CN109234701B - Device and method for chemical vapor deposition of rhenium layer - Google Patents
Device and method for chemical vapor deposition of rhenium layer Download PDFInfo
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- CN109234701B CN109234701B CN201811141729.5A CN201811141729A CN109234701B CN 109234701 B CN109234701 B CN 109234701B CN 201811141729 A CN201811141729 A CN 201811141729A CN 109234701 B CN109234701 B CN 109234701B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- 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
- C23C16/06—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 metallic material
- C23C16/08—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 metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- 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
- C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C16/448—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
- C23C16/4482—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material by bubbling of carrier gas through liquid source material
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Abstract
The invention relates to a device and a method for chemical vapor deposition of a rhenium layer, belongs to the technical field of preparation of spacecraft orbit/attitude control engine thrust rooms, and particularly relates to a high-efficiency green environment-friendly chemical vapor deposition device for depositing a metal rhenium layer, which is mainly used for preparing rhenium iridium engine thrust rooms. According to the invention, the precursor regeneration chamber and the condensation collection chamber are introduced, so that reaction tail gas is effectively utilized, the utilization rate of the precursor is greatly improved, and the deposition cost of the rhenium layer is reduced. According to the invention, the tail gas treatment device is introduced, so that the reaction tail gas is thoroughly treated in a water washing mode, the treated tail gas meets the emission standard, and the green and environment-friendly effect of the deposition process is realized.
Description
Technical Field
The invention relates to a device and a method for chemical vapor deposition of a rhenium layer, belongs to the technical field of preparation of spacecraft orbit/attitude control engine thrust rooms, and particularly relates to a high-efficiency green environment-friendly chemical vapor deposition device for depositing a metal rhenium layer, which is mainly used for preparing rhenium iridium engine thrust rooms.
Background
The rail/attitude control engine is mainly applied to the rail or attitude control of a space aircraft and a strategic tactical weapon, the combustion temperature of fuel in a thrust chamber is as high as 2700 ℃, and the temperature of the inner wall surface of the thrust chamber is still higher than 1000 ℃ by adopting the active liquid film cooling technology of the inner wall surface. In order to meet the high-temperature strength requirement of the engine thrust chamber, refractory metals (W, Mo, Ta, Nb, Re, etc.) or metal platinum must be used as the material of the thrust chamber body. However, these materials have poor high temperature oxidation resistance, and it is necessary to coat a high temperature oxidation resistant coating on the surface of the body material for protection. The rhenium substrate coated with the iridium coating is an engine thrust chamber material with the best performance at present, for example, an American R-4D-16 engine, the thrust is 445N, the specific impulse of the engine can reach more than 325s, the specific impulse is improved by 20s compared with the niobium alloy engine currently used in China, the service life of a satellite can be greatly prolonged, the effective load can be increased, or the weapon range can be improved, and the rhenium substrate coated with the iridium coating has extremely obvious military significance and economic value.
The forming of the rhenium substrate of the body part of the thrust chamber is an important link for preparing the rhenium iridium engine, and the mature preparation process is chemical vapor deposition. However, the existing preparation technology has the following defects: the deposition rate of the rhenium layer is low; the deposition uniformity of the rhenium layer is poor; the utilization rate of the precursor rhenium pentachloride is low; in the deposition process, chlorine is used as reaction gas, so that potential safety hazards exist to process personnel and the environment.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the device and the method for preparing the rhenium layer through the chemical vapor deposition are high in deposition rate, good in uniformity of the rhenium layer, high in utilization rate of the precursor and capable of achieving zero emission of toxic and harmful tail gas in the whole deposition process.
