CN109628909B - Chemical vapor deposition method for preparing Co-Re alloy coating - Google Patents
Chemical vapor deposition method for preparing Co-Re alloy coating Download PDFInfo
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- CN109628909B CN109628909B CN201910083948.0A CN201910083948A CN109628909B CN 109628909 B CN109628909 B CN 109628909B CN 201910083948 A CN201910083948 A CN 201910083948A CN 109628909 B CN109628909 B CN 109628909B
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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
- C23C16/06—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
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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
- C23C16/442—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 using fluidised bed process
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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
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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
- C23C16/52—Controlling or regulating the coating process
Abstract
The invention discloses a chemical vapor deposition method for preparing a Co-Re alloy coating, belongs to the field of CVD preparation, and aims to solve the problems of complex structure and high cost of the conventional equipment for preparing the Co-Re alloy coating by adopting a CVD method. The equipment adopted by the method comprises a sublimation unit, a first reaction gas generator, a second reaction gas generator, a reactor, a third reaction gas generator, a pipeline unit, a vacuum unit and a control system, wherein the third reaction gas generator is connected with the reactor through a pipeline and can charge reaction gas into the reactor, and the vacuum unit is connected with the reactor and can vacuumize the reactor. The invention can prepare the Co-Re alloy coating with better quality, and has the advantages of low cost, good product quality, higher application value and better application prospect. Meanwhile, the preparation method is mild in reaction conditions, high in safety and operability, and worthy of large-scale popularization and application.
Description
Technical Field
The invention relates to the field of CVD preparation, in particular to a chemical vapor deposition method for preparing a Co-Re alloy coating.
Background
Chemical vapor deposition is a method of generating a thin film by chemically reacting on the surface of a substrate with one or more vapor-phase compounds or simple substances containing thin film elements. Because the rocket engine needs to continuously bear the high temperature of more than 1000 ℃ and faces the erosion of corrosive high-temperature tail gas such as oxides, nitrogen oxides and the like for a long time, the high-temperature ablation resistant coating is more and more widely applied in the fields of aerospace, industry, military and the like. In addition, in order to further improve the specific impulse of the engine, prolong the service life, improve the pulse repeatability and put higher requirements on the performance of the attitude and orbit control engine thrust chamber material at high temperature, the development of a novel high-temperature ablation resistant coating is necessary.
In the research on CVD Ir/Re composite materials (university of south and central provinces, Huchanyi, 2002), an Re/Ir composite lance was fabricated by a CVD method using the excellent oxidation resistance of iridium (Ir) in order to improve the ablation resistance of a thrust chamber. The process flow is as follows: firstly, processing a Mo core into the shape of an inner cavity of a spray pipe, then depositing an Ir coating with the thickness of 30-50 mu m on the surface of the Mo core, further continuously depositing a Re layer with the thickness of 1000 mu m on the Ir coating, and finally removing the Mo core by a chemical or electrochemical method to obtain the Re-based composite spray pipe with the inner surface protected by the Ir anti-oxidation coating. However, the method has complex process flow, high equipment and raw material prices and difficult adjustment of equipment parameters.
Research on the mechanism related to the preparation of high-purity Re and Ir by chemical vapor deposition (Beijing university of Physician, Poisseria 2015) discloses a method for preparing Re coatings. In the method, the chemical vapor deposition of Re mainly adopts ReCl5Thermal decomposition or ReF6Depositing by a hydrogen reduction method. The deposition temperatures of both methods are high (as ReF)6As a precursor, the deposition temperature is 400-1500 ℃ and ReCl is used5Is used as a precursor, the deposition temperature is 1000-1300 ℃), and the heat treatment performance of the metal substrate is reduced; the byproduct is HF, and the byproduct is toxic; meanwhile, the chloride of rhenium is difficult to prepare and difficult to store.
The shallow talking MOCVD control system (major science and technology, tiandi, wang liang, ganyin, 2010 (12)) discloses an MOCVD control system, which mainly introduces the MOCVD control system developed by a research and development team, and the MOCVD control system consists of an upper computer, a Programmable Logic Controller (PLC), a touch screen and field instruments for controlling flow, pressure, temperature, speed and switching value. However, the device has a complex structure and high cost, and is difficult to meet the requirement of large-scale application.
