to make temperature in water bath 11 reach 50 deg.C, and keeping constant temperature for 10 min.
Heating the deposition reaction chamber 6, heating the deposition reaction chamber 6 by adopting a Mo-Si heating rod, heating the first zone to 1180 ℃, and then preserving the heat; then the temperature of the second area is heated to 1000 ℃ and then is kept.
The rate of temperature rise in the first zone temperature was 10 deg.C/min.
The temperature rise rate of the second zone temperature is 10 ℃/min.
Step four, carrying out co-permeation deposition on the silicon-aluminum coating by using a CVD (chemical vapor deposition) process;
closing the BA valve 21, pushing the push rod 5, pushing the crucible 64 into the second zone for heating, opening the AA valve 13, starting the carrier gas device 10, starting to introduce silicon tetrachloride gas and high-purity nitrogen, and adjusting the carrier gas device 10 so as to fix the gas inflow at a certain value (the gas inflow is 0.2L/min); adjusting the ventilation time according to the design thickness of the coating; after the aeration time is reached, the AA valve 13, the BB valve 22 and the CB valve 32 are closed, and the push rod 5 is pulled out, so that the crucible 64 is far away from the two areas.
Step five, in-situ vacuum diffusion annealing;
after the silicon-aluminum coating is deposited by the co-permeation, a mechanical pump 41 is started, a DA valve 42 is opened, and residual reaction gas in the deposition reaction chamber 6 is pumped away; closing the CA valve 31, adjusting the heating temperature of the first zone to 1200 ℃, and carrying out in-situ vacuum diffusion annealing treatment for 10 minutes;
step six, waste gas recovery treatment;
after the annealing is finished, opening the BA valve 21 and the BB valve 22, introducing high-purity nitrogen, and opening the CB valve 32 after the pressure of the deposition reaction chamber 6 reaches the atmospheric pressure until the deposition reaction chamber 6 is cooled to the room temperature; the BA valve 21 and CA valve 32 are closed. The end cap on the deposition reaction chamber 6 was opened to take out the sample.
Step seven, performance test;
fig. 5 shows the cross-sectional structure and element distribution of the 35% Al-2% Si coating, with the Al element distributed in a gradient along the cross-section, with the highest content at the surface, 35 w.t.%; the Si element is distributed more uniformly, and the average content is 2 w.t.%.
FIG. 6 is a graph of the 1150 ℃ oxidation weight gain of 35% Al-2% Si coating versus 30% Al-5% Si coating. 35 percent of Al-2 percent of Si coating at 1150 ℃ and the oxidation weight gain of 100h is 1.8mg/cm2Is less than 32.2mg/cm of 0% Al-5% Si coating2The AlSi coating of the component has better oxidation resistance.
Example 3 preparation of 25% Al-3% Si Coinfiltration coating
Selecting materials;
the silicon-permeating source arranged in the silicon-permeating source container 1 is silicon tetrachloride SiCl4。
The aluminising agent placed in the crucible 64 was 95 w.t.% Al-5 w.t.% NaF.
The sample holder 63 was placed with the type IC alloy, and the sample holder 13 loaded with the IC21 alloy was placed in the heating zone.
Step two, treating the CVD process in a protective atmosphere environment;
and (3) vacuumizing, closing the AA valve 13, the BA valve 21 and the CB valve six 32, opening the BB valve 22, the CA valve 31 and the DA valve 42, starting the mechanical pump 41, and vacuumizing the deposition reaction chamber 6 and the ventilation pipeline. A certain vacuum degree (1X 10) is achieved in the deposition reaction chamber 6－2Pa), the DA valve 42 is closed, the mechanical pump 41 is closed, and the evacuation is completed.
And (3) filling protective atmosphere, opening a BA valve 21, opening a protective gas device 20, introducing high-purity nitrogen, opening a CB valve 32 after the furnace pressure is equal to or slightly greater than the atmospheric pressure, and finishing the filling of the protective atmosphere after introducing gas for a period of time (10 min).
The steps of vacuumizing treatment and protective atmosphere filling treatment are repeated at least twice to ensure that the chemical vapor deposition process is in a high-purity nitrogen protection state.
Step three, processing the required environment temperature by the CVD process;
heating silicon source, setting frequency of induction coil 15 to make temperature in water bath 11 reach 55 deg.C, and keeping constant temperature for 5 min.