The technical solution of the invention is as follows:
a device for chemical vapor deposition of a rhenium layer comprises a carrier gas cylinder, a precursor cylinder, a reaction chamber, an air inlet pipe, an air outlet pipe, a precursor regeneration chamber, a condensation collection chamber, a filter, a vacuum pump, a motor and a tail gas treatment device;
the carrier gas bottle is internally stored with carrier gas, and the carrier gas is preferably inert gas Ar;
the precursor bottle is used for storing rhenium pentachloride, is a steel bottle, is placed in a resistance furnace, and is heated by electrifying a resistor;
the reaction chamber is made of quartz, an induction coil is arranged on the outer wall of the reaction chamber in a surrounding mode, and a workpiece to be deposited in the reaction chamber is heated through induction heating;
the gas inlet pipe is made of quartz, a slit is formed in the axial direction of the side wall, and the width of the slit is 1-2 mm;
the gas outlet pipe is made of quartz, a slit is formed in the axial direction of the side wall, and the width of the slit is 1-2 mm;
the gas inlet pipe and the gas outlet pipe are arranged in the reaction chamber;
the precursor regeneration chamber is filled with powdered rhenium, when chlorine passes through the precursor regeneration chamber, the rhenium reacts with the chlorine to generate rhenium pentachloride, the generated rhenium pentachloride enters the condensation collection chamber, and the rhenium pentachloride is condensed and then placed in the precursor bottle for recycling;
the filter is used for filtering the rhenium pentachloride which is not completely collected in the condensation collection chamber, and plays a role in protecting the vacuum pump;
the motor is used for driving a workpiece to be deposited to rotate;
the tail gas treatment device is used for treating unreacted chlorine, and the tail gas treatment mode is preferably a water washing treatment mode;
the carrier gas cylinder is connected with the precursor cylinder through a first pipeline, a first valve and a mass flow meter are mounted on the first pipeline, and the mass flow meter is used for controlling the flow of inert gas entering the precursor cylinder from the carrier gas cylinder;
the precursor bottle is connected with an air inlet pipe arranged in the reaction chamber through a second pipeline, a heating belt is wound outside the second pipeline and used for heating the second pipeline, and a second valve is also arranged on the second pipeline;
the air outlet pipe arranged in the reaction chamber is connected with the precursor regeneration chamber through a third pipeline, the precursor regeneration chamber is placed in a resistance furnace, and the precursor regeneration chamber is heated by electrifying a resistor; a heating belt is wound outside the third pipeline and used for heating the third pipeline;
the precursor regeneration chamber is connected with the condensation collection chamber through a fourth pipeline; a heating belt is wound on the outer surface of the fourth pipeline and used for heating the fourth pipeline;
the condensation collection chamber is connected with the filter through a fifth pipeline, and a vacuum gauge is arranged on the fifth pipeline;
the condensation collection chamber is connected with the vacuum pump through a sixth pipeline, and a third valve is arranged on the sixth pipeline;
the filter is connected with the vacuum pump through a seventh pipeline, and a butterfly valve and a fourth valve are installed on the seventh pipeline;
the vacuum pump is connected with the tail gas treatment device through an eighth pipeline;
the workpiece to be deposited is arranged in the reaction chamber, and the motor is used for driving the workpiece to be deposited to rotate.
A method of chemical vapour deposition of a re layer, the method comprising the steps of:
(1) the method comprises the following steps of placing a workpiece to be deposited on a sample table of a reaction chamber, wherein the sample table is connected with a motor, and when the motor rotates, the sample table can be driven to rotate, so that the workpiece to be deposited rotates;
(2) closing the first valve and the second valve, opening the third valve, the fourth valve, the fifth valve and the butterfly valve, using a vacuum pump to pump vacuum, measuring the vacuum degree by a vacuum gauge, opening the second valve when the vacuum degree reaches below 10Pa, continuing to pump vacuum, measuring the vacuum degree by the vacuum gauge, opening the first valve when the vacuum degree reaches below 10Pa, introducing inert gas, controlling the flow of the inert gas by a mass flowmeter and adjusting the opening degree of the butterfly valve to ensure that the vacuum degree measured by the vacuum gauge is 5 multiplied by 103-3×104Pa；
(3) Turning on a motor to enable the motor to drive a workpiece to be deposited to rotate;
(4) heating a workpiece to be deposited in the reaction chamber by induction heating, heating the second pipeline by a heating belt when the temperature of the workpiece to be deposited is 1000-1400 ℃, heating the third pipeline by the heating belt, heating the fourth pipeline by the heating belt, heating the precursor regeneration chamber by resistance electrification, wherein the heating temperature of the second pipeline is 200-400 ℃, the heating temperature of the third pipeline is 200-400 ℃, the heating temperature of the fourth pipeline is 200-400 ℃, the heating temperature of the precursor regeneration chamber is 600-800 ℃, and finally heating the precursor bottle by resistance electrification, wherein the heating temperature of the precursor bottle is 150-300 ℃;
(5) and (3) beginning to deposit a metal rhenium layer on the workpiece to be deposited, wherein the deposition rate is about 50 mu m/h or more, the thickness uniformity is +/-10 mu m when the thickness is not more than 300 mu m, the workpiece with the metal rhenium layer deposited is obtained, and the rhenium pentachloride collected in the condensation collection chamber can be recycled.