Therefore, a new method and/or apparatus is needed to solve the above problems.
Disclosure of Invention
The invention aims to: aiming at the problems of complex structure and higher cost of the existing equipment for preparing the Co-Re alloy coating by adopting a CVD method, the chemical vapor deposition method for preparing the Co-Re alloy coating is provided. The invention can prepare the Co-Re alloy coating with better quality, and has the advantages of low cost, good product quality, higher application value and better application prospect. Meanwhile, the preparation method is mild in reaction conditions and high in safety and operability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chemical vapor deposition method for preparing a Co-Re alloy coating adopts equipment comprising a sublimation unit, a first reaction gas generator, a second reaction gas generator, a reactor, a third reaction gas generator, a pipeline unit, a vacuum unit and a control system, wherein the third reaction gas generator is connected with the reactor through a pipeline and can charge reaction gas into the reactor, the vacuum unit is connected with the reactor and can vacuumize the reactor;
the sublimation unit includes the sublimation room, is used for carrying out the first electric heater unit that heats to the sublimation room, the sublimation unit is two, the sublimation room is including being used for Re2(CO)10A first sublimation chamber for sublimating, for co (acac)2A second sublimation chamber for sublimation, wherein the first reaction gas generator is connected with the first sublimation chamber, and the reaction gas in the first reaction gas generator and the Re sublimated in the first sublimation chamber2(CO)10The mixed gas can enter a reactor to react, the second reaction gas generator is connected with the second sublimation chamber, and the reaction gas in the second reaction gas generator and the sublimed Co (acac) in the second sublimation chamber2The gas can enter a reactor for reaction after being mixed;
the pipeline unit comprises a pipeline with a first sublimation unit connected with the reactor, a pipeline with a second sublimation unit connected with the reactor, and a third electric heating device, wherein the third electric heating device is respectively arranged on the pipeline with the first sublimation unit connected with the reactor and the pipeline with the second sublimation unit connected with the reactor, and can heat the pipelines;
the first reaction gas generator, the second reaction gas generator, the third reaction gas generator, the pipeline unit, the vacuum unit, the first electric heating device and the third electric heating device are respectively connected with the control system;
the reactor comprises a reaction main body, a temperature measuring device, a pressure gauge, a heat insulation structure, a second electric heating device, a temperature control device, a high-temperature valve and a mass flow meter, wherein the reaction main body, the temperature measuring device, the pressure gauge, the heat insulation structure, the second electric heating device, the temperature measuring device and the control system are used for carrying out chemical vapor deposition reaction, the temperature measuring device is connected with the control system, the temperature measuring device can measure the internal temperature of the reaction main body, the pressure gauge is arranged on the reaction main body, the pressure gauge can measure the pressure in the reaction main body, the heat insulation structure is arranged on the reaction main body, the heat insulation structure can keep warm of the reaction main body, the second electric heating device is arranged on the reaction main body, the second electric heating device can heat the reaction main body, the second electric heating device is connected with the control system through the temperature control device, the high-temperature valve is arranged on the reaction main body, and the, The pipeline is connected with the reaction main body, the mass flow meter is arranged on the gas flow passage pipeline connected with the reaction main body, and the mass flow meter can meter the gas flow flowing through the pipeline;
the method comprises the following steps:
(1) firstly, placing a substrate to be reacted in a reaction main body, and then introducing inert gas into the reaction main body to exhaust air in the reaction main body; then, carrying out vacuum pumping treatment on the reaction main body through a vacuum unit, and closing the vacuum unit for later use after the vacuum degree of the reaction main body reaches a preset value;
(2) with Re2(CO)10、Co(acac)2As a raw material, Re2(CO)10Placing in a first sublimation chamber, adding Co (acac)2Is arranged in the second sublimation chamber and is heated by the first electric heaterThe sublimation chamber is electrically heated, and then the raw material Re in the sublimation chamber is heated2(CO)10、Co(acac)2Carrying out sublimation treatment, and after the pressure in the sublimation chamber reaches a set value, adding Re in the first sublimation chamber2(CO)10Gas of gas and first reaction gas generator, Co (acac) in second sublimation chamber2The gas is respectively mixed with the gas of the second reaction gas generator and is introduced into the reaction main body for reaction; meanwhile, the vacuum unit is opened to maintain the vacuum degree of the reaction body, and reaction gas is introduced into the reaction body through the third reaction gas generator to maintain Re2(CO)10、Co(acac)2The partial pressure of (a) is constant;
(3) the control system controls the second electric heating device to heat through the temperature control system, so that the temperature in the reaction main body is 400-600 ℃, and the Re in the reaction chamber is maintained2(CO)10、Co(acac)2To ensure the reaction; and after the reaction is finished, closing the third reaction gas generator, the temperature control system and the vacuum unit, introducing inert gas into the reaction main body until the normal pressure in the reaction main body is recovered, and taking out the sample after the temperature of the reaction main body is reduced to the room temperature.