Heating the deposition reaction chamber 6 to heat the temperature of one zone to 1180 ℃ and then preserving the heat; then the temperature of the second area is heated to 1000 ℃ and then is kept.
The rate of temperature rise in the first zone temperature was 10 deg.C/min.
The temperature rise rate of the second zone temperature is 10 ℃/min.
Step four, carrying out co-permeation deposition on the silicon-aluminum coating by using a CVD (chemical vapor deposition) process;
closing the BA valve 21, pushing the push rod 5, pushing the crucible 64 into the second zone for heating, opening the AA valve 13, starting the carrier gas device 10, starting to introduce silicon tetrachloride gas and high-purity nitrogen, and adjusting the carrier gas device 10 so as to fix the gas inflow at a certain value (the gas inflow is 0.1-0.5L/min); adjusting the ventilation time according to the design thickness of the coating; after the aeration time is reached, the AA valve 13, the BB valve 22 and the CB valve 32 are closed, and the push rod 5 is pulled out to enable the crucible 64 to be far away from the two areas.
Step five, in-situ vacuum diffusion annealing;
after the silicon-aluminum coating is deposited by the co-permeation, a mechanical pump 41 is started, a DA valve 42 is opened, and residual reaction gas in the deposition reaction chamber 6 is pumped away; closing the CA valve 31, adjusting the heating temperature of the first zone to 1200 ℃, and carrying out in-situ vacuum diffusion annealing for 15 minutes;
step six, waste gas recovery treatment;
after the annealing is finished, opening the BA valve 21 and the BB valve 22, introducing high-purity nitrogen, and opening the CB valve 32 after the pressure of the deposition reaction chamber 6 reaches the atmospheric pressure until the deposition reaction chamber 6 is cooled to the room temperature; the BA valve 21 and CA valve 32 are closed. The end cap on the deposition reaction chamber 6 was opened to take out the sample.
Step seven, performance test;
fig. 7 shows the cross-sectional structure and element distribution of the 25% Al-3% Si coating, with the Al element distributed in a gradient along the cross-section, with the highest content at the surface, 25-30 w.t.%; the Si element is distributed more uniformly, and the average content is 3 w.t.%.
FIG. 8 is an oxidation weight gain curve for a 25% Al-3% Si coating at 1150 ℃. The oxidation weight gain is 3.5mg/cm at 1150 ℃ for 100h2. The AlSi coating of the composition has better oxidation resistance than the coatings in examples 1 and 2 before 70 hours, and has sharply reduced oxidation resistance after the oxidation time is more than 70 hours, which is inferior to the coatings in examples 1 and 2. FIG. 8(a) an oxidation weight gain curve at 1150 ℃ before and after co-infiltration of an IC21 alloy with a 25% Al-3% Si coating; FIG. 8(b) oxidation weight gain curves for 25% Al-3% Si coating versus 35% Al-2% Si coating, 30% Al-5% Si coating.
Claims (4)
1. An improved CVD device consists of an air source control component, a deposition reaction chamber, a deposition temperature control single piece, a vacuum exhaust component and a pressure control component; the method is characterized in that: the first aspect improves the deposition reaction chamber; in the second aspect, a silicon source pipeline for conveying carrier gas is improved and is called as a reaction gas supply unit after the improvement;
when an improved CVD device is used for carrying out improved CVD process processing, a first area temperature field is used for carrying out chemical vapor deposition, and a second area temperature field is used for carrying out in-situ vacuum diffusion annealing;
the reaction gas supply unit comprises a gas carrying device (10), a protective gas device (20), a siliconizing source container (1), a gas carrying channel and a protective channel;
the siliconizing source container (1) is connected with a BA pipeline (2) through an AA pipeline (12) on one hand, and the siliconizing source container (1) is connected with a carrier gas device (10) through an AB pipeline (14) on the other hand; a silicon source is placed in the siliconizing source container (1), the siliconizing source container (1) is placed in a water bath pot (11), and the water bath pot (11) is heated by an induction coil (15); the power of the induction coil (15) is 100-350W/220V; an AA valve (13) is arranged on the AA pipeline (12); a BA pipeline (2) is connected between the protective gas device (20) and an FC through hole (601C) on a countersunk head cavity (601B) at the right end of the FA flange plate (601); a BA valve (21) and a BB valve (22) are arranged on the BA pipeline (2); one end of the AA pipeline (12) is arranged between the BA valve (21) and the BB valve (22);
the improved CVD unit comprises a deposition reaction chamber (6), 4 flange plates (601, 602, 603 and 604), a mullite end cover, a sample holder (63), a crucible (64), an FA thermocouple (65) and an FB thermocouple (66);