Advantageous effects
(1) The invention provides a device and a method for chemical vapor deposition of a metal rhenium layer. By adopting rhenium pentachloride as a precursor, reducing the opening of a butterfly valve to realize high-pressure deposition, adjusting the temperature of a precursor bottle to improve the partial pressure of rhenium pentachloride, and realizing the high deposition rate of a rhenium layer more than 50 mu m/h;
(2) the invention designs the size of the reaction chamber and the air inlet/outlet pipe according to the size of the deposition workpiece, thereby not only ensuring that the temperature of the inner wall of the quartz reaction chamber reaches a certain temperature range in the deposition process, avoiding the condensation of rhenium pentachloride, but also realizing that different parts of the workpiece obtain rhenium layers with uniform thickness.
(3) According to the invention, the precursor regeneration chamber and the condensation collection chamber are introduced, so that reaction tail gas is effectively utilized, the utilization rate of the precursor is greatly improved, and the deposition cost of the rhenium layer is reduced.
(4) According to the invention, the tail gas treatment device is introduced, so that the reaction tail gas is thoroughly treated in a water washing mode, the treated tail gas meets the emission standard, and the green and environment-friendly effect of the deposition process is realized.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is a microscopic surface topography photograph of the rhenium layer obtained in example 1;
FIG. 3 is a photograph of a cross section of the rhenium layer obtained in example 1;
fig. 4 a microscopic morphology photograph of a needle-like structure rhenium layer was obtained as a microstructure in example 2.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1
As shown in fig. 1, a device for chemical vapor deposition of a rhenium layer comprises a carrier gas cylinder, a precursor cylinder, a reaction chamber, an air inlet pipe, an air outlet pipe, a precursor regeneration chamber, a condensation collection chamber, a filter, a vacuum pump, a motor and a tail gas treatment device;
the carrier gas bottle is internally stored with carrier gas, and the carrier gas is preferably inert gas Ar;
the precursor bottle is used for storing rhenium pentachloride, is a steel bottle, is placed in a resistance furnace, and is heated by electrifying a resistor;
the reaction chamber is made of quartz, an induction coil is arranged around the outside of the reaction chamber, and a workpiece to be deposited in the reaction chamber is heated through induction heating;
the air inlet pipe is made of quartz, a slit is formed in the axial direction of the side wall of the air inlet pipe, and the width of the slit is 1 mm;
the gas outlet pipe is made of quartz, a slit is formed in the axial direction of the side wall, and the width of the slit is 1 mm;
the gas inlet pipe and the gas outlet pipe are arranged in the reaction chamber;
the precursor regeneration chamber is filled with powdered rhenium, when chlorine passes through the precursor regeneration chamber, the rhenium reacts with the chlorine to generate rhenium pentachloride, the generated rhenium pentachloride enters the condensation collection chamber, and the rhenium pentachloride is condensed and then placed in the precursor bottle for recycling;
the filter is used for filtering the rhenium pentachloride which is not completely collected in the condensation collection chamber, and plays a role in protecting the vacuum pump;
the motor is used for driving a workpiece to be deposited to rotate;
the tail gas treatment device is used for treating unreacted chlorine, and the tail gas treatment mode is preferably a water washing treatment mode;
the carrier gas cylinder is connected with the precursor cylinder through a first pipeline, a first valve and a mass flow meter are mounted on the first pipeline, and the mass flow meter is used for controlling the flow of inert gas entering the precursor cylinder from the carrier gas cylinder;