The temperature measuring device is a thermocouple, the thermocouple is respectively arranged in the sublimation chamber, in the reactor and on the pipeline, and the thermocouple can measure the temperature in the sublimation chamber, in the reactor and in the pipeline.
The gas in the first reaction gas generator, the second reaction gas generator and the third reaction gas generator is hydrogen. The inert gas is one or more of argon and nitrogen.
The reaction gas in the first reaction gas generator and the sublimed Re in the first sublimation chamber2(CO)10The gas is mixed in the pipeline and then enters the reactor through the pipeline, the reaction gas in the second reaction gas generator and the sublimed Co (acac) in the second sublimation chamber2The gases are mixed in the pipeline and then enter the reactor through the pipeline.
In the step (2), the sublimation temperature is 140-180 ℃.
In the step (3), the reaction temperature is 400-600 ℃.
In the step (3), the time of the vapor deposition reaction is 30-600 min.
In the step (3), the pressure in the reaction body is 10-1-105Pa。
The sublimation chamber adopts a fluidized bed.
In order to solve the problems, the application provides a chemical vapor deposition method for preparing a Co-Re alloy coating, based on the chemical vapor deposition method, the Co-Re alloy coating with better quality can be deposited, and the chemical vapor deposition method is simple in equipment structure, low in cost, good in product quality, higher in application value and better in application prospect.
The preparation method can complete the preparation work of the Co-Re alloy coating, and has the advantages of low deposition temperature and simple process. Meanwhile, no toxic and harmful byproducts are generated in the deposition process, and the method has good environmental benefit. Compared with the prior art, the method can realize the preparation of the Co-Re alloy coating at low temperature, and provides a brand new solution for solving the problem of high-temperature ablation. Further, the sublimation chamber may employ a fluidized bed to increase the sublimation rate of the precursor, providing a stable partial pressure of the precursor.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic view of a Co-Re alloy chemical vapor deposition apparatus according to the present invention.
FIG. 2 is a simplified diagram of a chemical vapor deposition apparatus for Co-Re alloy.
The labels in the figure are: 1. first sublimation room, 2, second sublimation room, 3, reaction main part, 5, temperature control device, 6, mass flowmeter, 7, pipeline temperature control appearance, 8, vacuum unit, 9, treat the reaction base member, 10, objective table, 11, first reaction gas generator, 12, second reaction gas generator, 13, first electric heater unit, 14, second electric heater unit, 15, insulation construction.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
As shown in the figure, the apparatus used in the preparation method of this embodiment includes a sublimation unit, a first reactive gas generator, a second reactive gas generator, a reactor, a third reactive gas generator, a pipeline unit, a vacuum unit, and a control system.
Wherein, the sublimation unit includes the sublimation room, is used for carrying out the first electric heater unit that heats to the sublimation room. In this embodiment, there are two sublimation units; wherein the sublimation chamber comprises a chamber for collecting Re2(CO)10A first sublimation chamber for sublimating, for co (acac)2A second sublimation chamber for sublimation; the first reaction gas generator is connected with the first sublimation chamber, and the reaction gas in the first reaction gas generator and the sublimed Re in the first sublimation chamber2(CO)10The gas can enter a reactor for reaction after being mixed; the second reaction gas generator is connected with the second sublimation chamber, and the reaction gas in the second reaction gas generator and the sublimed Co (acac) in the second sublimation chamber2The gas can enter the reactor for reaction after being mixed. In this structure, the sublimation unit can realize heating sublimation and the regulation and control gas flow who lets in the reactor to the precursor, and the accuse temperature can freely be set for between 100 and 500 ℃, realizes the automatic procedure lift of sublimation room temperature, accuse temperature precision by K graduation number thermocouple + accurate digital display procedure temperature control appearance: 1 ℃ C.