the center of the deposition reaction chamber (6) is a cavity; a sample rack (63) and a crucible (64) are arranged in the cavity; a base body is arranged on the sample frame (63); an aluminizing agent is placed in the crucible (64);
a front group of Mo-Si resistance heating rods (6A 1) are arranged on a front panel (6A) of the deposition reaction chamber (6);
a rear group of Mo-Si resistance heating rods (6B 1) are arranged on a rear panel (6B) of the deposition reaction chamber (6);
the Mo-Si resistance heating rods are arranged in an array mode, and one Mo-Si resistance heating rod can be independently heated, so that temperature adjustment of different areas in a cavity of the deposition reaction chamber (6) is realized, different temperature environments of different areas are achieved, and temperature fields of a first area and a second area at least exist in the cavity;
an FA through hole (6C 1) and an FB through hole (6C 2) are arranged on an upper panel (6C) of the deposition reaction chamber (6); the FA through hole (6C 1) is used for the sensitive end of the FA thermocouple (65) to pass through and is arranged in the second area; the FB through hole (6C 2) is used for the sensitive end of the FB thermocouple (66) to pass through and is arranged in a zone;
the right end of the deposition reaction chamber (6) is provided with a right-end cylindrical joint (6D), and the right-end cylindrical joint (6D) is sleeved on a countersunk circular ring section (602B) of the FB flange (602);
the left end of the deposition reaction chamber (6) is provided with a left-end cylindrical joint which is sleeved on a countersunk circular ring section (604B) of the FD flange plate (604);
one end of the FA flange plate (601) is a connecting disc (601A), and the other end of the FA flange plate (601) is a right countersunk cavity (601B); an FA mullite end cover (61) is arranged in the right countersunk head cavity (601B); an FC through hole (601C) and an FD through hole (601D) are formed in the right countersunk head cavity (601B); the FC through hole (601C) is used for installing the other end of the BA pipeline (2), and one end of the BA pipeline (2) is connected to the protective gas device (20); the FD through hole (601D) is used for installing the push rod (5); one end of the push rod (5) sequentially passes through the FD through hole (601D) and the through hole on the FA mullite end cover (61) and then is connected in a threaded hole on the side wall of the crucible (64) in a threaded manner; the push rod (5) is in threaded connection with the crucible (64); the position of the crucible (64) in the cavity of the deposition reaction chamber (6) is adjusted by the axial translation of the push rod (5) along the deposition reaction chamber (6);
one end of the FB flange plate (602) is a connecting disc (602A), and the other end of the FB flange plate (602) is a countersunk circular ring section (602B); a connecting disc (602A) of the FB flange (602) is fixed with a connecting disc (601A) of the FA flange (601) through the matching of a screw and a nut; a countersunk circular ring section (602B) of the FB flange plate (602) is sleeved on a right end cylindrical joint (6D) of the deposition reaction chamber (6);
one end of the FC flange plate (603) is a connecting disc (603A), and the other end of the FC flange plate (603) is a left-end countersunk cavity (603B); an FB mullite end cover (62) is arranged in the left countersunk head cavity (603B); an FE through hole (603C) is arranged on the left countersunk head cavity (603B); the FE through hole (603C) is used for installing the other end of the CA pipeline (3), and one end of the CA pipeline (3) is connected to the waste gas collecting device (30);
one end of the FD flange plate (604) is a connecting disc (604A), and the other end of the FD flange plate (604) is a sunk circular ring section (604B); a connecting disc (604A) of the FD flange plate (604) and a connecting disc (603A) of the FC flange plate (603) are fixed through the matching of a screw and a nut; a countersunk circular ring section (604B) of the FD flange plate (604) is sleeved on a cylindrical joint at the left end of the deposition reaction chamber (6);
an FA mullite end cover (61) is provided with FA array micropores (61A) and a through hole for the push rod (5) to pass through; the FA array micropores (61A) are beneficial to the uniform entry of the protective gas into the inner cavity of the deposition reaction chamber (6);
an FB array micropore (62A) is arranged on the FB mullite end cover (62); the FB array micropores (62A) are beneficial to the uniform collection of the reaction gas in the inner cavity of the deposition reaction chamber (6) by the waste gas collecting device (30);
the temperature environment of the cavity of the deposition reaction chamber (6) is provided by adopting a front group of Mo-Si resistance heating rods (6A 1) arranged on a front panel (6A) and a rear group of Mo-Si resistance heating rods (6B 1) arranged on a rear panel (6B); the power of the Mo-Si resistance heating rod is 150 kW/380V;