the precursor bottle is connected with an air inlet pipe arranged in the reaction chamber through a second pipeline, a heating belt is wound outside the second pipeline and used for heating the second pipeline, and a second valve is also arranged on the second pipeline;
the air outlet pipe arranged in the reaction chamber is connected with the precursor regeneration chamber through a third pipeline, the precursor regeneration chamber is placed in a resistance furnace, and the precursor regeneration chamber is heated by electrifying a resistor; a heating belt is wound outside the third pipeline and used for heating the third pipeline;
the precursor regeneration chamber is connected with the condensation collection chamber through a fourth pipeline; a heating belt is wound on the outer surface of the fourth pipeline and used for heating the fourth pipeline;
the condensation collection chamber is connected with the filter through a fifth pipeline, and a vacuum gauge is arranged on the fifth pipeline;
the condensation collection chamber is connected with the vacuum pump through a sixth pipeline, and a third valve is arranged on the sixth pipeline;
the filter is connected with the vacuum pump through a seventh pipeline, and a butterfly valve and a fourth valve are installed on the seventh pipeline;
the vacuum pump is connected with the tail gas treatment device through an eighth pipeline;
the workpiece to be deposited is arranged in the reaction chamber, and the motor is used for driving the workpiece to be deposited to rotate.
The workpiece to be deposited is of a rod-shaped structure, the diameter is 10mm, the height is 50mm, and the size of an inner cavity of the reaction chamber is phi 60mm multiplied by 80 mm;
a method of chemical vapour deposition of a re layer, the method comprising the steps of:
(1) the method comprises the following steps of placing a workpiece to be deposited on a sample table of a reaction chamber, wherein the sample table is connected with a motor, and when the motor rotates, the sample table can be driven to rotate, so that the workpiece to be deposited rotates;
(2) closing the first valve and the second valve, opening the third valve, the fourth valve, the fifth valve and the butterfly valve, vacuumizing by using a vacuum pump, measuring the vacuum degree by using a vacuum gauge, opening the second valve when the vacuum degree reaches below 10Pa, continuing vacuumizing, measuring the vacuum degree by using the vacuum gauge, opening the first valve when the vacuum degree reaches below 10Pa, introducing inert gas, wherein the flow rate of the inert gas is 300 sccm;
(3) turning on a motor to enable the motor to drive a workpiece to be deposited to rotate;
(4) heating a workpiece to be deposited in a reaction chamber by induction heating, heating a second pipeline by a heating belt when the temperature of the workpiece to be deposited is 1300 ℃, heating a third pipeline by the heating belt, heating a fourth pipeline by the heating belt, heating a precursor regeneration chamber by resistance electrification, wherein the heating temperature of the second pipeline is 300 ℃, the heating temperature of the third pipeline is 300 ℃, the heating temperature of the fourth pipeline is 300 ℃, the heating temperature of the precursor regeneration chamber is 800 ℃, and finally heating a precursor bottle by resistance electrification, wherein the heating temperature of the precursor bottle is 200 ℃;
(5) and (3) beginning to deposit a metal rhenium layer on the workpiece to be deposited, wherein the deposition time is 2.5h, and obtaining the workpiece on which the metal rhenium layer is deposited. The microscopic morphology and the cross-sectional morphology of the workpiece deposited with the metal rhenium layer are respectively shown in fig. 2 and 3, and it can be seen from the graphs that the deposited rhenium layer is uniform and compact, the deposition rate of the rhenium layer is more than 50 μm/h, and the thickness uniformity is less than +/-10 μm.