Wherein, the pipeline unit includes pipeline, the second that first sublimation unit and reactor link to each other sublimes the pipeline, the third electric heater unit that the unit and reactor link to each other of first sublimation, and the third electric heater unit sets up respectively on pipeline, the second that first sublimation unit and reactor link to each other sublimes the pipeline that the unit and reactor link to each other. The third electric heating device is connected with the control system through the temperature control device and is used for ensuring the temperature of gas flowing through the pipeline. Meanwhile, a third reaction gas generator is connected with the reactor through a pipeline and used for filling reaction gas into the reactor. In the gas transportation, need heat the heat preservation to the pipeline and handle, prevent that the mist from taking place the condensation in the transportation, heating system realizes the temperature control of gas circuit pipeline, accuse temperature precision by K graduation number thermocouple + intelligent digital display accuse temperature appearance + electric heating alloy silk heat-generating body: 1 ℃ C.
Further, the reactor comprises a reaction main body for carrying out chemical vapor deposition reaction, a temperature measuring device, a pressure gauge, a heat insulation structure, a second electric heating device, a temperature control device, a high-temperature valve and a mass flow meter, wherein the temperature measuring device is connected with the control system and can measure the temperature in the reaction main body, the pressure gauge is arranged on the reaction main body and can measure the pressure in the reaction main body, the heat insulation structure is arranged on the reaction main body and can insulate the temperature of the reaction main body, the second electric heating device is arranged on the reaction main body and can heat the reaction main body, the second electric heating device is connected with the control system through the temperature control device, the high-temperature valve is arranged on the reaction main body and can respectively pass through the high-temperature valve, and the first reaction gas generator, the second reaction gas generator and the third reaction gas generator, The pipeline is connected with the reaction main body, the mass flow meter is arranged on the gas flow passage pipeline connected with the reaction main body, and the mass flow meter can meter the gas flow flowing through the pipeline. Furthermore, an objective table is arranged in the reaction main body, and a matrix to be reacted is placed on the objective table. In the structure, the temperature control temperature of the reactor can be freely set between 100-800 ℃, the automatic program lifting of the temperature of the reaction chamber is realized by the K graduation number thermocouple and the precise digital display program temperature controller, and the temperature control precision is as follows: 1 ℃ C.
In the embodiment, the vacuum unit is connected with the reactor and can vacuumize the reactor (the vacuum unit is mainly used for controlling the pressure in the reaction main body and ensuring that the chemical vapor deposition reaction can carry out an experiment under the preset pressure, and the vacuum unit consists of a 2XZ-1 double-rotor mechanical vacuum pump, a stainless steel valve and a spring tube vacuum meter so as to realize the acquisition, detection and control of the system vacuum); the first reaction gas generator, the second reaction gas generator, the third reaction gas generator, the pipeline unit, the vacuum unit, the first electric heating device and the third electric heating device are respectively connected with the control system.
In this example, the procedure for preparing a Co-Re alloy based on the foregoing apparatus was as follows.
(1) Firstly, a substrate to be reacted is placed in a reaction main body and is placed on an objective table; then argon is introduced into the reaction main body to exhaust the air in the reaction main body. And then, closing the two high-temperature valves on the reactor to prevent gas from entering the reactor, vacuumizing the reaction main body through the vacuum unit, and closing the vacuum unit for later use after the vacuum degree of the reaction main body reaches a preset value.
(2) With Re2(CO)10、Co(acac)2As a raw material, Re2(CO)10Placing in a first sublimation chamber, adding Co (acac)2Arrange the second in the sublimation chamber to carry out electrical heating to the sublimation chamber through first electrical heating device, and then to the raw materials Re in the sublimation chamber2(CO)10、Co(acac)2Carrying out sublimation treatment. In this embodiment, the sublimation temperature is 140-. Meanwhile, the reaction matrix in the reaction main body is heated through a second electric heating device, and heat preservation is carried out when the temperature reaches 400-600 ℃.