the waste gas treatment unit comprises a waste gas collecting device (30), a mechanical pump (41) and a gas receiving channel;
one end of a CA pipeline (3) is arranged on an FE through hole (603C) on a left end countersunk cavity (603B) of an FC flange plate (603), the other end of the CA pipeline (3) is arranged on an exhaust gas collecting device (30), a CA valve (31) and a CB valve (32) are arranged on the CA pipeline (3), one end of a DA pipeline (4) is arranged between the CA valve (31) and the CB valve (32), and a mechanical pump (41) is arranged at the other end of the DA pipeline (4); a DA valve (42) is arranged on the DA pipeline (4);
the mechanical pump (41) is used for vacuumizing the deposition reaction chamber (6) and the pipeline so as to reduce the oxygen content in the deposition reaction chamber (6) and the pipeline;
the off-gas collection device (30) is used to absorb solutions of contaminating products produced during the manufacturing process.
2. An improved CVD apparatus according to claim 1, wherein: the method is used for preparing the aluminum-silicon co-infiltration coating of the hot-end component of the turbine engine.
3. The method of forming an Al-Si co-infiltrated coating on a hot end member of a turbine engine subjected to an improved CVD process using an improved CVD apparatus according to claim 1, comprising the steps of:
selecting materials;
a siliconizing source placed in the siliconizing source container (1);
an aluminizing agent disposed in the crucible (64);
placing an IC21 substrate on the sample holder (63), and placing the sample holder (63) loaded with the IC21 substrate in a heating first zone;
step two, treating the CVD process in a protective atmosphere environment;
vacuumizing, namely closing the AA valve (13), the BA valve (21) and the CB valve (32), opening the BB valve (22), the CA valve (31) and the DA valve (42), starting a mechanical pump (41), and vacuumizing the deposition reaction chamber (6) and an air duct; up to 10 in the deposition reaction chamber (6)－2 After the vacuum degree of Pa, closing the DA valve (42), closing the mechanical pump (41) and finishing vacuumizing;
filling protective atmosphere, opening a BA valve (21), starting a protective gas device (20), introducing high-purity nitrogen, opening a CB valve (32) after the furnace pressure is equal to or slightly greater than the atmospheric pressure, and finishing the filling of the protective atmosphere after introducing gas for 5-15 min;
repeating the steps of vacuumizing and processing by filling protective atmosphere at least twice to ensure that the chemical vapor deposition process is in a high-purity nitrogen protection state;
step three, processing the required environment temperature by the CVD process;
heating a silicon source, and setting the frequency of the induction coil (15) to ensure that the temperature in the water bath 11 reaches 50-60 ℃, and keeping the temperature for 10 min;
heating the deposition reaction chamber (6), heating the deposition reaction chamber (6) by adopting a Mo-Si resistance heating rod, heating the temperature of one zone to 1180 ℃, and then preserving the heat; heating the second zone to 1000 ℃ and then preserving heat;
the temperature rise rate of the first zone temperature is 5-10 ℃/min;
the temperature rise rate of the second zone temperature is 5-10 ℃/min;
step four, carrying out co-permeation deposition on the silicon-aluminum coating by using a CVD (chemical vapor deposition) process;
closing the BA valve (21), pushing the push rod (5), pushing the crucible (64) into the second zone for heating, opening the AA valve (13), starting the carrier gas device (10), starting to introduce silicon tetrachloride gas and high-purity nitrogen, and adjusting the carrier gas device (10) so as to fix the gas inlet flow at 0.1-0.5L/min; adjusting the ventilation time according to the design thickness of the coating; after the ventilation time is up, closing the AA valve (13), the BB valve (22) and the CB valve (32), and pulling out the push rod (5) to enable the crucible (64) to be far away from the second area;
step five, in-situ vacuum diffusion annealing;
after the silicon-aluminum coating is deposited by the co-permeation, a mechanical pump (41) is opened, a DA valve (42) is opened, and residual reaction gas in a deposition reaction chamber (6) is pumped away; closing the CA valve (31), adjusting the heating temperature of the first zone to 1200 ℃, and carrying out in-situ vacuum diffusion annealing treatment for 5-5 minutes;
step six, waste gas recovery treatment;
after the annealing is finished, opening a BA valve (21) and a BB valve (22), introducing high-purity nitrogen, and opening a CB valve (32) until the temperature of the deposition reaction chamber (6) is reduced to the room temperature after the pressure of the deposition reaction chamber (6) reaches the atmospheric pressure; closing the BA valve (21) and the CB valve (32); and opening an end cover on the deposition reaction chamber (6) to take out a sample.