Example 2
As shown in fig. 1, a device for chemical vapor deposition of a rhenium layer comprises a carrier gas cylinder, a precursor cylinder, a reaction chamber, an air inlet pipe, an air outlet pipe, a precursor regeneration chamber, a condensation collection chamber, a filter, a vacuum pump, a motor and a tail gas treatment device;
the carrier gas bottle is internally stored with carrier gas, and the carrier gas is preferably inert gas Ar;
the precursor bottle is used for storing rhenium pentachloride, is a steel bottle, is placed in a resistance furnace, and is heated by electrifying a resistor;
the reaction chamber is made of quartz, an induction coil is arranged on the outer wall of the reaction chamber in a surrounding mode, and a workpiece to be deposited in the reaction chamber is heated through induction heating;
the air inlet pipe is made of quartz, a slit is formed in the axial direction of the side wall of the air inlet pipe, and the width of the slit is 1 mm;
the gas outlet pipe is made of quartz, a slit is formed in the axial direction of the side wall, and the width of the slit is 1 mm;
the gas inlet pipe and the gas outlet pipe are arranged in the reaction chamber;
the precursor regeneration chamber is filled with powdered rhenium, when chlorine passes through the precursor regeneration chamber, the rhenium reacts with the chlorine to generate rhenium pentachloride, the generated rhenium pentachloride enters the condensation collection chamber, and the rhenium pentachloride is condensed and then placed in the precursor bottle for recycling;
the filter is used for filtering the rhenium pentachloride which is not completely collected in the condensation collection chamber, and plays a role in protecting the vacuum pump;
the motor is used for driving a workpiece to be deposited to rotate;
the tail gas treatment device is used for treating unreacted chlorine, and the tail gas treatment mode is preferably a water washing treatment mode;
the carrier gas cylinder is connected with the precursor cylinder through a first pipeline, a first valve and a mass flow meter are mounted on the first pipeline, and the mass flow meter is used for controlling the flow of inert gas entering the precursor cylinder from the carrier gas cylinder;
the precursor bottle is connected with an air inlet pipe arranged in the reaction chamber through a second pipeline, a heating belt is wound outside the second pipeline and used for heating the second pipeline, and a second valve is also arranged on the second pipeline;
the air outlet pipe arranged in the reaction chamber is connected with the precursor regeneration chamber through a third pipeline, the precursor regeneration chamber is placed in a resistance furnace, and the precursor regeneration chamber is heated by electrifying a resistor; a heating belt is wound outside the third pipeline and used for heating the third pipeline;
the precursor regeneration chamber is connected with the condensation collection chamber through a fourth pipeline; a heating belt is wound on the outer surface of the fourth pipeline and used for heating the fourth pipeline;
the condensation collection chamber is connected with the filter through a fifth pipeline, and a vacuum gauge is arranged on the fifth pipeline;
the condensation collection chamber is connected with the vacuum pump through a sixth pipeline, and a third valve is arranged on the sixth pipeline;
the filter is connected with the vacuum pump through a seventh pipeline, and a butterfly valve and a fourth valve are installed on the seventh pipeline;
the vacuum pump is connected with the tail gas treatment device through an eighth pipeline;
the workpiece to be deposited is arranged in the reaction chamber, and the motor is used for driving the workpiece to be deposited to rotate.