(3) After the pressure in the sublimation chamber reaches a set value, the Re in the first sublimation chamber is added2(CO)10Hydrogen gas of gas and first reaction gas generator, Co (acac) in second sublimation chamber2The gas is respectively mixed with hydrogen of a second reaction gas generator and is introduced into the reaction main body for reaction; and the vacuum degree of the reaction main body is ensured while the reaction is carried out. When the mixed gas is introduced, the pressure of the mixed gas changes. At this time, hydrogen gas needs to be introduced into the reaction main body through the third reaction gas generator to maintain the partial pressure of the precursor constant.
In this example, the reactionThe temperature in the main body is 400-600 ℃, and the Re in the reaction chamber is maintained2(CO)10、Co(acac)2The reaction time is 120min, and the reaction pressure in the reaction main body is 10-1-105Pa. in the experiment, the total air input in the reaction is 50-200ml/min, the size of the reaction chamber is calculated under the above conditions, the size of the reaction chamber is 30ml-30000L according to the Dalton partial pressure law PV = nrT, the size of the reaction chamber can be phi 30 × 200mm considering the sample placement and the carrier gas input in the experiment process, the pressure of the sublimation chamber is controlled to be 10 mm-1-105Pa, sublimation temperature of 140--1-105Pa。
After the reaction is finished, the third reaction gas generator, the temperature control system, the pipeline unit and the vacuum unit are closed, and argon is introduced into the reaction main body until the normal pressure in the reaction main body is recovered. And (5) taking out the sample after the temperature of the reaction main body is reduced to room temperature.
In this example, Co (acac) is used respectively2And Re2(CO)10As a precursor, Co atoms and Re atoms are simultaneously deposited on a tube steel substrate (0CrNi2MoVA type steel) to generate the Co-Re alloy anti-ablation coating. The experimental results show that: the Co-Re alloy prepared by the embodiment has better quality. Meanwhile, the reaction temperature of the method is 400-600 ℃, and the method has the advantages of low deposition temperature and simple process. Meanwhile, the Co-Re alloy of the invention has no toxic and harmful by-products in the deposition process, and is environment-friendly.
In the application, five temperature control systems are designed in the Co-Re chemical vapor deposition integrated system, which are respectively as follows: the two sets of sublimation chamber control systems are separately and independently controlled to achieve the purposes of independent temperature control and respective sublimation, and the three temperature control systems are controlled by programs; the other two sets of temperature control systems are applied to the pipeline, and the difference is that the two sets of pipeline temperature control systems adopt fixed value control to prevent the sublimation precursor from being solidified on the pipeline to cause raw material waste.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (10)
1. The chemical vapor deposition method for preparing the Co-Re alloy coating is characterized in that the adopted equipment comprises a sublimation unit, a first reaction gas generator, a second reaction gas generator, a reactor, a third reaction gas generator, a pipeline unit, a vacuum unit and a control system, wherein the third reaction gas generator is connected with the reactor through a pipeline and can charge reaction gas into the reactor, the vacuum unit is connected with the reactor and can vacuumize the reactor;
the sublimation unit includes the sublimation room, is used for carrying out the first electric heater unit that heats to the sublimation room, the sublimation unit is two, the sublimation room is including being used for Re2(CO)10A first sublimation chamber for sublimating, for co (acac)2A second sublimation chamber for sublimation, wherein the first reaction gas generator is connected with the first sublimation chamber, and the reaction gas in the first reaction gas generator and the Re sublimated in the first sublimation chamber2(CO)10The mixed gas can enter a reactor to react, the second reaction gas generator is connected with the second sublimation chamber, and the reaction gas in the second reaction gas generator and the sublimed Co (acac) in the second sublimation chamber2The gas can enter a reactor for reaction after being mixed;
the pipeline unit comprises a pipeline with a first sublimation unit connected with the reactor, a pipeline with a second sublimation unit connected with the reactor, and a third electric heating device, wherein the third electric heating device is respectively arranged on the pipeline with the first sublimation unit connected with the reactor and the pipeline with the second sublimation unit connected with the reactor, and can heat the pipelines;
the first reaction gas generator, the second reaction gas generator, the third reaction gas generator, the pipeline unit, the vacuum unit, the first electric heating device and the third electric heating device are respectively connected with the control system;