4. The method of claim 3 for forming an Al-Si co-infiltrated coating on a hot end component of a turbine engine using an improved CVD process, wherein: the oxidation weight gain of the co-permeation deposition aluminum-silicon coating is 1.5mg/cm at 1150 ℃ for 100h2 ~3.5mg/cm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110147304.0A CN112981368B (en) | 2021-02-03 | 2021-02-03 | Improved CVD equipment and preparation method for realizing co-infiltration deposition of aluminum-silicon coating by using improved CVD equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110147304.0A CN112981368B (en) | 2021-02-03 | 2021-02-03 | Improved CVD equipment and preparation method for realizing co-infiltration deposition of aluminum-silicon coating by using improved CVD equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112981368A CN112981368A (en) | 2021-06-18 |
| CN112981368B true CN112981368B (en) | 2022-06-07 |
Family
ID=76346374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110147304.0A Active CN112981368B (en) | 2021-02-03 | 2021-02-03 | Improved CVD equipment and preparation method for realizing co-infiltration deposition of aluminum-silicon coating by using improved CVD equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112981368B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113529011B (en) * | 2021-07-21 | 2023-03-31 | 昆明理工大学 | Preparation process of ultra-thick aluminized coating |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047783A1 (en) * | 1996-06-14 | 1997-12-18 | The Research Foundation Of State University Of New York | Methodology and apparatus for in-situ doping of aluminum coatings |
| CN102094185A (en) * | 2011-01-27 | 2011-06-15 | 方文卿 | Barrel-shaped metal organic chemical vapor deposition reaction tube |
| CN202063992U (en) * | 2011-04-19 | 2011-12-07 | 西安电炉研究所有限公司 | Chemical vapor deposition furnace |
| CN107119264A (en) * | 2017-06-14 | 2017-09-01 | 东南大学 | Iridium alumina high temperature coating apparatus and technique are deposited with chamber In-situ reaction |
| CN107628605A (en) * | 2017-10-27 | 2018-01-26 | 武汉网信安全技术股份有限公司 | A kind of three-step approach prepares the method for graphene and the graphene of acquisition without transfer |
| CN107964653A (en) * | 2018-01-15 | 2018-04-27 | 夏禹纳米科技（深圳）有限公司 | The heating control apparatus and method for heating and controlling of a kind of chemical vapor deposition |
| CN108277534A (en) * | 2018-04-27 | 2018-07-13 | 济南金曼顿自动化技术有限公司 | A kind of graphite resistance heating SiC crystal growth furnace |
| CN110344025A (en) * | 2019-08-30 | 2019-10-18 | 福州大学 | A kind of two dimension Zn doping Ca2Si nano thin-film and its chemical vapor deposition method |
| CN111607776A (en) * | 2020-04-14 | 2020-09-01 | 陈牧 | Continuous vacuum coating production equipment and production method thereof |
| CN112086362A (en) * | 2020-08-13 | 2020-12-15 | 深圳大学 | Gallium nitride enhanced HEMT device and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020015855A1 (en) * | 2000-06-16 | 2002-02-07 | Talex Sajoto | System and method for depositing high dielectric constant materials and compatible conductive materials |
| TWI377602B (en) * | 2005-05-31 | 2012-11-21 | Japan Science & Tech Agency | Growth of planar non-polar {1-100} m-plane gallium nitride with metalorganic chemical vapor deposition (mocvd) |
-
2021
- 2021-02-03 CN CN202110147304.0A patent/CN112981368B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047783A1 (en) * | 1996-06-14 | 1997-12-18 | The Research Foundation Of State University Of New York | Methodology and apparatus for in-situ doping of aluminum coatings |
| CN102094185A (en) * | 2011-01-27 | 2011-06-15 | 方文卿 | Barrel-shaped metal organic chemical vapor deposition reaction tube |
| CN202063992U (en) * | 2011-04-19 | 2011-12-07 | 西安电炉研究所有限公司 | Chemical vapor deposition furnace |