The workpiece to be deposited is of a rod-shaped structure, the diameter is 10mm, the height is 50mm, and the size of an inner cavity of the reaction chamber is phi 60mm multiplied by 80 mm;
a method of chemical vapour deposition of a re layer, the method comprising the steps of:
(1) the method comprises the following steps of placing a workpiece to be deposited on a sample table of a reaction chamber, wherein the sample table is connected with a motor, and when the motor rotates, the sample table can be driven to rotate, so that the workpiece to be deposited rotates;
(2) closing the first valve and the second valve, opening the third valve, the fourth valve, the fifth valve and the butterfly valve, vacuumizing by using a vacuum pump, measuring the vacuum degree by using a vacuum gauge, opening the second valve when the vacuum degree reaches below 10Pa, continuing vacuumizing, measuring the vacuum degree by using the vacuum gauge, opening the first valve when the vacuum degree reaches below 10Pa, introducing inert gas, wherein the flow rate of the inert gas is 300 sccm;
(3) turning on a motor to enable the motor to drive a workpiece to be deposited to rotate;
(4) heating a workpiece to be deposited in a reaction chamber by induction heating, heating a second pipeline by a heating belt when the temperature of the workpiece to be deposited is 1050 ℃, heating a third pipeline by the heating belt, heating a fourth pipeline by the heating belt, heating a precursor regeneration chamber by resistance electrification, wherein the heating temperature of the second pipeline is 300 ℃, the heating temperature of the third pipeline is 300 ℃, the heating temperature of the fourth pipeline is 300 ℃, the heating temperature of the precursor regeneration chamber is 800 ℃, and finally heating a precursor bottle by resistance electrification, wherein the heating temperature of the precursor bottle is 200 ℃;
(5) and (3) beginning to deposit a metal rhenium layer on the workpiece to be deposited, wherein the deposition time is 2h, and obtaining the workpiece on which the metal rhenium layer is deposited. The micro-morphology of the rhenium layer is shown in fig. 4, and it can be seen from the graph that rhenium crystal grains are needle-shaped or cone-shaped, the rhenium layer with the special micro-structure has high heat radiation capability, and the heat radiation coefficient of the rhenium layer reaches more than 0.9.
Claims (10)
1. The utility model provides a device of chemical vapor deposition rhene layer which characterized in that: the device comprises a carrier gas cylinder, a precursor cylinder, a reaction chamber, an air inlet pipe, an air outlet pipe, a precursor regeneration chamber, a condensation collection chamber, a filter, a vacuum pump, a motor and a tail gas treatment device;
carrier gas is stored in the carrier gas cylinder;
the precursor bottle is used for storing rhenium pentachloride, is placed in a resistance furnace and is heated by electrifying a resistor;
the reaction chamber is made of quartz, an induction coil is arranged on the outer wall of the reaction chamber in a surrounding mode, and a workpiece to be deposited in the reaction chamber is heated through induction heating;
the air inlet pipe is made of quartz, and a slit is formed in the axial direction of the side wall of the air inlet pipe;
the gas outlet pipe is made of quartz, and a slit is formed in the axial direction of the side wall of the gas outlet pipe;
the gas inlet pipe and the gas outlet pipe are arranged in the reaction chamber;
the carrier gas cylinder is connected with the precursor cylinder through a first pipeline, and a first valve and a mass flow meter are mounted on the first pipeline;
the precursor bottle is connected with an air inlet pipe arranged in the reaction chamber through a second pipeline, a heating belt is wound outside the second pipeline and used for heating the second pipeline, and a second valve is also arranged on the second pipeline;
the air outlet pipe arranged in the reaction chamber is connected with the precursor regeneration chamber through a third pipeline, the precursor regeneration chamber is placed in a resistance furnace, and the precursor regeneration chamber is heated by electrifying a resistor; a heating belt is wound outside the third pipeline and used for heating the third pipeline;
the precursor regeneration chamber is connected with the condensation collection chamber through a fourth pipeline; a heating belt is wound on the outer surface of the fourth pipeline and used for heating the fourth pipeline;
the condensation collection chamber is connected with the filter through a fifth pipeline, and a vacuum gauge is arranged on the fifth pipeline;
the condensation collection chamber is connected with the vacuum pump through a sixth pipeline, and a third valve is arranged on the sixth pipeline;
the filter is connected with the vacuum pump through a seventh pipeline, and a butterfly valve and a fourth valve are installed on the seventh pipeline;
and the vacuum pump is connected with the tail gas treatment device through an eighth pipeline.
2. The apparatus for chemical vapor deposition of the rhenium layer according to the claim 1, characterized in that: the carrier gas is inert gas Ar gas, and the precursor bottle is a steel bottle.
3. The apparatus for chemical vapor deposition of the rhenium layer according to the claim 1, characterized in that: the width of the slit on the air inlet pipe is 1-2mm, and the width of the slit on the air outlet pipe is 1-2 mm.
4. The apparatus for chemical vapor deposition of the rhenium layer according to the claim 1, characterized in that: the precursor regeneration chamber is filled with powdered rhenium, when chlorine passes through the precursor regeneration chamber, the rhenium reacts with the chlorine to generate rhenium pentachloride, the generated rhenium pentachloride enters the condensation collection chamber, and the rhenium pentachloride is condensed and then placed in the precursor bottle for recycling.
5. The apparatus for chemical vapor deposition of the rhenium layer according to the claim 1, characterized in that: the filter is used for filtering rhenium pentachloride which is not completely collected in the condensation collection chamber, and plays a role in protecting the vacuum pump.
6. The apparatus for chemical vapor deposition of the rhenium layer according to the claim 1, characterized in that: the motor is used for driving a workpiece to be deposited to rotate; the tail gas treatment device is used for treating unreacted chlorine, and the mass flow meter is used for controlling the flow of inert gas entering the precursor bottle from the carrier gas bottle.
7. The apparatus for chemical vapor deposition of the rhenium layer as claimed in claim 6, characterized in that: the tail gas treatment mode is a water washing treatment mode.
8. A method for chemical vapor deposition of a re layer by using the apparatus for chemical vapor deposition of a re layer according to claim 1, characterized in that the method comprises the following steps:
(1) the method comprises the following steps of placing a workpiece to be deposited on a sample table of a reaction chamber, wherein the sample table is connected with a motor, and when the motor rotates, the sample table can be driven to rotate, so that the workpiece to be deposited rotates;
(2) closing the first valve and the second valve, opening the third valve, the fourth valve, the fifth valve and the butterfly valve, using a vacuum pump to pump vacuum, measuring the vacuum degree by a vacuum gauge, opening the second valve when the vacuum degree reaches below 10Pa, continuing to pump vacuum, measuring the vacuum degree by the vacuum gauge, opening the first valve when the vacuum degree reaches below 10Pa, introducing inert gas, controlling the flow of the inert gas by a mass flowmeter and adjusting the opening degree of the butterfly valve to ensure that the vacuum degree measured by the vacuum gauge is 5 multiplied by 103-3×104Pa；
(3) Turning on a motor to enable the motor to drive a workpiece to be deposited to rotate;
(4) heating a workpiece to be deposited in the reaction chamber by induction heating, when the temperature of the workpiece to be deposited reaches a set temperature, heating the second pipeline by a heating belt, heating the third pipeline by the heating belt, heating the fourth pipeline by the heating belt, and heating the precursor regeneration chamber by resistance electrification; finally, the precursor bottle is heated by electrifying the resistor;
(5) and starting to deposit a metal rhenium layer on the workpiece to be deposited to obtain the workpiece deposited with the metal rhenium layer.
9. The method of claim 8, wherein: in the step (4), the temperature of the workpiece to be deposited reaches the set temperature of 1000-.
10. The method of claim 8, wherein: in the step (4), the heating temperature of the second pipeline is 200-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811141729.5A CN109234701B (en) | 2018-09-28 | 2018-09-28 | Device and method for chemical vapor deposition of rhenium layer |
Applications Claiming Priority (1)
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| CN113512713A (en) * | 2021-07-08 | 2021-10-19 | 贵研铂业股份有限公司 | Rhenium crucible and preparation method and application thereof |
| CN114574834A (en) * | 2021-12-02 | 2022-06-03 | 贵研铂业股份有限公司 | Ta-Re layered composite material and preparation method and application thereof |
| CN114152322B (en) * | 2021-12-06 | 2022-12-30 | 中国科学院光电技术研究所 | Monitoring device for chemical vapor deposition liquid source material |
| CN115747762A (en) * | 2022-10-21 | 2023-03-07 | 航天材料及工艺研究所 | Method for efficiently preparing refractory metal coating on inner surface and outer surface of engine thrust chamber body |
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