the reactor comprises a reaction main body, a temperature measuring device, a pressure gauge, a heat insulation structure, a second electric heating device, a temperature control device, a high-temperature valve and a mass flow meter, wherein the reaction main body, the temperature measuring device, the pressure gauge, the heat insulation structure, the second electric heating device and the third reaction gas generator are used for carrying out chemical vapor deposition reaction, the temperature measuring device is connected with a control system, the temperature measuring device can measure the internal temperature of the reaction main body, the pressure gauge is arranged on the reaction main body, the pressure gauge can measure the pressure in the reaction main body, the heat insulation structure is arranged on the reaction main body, the heat insulation structure can keep the temperature of the reaction main body, the second electric heating device is arranged on the reaction main body, the second electric heating device can heat the reaction main body, the second electric heating device is connected with the control system through the temperature control device, the high-temperature valve is arranged on the reaction main body, and the first reaction gas generator, The pipeline is connected with the reaction main body, the mass flow meter is arranged on the gas flow passage pipeline connected with the reaction main body, and the mass flow meter can meter the gas flow flowing through the pipeline;
the method comprises the following steps:
(1) firstly, placing a substrate to be reacted in a reaction main body, and then introducing inert gas into the reaction main body to exhaust air in the reaction main body; then, carrying out vacuum pumping treatment on the reaction main body through a vacuum unit, and closing the vacuum unit for later use after the vacuum degree of the reaction main body reaches a preset value;
(2) with Re2(CO)10、Co(acac)2As a raw material, Re2(CO)10Placing in a first sublimation chamber, adding Co (acac)2Arrange the second in the sublimation chamber to carry out electrical heating to the sublimation chamber through first electrical heating device, and then to the raw materials Re in the sublimation chamber2(CO)10、Co(acac)2Carrying out sublimation treatment to the pressure in the sublimation chamberAfter the set value is forcibly reached, the Re in the first sublimation chamber is added2(CO)10Gas of gas and first reaction gas generator, Co (acac) in second sublimation chamber2The gas is respectively mixed with the gas of the second reaction gas generator and is introduced into the reaction main body for reaction; meanwhile, the vacuum unit is opened to maintain the vacuum degree of the reaction body, and reaction gas is introduced into the reaction body through the third reaction gas generator to maintain Re2(CO)10、Co(acac)2The partial pressure of (a) is constant;
(3) the control system controls the second electric heating device to heat through the temperature control system, so that the temperature in the reaction main body is 400-600 ℃, and the Re in the reaction chamber is maintained2(CO)10、Co(acac)2To ensure the reaction; after the reaction is finished, the third reaction gas generator, the temperature control system, the pipeline unit and the vacuum unit are closed, inert gas is introduced into the reaction main body until the normal pressure in the reaction main body is recovered, and after the temperature of the reaction main body is reduced to the room temperature, the sample is taken out.
2. The method according to claim 1, wherein the temperature measuring means are thermocouples disposed in the sublimation chamber, the reactor and the piping, respectively, and the thermocouples are capable of measuring the temperature in the sublimation chamber, the reactor and the piping.
3. The method of claim 1, wherein the reactant gas in the first, second, and third reactant gas generators is hydrogen.
4. The method of claim 1, wherein the inert gas introduced into the reactor is one or more of argon and nitrogen.
5. A method according to claim 3, characterized in that the reaction gas in the first reaction gas generator and the first sublimation chamberInternal sublimating Re2(CO)10The gas is mixed in the pipeline and then enters the reactor through the pipeline, the reaction gas in the second reaction gas generator and the sublimed Co (acac) in the second sublimation chamber2The gases are mixed in the pipeline and then enter the reactor through the pipeline.
6. The method according to claim 1, wherein in the step (2), the sublimation temperature is 140 to 180 ℃.
7. The method as claimed in claim 1, wherein the reaction temperature in step (3) is 400-600 ℃.
8. The method according to claim 6, wherein in the step (3), the vapor deposition reaction time is 30-600 min.
9. The method according to any one of claims 1 to 8, wherein in the step (3), the pressure in the reaction body is 10-1-105Pa。
10. The method of claim 1, wherein the sublimation chamber employs a fluidized bed.
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