| CN107119264A (en) * | 2017-06-14 | 2017-09-01 | 东南大学 | Iridium alumina high temperature coating apparatus and technique are deposited with chamber In-situ reaction |
| CN107628605A (en) * | 2017-10-27 | 2018-01-26 | 武汉网信安全技术股份有限公司 | A kind of three-step approach prepares the method for graphene and the graphene of acquisition without transfer |
| CN107964653A (en) * | 2018-01-15 | 2018-04-27 | 夏禹纳米科技（深圳）有限公司 | The heating control apparatus and method for heating and controlling of a kind of chemical vapor deposition |
| CN108277534A (en) * | 2018-04-27 | 2018-07-13 | 济南金曼顿自动化技术有限公司 | A kind of graphite resistance heating SiC crystal growth furnace |
| CN110344025A (en) * | 2019-08-30 | 2019-10-18 | 福州大学 | A kind of two dimension Zn doping Ca2Si nano thin-film and its chemical vapor deposition method |
| CN111607776A (en) * | 2020-04-14 | 2020-09-01 | 陈牧 | Continuous vacuum coating production equipment and production method thereof |
| CN112086362A (en) * | 2020-08-13 | 2020-12-15 | 深圳大学 | Gallium nitride enhanced HEMT device and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112981368A (en) | 2021-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5348774A (en) | Method of rapidly densifying a porous structure | |
| US3603284A (en) | Vapor deposition apparatus | |
| JP5647977B2 (en) | Processing equipment for specifically processing stacked objects to be processed | |
| CN112981368B (en) | Improved CVD equipment and preparation method for realizing co-infiltration deposition of aluminum-silicon coating by using improved CVD equipment | |
| JP2003113473A (en) | Apparatus and method for chemical vapor deposition | |
| CN116444296B (en) | Method for preparing tantalum carbide coating on graphite substrate by molten salt method | |
| CN113652644B (en) | TiAl coating capable of improving high-temperature oxidation resistance of titanium alloy and preparation method thereof | |
| CN108004522A (en) | A kind of device and method of plasma enhanced atomic layer deposition carbonization nickel film | |
| CN111235518B (en) | Method for improving high-temperature oxidation resistance of titanium-based alloy through high-temperature fluorination treatment | |
| CN115108852A (en) | Graphite composite material and preparation method and application thereof | |
| CN1062795C (en) | Sintering heat isostatic device and cooling method thereof | |
| Sasaki et al. | Thermal fatigue resistance of CVD SiC/C functionally gradient material | |
| US6488986B2 (en) | Combined coat, heat treat, quench method for gas turbine engine components | |
| CN111575643A (en) | Method for preparing tantalum diffusion layer on surface of titanium alloy | |
| CN115652267A (en) | Preparation method of TiCrAlNbSi alloy high-temperature oxidation resistant coating | |
| CN107002228A (en) | Plasma treatment and reactor for the hot chemical treatment on metal parts surface | |
| CN212955340U (en) | Device for atomic layer deposition process | |
| TWI496938B (en) | A heat treatment method including a heating step, a processing step and a cooling step | |
| CN114315424A (en) | Preparation method of high-temperature-resistant coating and application of high-temperature-resistant coating in graphite product | |
| TW200404912A (en) | Method of producing vapor from solid precursor and substrate processing system using the same | |
| CN105671514B (en) | A kind of method that two-step method prepares porous iridium | |
| Gaitan et al. | Development of a system for coating SRF cavities using Remote Plasma CVD | |
| CN116462517B (en) | Method for preparing silicon nitride coating on graphite substrate by molten salt method | |
| CN109112501B (en) | A kind of hafnium oxide coating and preparation method thereof | |
| JP2003042664A (en) | Vacuum heating furnace |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |