CN113512713A - Rhenium crucible and preparation method and application thereof - Google Patents

Rhenium crucible and preparation method and application thereof Download PDF

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Publication number
CN113512713A
CN113512713A CN202110771475.0A CN202110771475A CN113512713A CN 113512713 A CN113512713 A CN 113512713A CN 202110771475 A CN202110771475 A CN 202110771475A CN 113512713 A CN113512713 A CN 113512713A
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rhenium
crucible
deposition
die core
preparation
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魏燕
胡昌义
蔡宏中
胡晋铨
周利民
张诩翔
王献
闻明
张贵学
崔浩
陈力
汪星强
黎玉盛
刘盼
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Sino Platinum Metals Co Ltd
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Sino Platinum Metals Co Ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/002—Crucibles or containers

Abstract

The invention provides a rhenium crucible, a preparation method and application thereof, and belongs to the technical field of metal material preparation. The invention provides a preparation method of a rhenium crucible, which comprises the following steps: under the vacuum condition, rhenium and chlorine are subjected to chlorination reaction to obtain ReCl5A gas; processing the matrix to obtain a die core for the rhenium deposition crucible; preheating the die core for the rhenium deposition crucible to obtain the die core for the preheated rhenium deposition crucible; subjecting the ReCl5And conveying the gas to the surface of the die core for preheating and depositing the rhenium crucible for chemical vapor deposition to obtain the rhenium crucible. The method adopts an on-site chlorination Chemical Vapor Deposition (CVD) method to prepare the rhenium crucible, has the advantages of short flow, mature process, high deposition rate and high utilization rate of raw materials, and can obtain the rhenium crucible with high compactness and high purity.

Description

Rhenium crucible and preparation method and application thereof
Technical Field
The invention relates to the technical field of metal material preparation, in particular to a rhenium crucible and a preparation method and application thereof.
Background
In recent years, 2 μm band lasers have been widely used in many fields such as optical communication, medicine, remote sensing, and military. Laser materials are the basis for lasers. At present, the crucible for preparing the laser crystal by adopting the pulling method is mainly a noble metal iridium crucible. The iridium crucible is mainly used for the preparation of crystals having a melting point not exceeding 2200 ℃ limited by the melting point of iridium. The high melting point rare earth oxide crystal has the performance characteristics of high-power laser, high thermal conductivity and low phonon energy, has important application in the field of high-energy, high-power or low phonon lasers, and becomes a research and development hotspot of laser crystals in recent years. Since the melting point of such crystals is high, e.g. Sc2O3、Y2O3And Lu2O3The melting points of the crystal are 2430 ℃, 2430 ℃ and 2450 ℃, and the growth cannot be carried out by using the current mainstream growth method of the laser crystal, namely an iridium crucible pulling method. Rare earth refractoryThe high melting point of the molten oxide crystals places extreme limitations on the choice of crucible materials. At high temperatures above the melting point of the crystal, the crucible must remain stable and not chemically react with the crystal melt. Researchers have used tungsten, rhenium and carbon materials with melting points in excess of 3000 ℃ as crucible materials, and have shown that only rhenium crucibles can meet the above specifications to the greatest extent. The melting point of rhenium is as high as 3180 ℃, and the rhenium has excellent high-temperature mechanical property and extremely strong corrosion resistance, can be used at the high temperature of 2500-2800 ℃, does not react with refractory crystals such as rare earth oxide and the like, and is an ideal crucible material for preparing refractory laser crystals.
At present, a rhenium crucible is mainly prepared at home and abroad by a Powder Metallurgy (PM) method. For example, a foreign Heley company adopts a powder cold isostatic pressing-hot isostatic pressing-2500 ℃ high-temperature sintering-grinding processing technical scheme to prepare a rhenium crucible (US 5993545A), and the density of the obtained rhenium crucible material is 88-95% of the theoretical density; domestic CN201610588625.3 discloses a crucible prepared by a PM method, and the process route is as follows: powder injection molding, ingot blank degreasing and high-temperature sintering at 2400 ℃, and the obtained rhenium crucible has the density of about 95-98% of the theoretical density and lower purity (99.38%).
In the prior art, the problems of low density and low purity exist in the rhenium crucible prepared by adopting a powder metallurgy method.
Disclosure of Invention
In view of the above, the present invention aims to provide a rhenium crucible, a preparation method and an application thereof. The preparation method can obtain the rhenium crucible with high compactness and high purity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a rhenium crucible, which comprises the following steps;
under the vacuum condition, rhenium and chlorine are subjected to chlorination reaction to obtain ReCl5A gas;
processing the matrix to obtain a die core for the rhenium deposition crucible;
preheating the die core for the rhenium deposition crucible to obtain the die core for the preheated rhenium deposition crucible;
subjecting the ReCl5And conveying the gas to the surface of the die core for preheating and depositing the rhenium crucible for chemical vapor deposition to obtain the rhenium crucible.
Preferably, the molar ratio of rhenium to chlorine gas is 2: 5.
Preferably, the flow rate of the chlorine gas is 50-100 mL/min.
Preferably, the material of the substrate is graphite or a metal rod.
Preferably, the metal rod is a molybdenum rod, a niobium rod, a molybdenum alloy rod or a niobium alloy rod.
Preferably, the preheating temperature is 1100-1300 ℃.
Preferably, the temperature of the chemical vapor deposition is 1100-1300 ℃, and the pressure is 800-1200 Pa.
Preferably, the temperature of the chlorination reaction is 600-900 ℃.
The invention also provides the rhenium crucible prepared by the preparation method in the technical scheme.
The invention also provides the application of the rhenium crucible in the technical scheme in the preparation of rare earth refractory oxide crystals.
The invention provides a preparation method of a rhenium crucible, which comprises the following steps: under the vacuum condition, rhenium and chlorine are subjected to chlorination reaction to obtain ReCl5A gas; processing the matrix to obtain a die core for the rhenium deposition crucible; preheating the die core for the rhenium deposition crucible to obtain the die core for the preheated rhenium deposition crucible; subjecting the ReCl5And conveying the gas to the surface of the die core for preheating and depositing the rhenium crucible for chemical vapor deposition to obtain the rhenium crucible. The method adopts an on-site chlorination Chemical Vapor Deposition (CVD) method to prepare the rhenium crucible, has the advantages of short flow, mature process, high deposition rate and high utilization rate of raw materials, and can obtain the rhenium crucible with high compactness and high purity. And the rhenium prepared by the CVD method has the advantages of reinforced microstructure, high-temperature creep strength, low creep rate and difficult deformation of a rhenium substrate in ultrahigh-temperature application.
Compared with the prior art, the method has the following advantages:
(1) the preparation process flow is short. The chlorination reaction of the rhenium raw material and the CVD method of the rhenium material are carried out simultaneously, and the reaction process is simple; and after the deposition is finished, the spray pipe is subjected to fine finishing to obtain the rhenium crucible, and the preparation process is short.
(2) The deposition rate is high, and the utilization rate of raw materials is high. In the temperature range of 1100-1300 ℃, ReCl5Rhenium atoms can be fully decomposed and separated out, and the deposition rate of the rhenium material reaches more than 0.2 mm/h; the invention adopts an induction heating mode to heat the mold core, and rhenium atoms are only precipitated on the surface of the mold core. The walls of the deposition chamber are cold and no rhenium atoms are deposited. Under the process conditions determined by the invention, the deposition efficiency of rhenium is high, and the utilization rate of rhenium of the raw material exceeds 90 percent.
(3) The rhenium material has high density and high purity. Preparation of rhenium crucible by CVD method mainly through in-situ chlorination reaction to form ReCl5Rhenium atoms are separated out and stacked one by one to form a rhenium layer, the density of the obtained rhenium material exceeds 99.5 percent of the theoretical density, and the compactness is high; chemical vapor deposition is a material purification method, impurities in raw materials can be effectively removed, and the purity of the obtained deposited rhenium material exceeds 99.9%.
(4) The rhenium material has excellent high-temperature mechanical property. As a nano twin crystal strengthening structure is formed in the deposition process of rhenium atoms, the rhenium material prepared by the CVD method has higher high-temperature creep strength and much lower creep rate than powder metallurgy rhenium.
(5) The machining amount is small, and the dimensional accuracy is high. CVD is a near-net-shape forming technology, the rhenium layer is uniformly deposited on the surface of the die core in a coating mode, and the rhenium crucible finished product can be obtained only by a small amount of fine finishing.
(6) The rhenium crucible has lower cost. The rhenium crucible preparation method has the advantages of short process flow, high utilization rate of raw materials in the deposition process and less processing turning amount, and the used waste rhenium crucible can be completely used as the raw materials for repeated recycling, so that the production cost of the rhenium crucible product is greatly reduced compared with the existing method.
The data of the embodiment show that the deposition rate of rhenium is 0.2-0.3 mm/h, the size of the crucible after deposition is uniform, and the utilization rate of rhenium is over 90%; chemical vapor phaseThe deposition is by Recl5The gas is thermally decomposed to obtain rhenium atoms, the rhenium atoms are stacked on the outer surface of the preheated mold core one by one to form a rhenium material, the relative density of the rhenium crucible material is 99.5-99.8%, and the purity is 99.9-99.93%; the rhenium material forms a growth twin crystal structure in the deposition process, and the high-temperature performance of the rhenium material is excellent: the creep strain amount under the experimental conditions that the tensile strength is 122.5-130.9 MPa at 1800 ℃, the temperature is 1649 ℃ and the stress is 27.56MPa is only 0.22-0.24%; the size precision of the rhenium crucible is less than or equal to 0.03mm, and the roughness of the inner surface is less than or equal to 1.6 mu m.
Drawings
FIG. 1 is a schematic view of an apparatus for a method of producing a rhenium crucible in an embodiment of the present invention;
FIG. 2 is a schematic view of a rhenium crucible in a deposited state obtained in example 1;
FIG. 3 is a pictorial view of a rhenium crucible product made in example 1;
fig. 4 is a TEM microstructure micrograph of the rhenium material obtained in example 1.
Detailed Description
The invention provides a preparation method of a rhenium crucible, which comprises the following steps;
under the vacuum condition, rhenium and chlorine are subjected to chlorination reaction to obtain ReCl5A gas;
processing the matrix to obtain a die core for the rhenium deposition crucible;
preheating the die core for the rhenium deposition crucible to obtain the die core for the preheated rhenium deposition crucible;
subjecting the ReCl5And conveying the gas to the surface of the die core for preheating and depositing the rhenium crucible for chemical vapor deposition to obtain the rhenium crucible.
The apparatus for preparing the rhenium crucible is not particularly limited, and an apparatus known to those skilled in the art can be adopted, and in the specific embodiment of the invention, the apparatus used is the chemical vapor deposition device disclosed in CN200510010838. X.
In the invention, rhenium and chlorine are subjected to chlorination reaction under vacuum condition to obtain ReCl5A gas;
in the present invention, the pressure of the vacuum condition is preferably 0.8 Pa.
In the present invention, the molar ratio of rhenium to chlorine gas is preferably 2: 5.
In the invention, the flow rate of the chlorine gas is preferably 50-100 mL/min, and more preferably 60-80 mL/min.
The matrix is processed to obtain the die core for the rhenium deposition crucible. The specific process of the processing is not particularly limited, and the processing is preferably turning and grinding.
In the present invention, the material of the substrate is preferably graphite or a metal rod, and the metal rod is more preferably a molybdenum rod, a niobium rod, a molybdenum alloy rod, or a niobium alloy rod.
In the present invention, the rhenium deposition crucible core is preferably cylindrical, and the size of the outer surface of the rhenium deposition crucible core corresponds to the size of the rhenium crucible inner profile.
After the processing is finished, the method preferably further comprises the steps of sequentially carrying out surface polishing, ultrasonic cleaning and drying treatment to obtain the die core for the rhenium deposition crucible. The specific modes of the surface polishing, ultrasonic cleaning and drying treatment are not particularly limited, and the operation mode known by the skilled person can be adopted.
After the die core for the rhenium deposition crucible is obtained, the die core for the rhenium deposition crucible is preheated, and the die core for the preheated rhenium deposition crucible is obtained.
In the invention, the preheating temperature is preferably 1100-1300 ℃, more preferably 1150-1250 ℃, and the preheating function is to realize chemical vapor deposition.
To obtain ReCl5After gas and preheating of a die core for rhenium deposition crucible, the invention uses the Recl5And conveying the gas to the surface of the die core for preheating and depositing the rhenium crucible for chemical vapor deposition to obtain the rhenium crucible.
In the invention, the temperature of the chemical vapor deposition is preferably 1100-1300 ℃, more preferably 1150-1250 ℃, and the pressure is preferably 800-1200 Pa, more preferably 1000Pa, the time of the chemical vapor deposition is not specially limited, and the chemical vapor deposition is stopped when the thickness of the crucible reaches the design requirement.
In the present invention, the chemical vapor deposition is preferably performed in a deposition chamber, and the preheated rhenium deposition crucible is preferably mounted on a rotary table of the deposition chamber, and the rotary table can rotate and move up and down, so that the deposited rhenium layer is more uniform in the circumferential direction and the height direction.
After the chemical vapor deposition is finished, the method preferably further comprises the steps of machining and removing the mold core in sequence, wherein the machining preferably comprises the steps of machining and grinding the outer profile of the obtained chemical vapor deposition by adopting a numerical control machine to meet the size requirement of a crucible drawing, the mold core is preferably removed by utilizing a turning method, then the inner profile of the crucible is polished, and finally the rhenium crucible is obtained. The present invention is not limited to the specific manner of turning, grinding and polishing, and can be performed in a manner known to those skilled in the art.
The invention also provides the rhenium crucible prepared by the preparation method in the technical scheme.
The invention also provides the application of the rhenium crucible in the technical scheme in the preparation of rare earth refractory oxide crystals.
In order to further illustrate the present invention, the rhenium crucible and the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
FIG. 1 is a schematic view of the apparatus for the method of preparing a rhenium crucible of the present invention, the deposition apparatus being a cold wall (induction heating) open-tube gas flow system. FIG. 1 includes chlorine gas inlet, rhenium chlorination chamber, resistance heating furnace, deposition chamber, rotary platform for placing the substrate to be deposited (mold core), induction heating coil and exhaust system. The method is characterized in that graphite or metal rods are used as a base body of a crucible for depositing rhenium, the base body is firstly processed into a cylindrical shape according to the shape and the dimensional drawing requirements of the inner surface of the crucible, a mold core is arranged on a rotating platform of a deposition chamber, a raw material metal rhenium block is filled into a chlorination chamber, and then a mechanical vacuum is drawn on a deposition system. Will be provided withThe mold core is inductively heated to the deposition temperature, chlorine gas after drying and purifying treatment is introduced into a chlorination chamber, and Cl is added2Chemically react with Re in the chlorination chamber to form ReCl5A gas. Recl5The gas is transported to the surface of the mold core which is heated to the deposition temperature, the thermal decomposition reaction is carried out to separate out Re atoms, and the Re atoms are gradually accumulated into the high-density rhenium crucible material along with the continuous progress of the deposition process.
Example 1
Processing a graphite rod into a cylindrical mold core with the diameter of 80mm multiplied by 80mm, polishing, ultrasonically cleaning and drying the surface of the mold core, mounting the mold core to be deposited with rhenium on a rotating platform of a deposition chamber, and positioning the mold core in the middle of an induction coil.
The rhenium block material was placed in the quartz chamber of the chlorination chamber, the deposition system was sealed and evacuated to 0.8 Pa.
The chlorination chamber is heated to 800 ℃ and the deposition die core is heated to 1250 ℃. Then chlorine gas is introduced into the chamber at a rate of 100mL/min, and the pressure in the deposition chamber is adjusted to 1000 Pa.
The deposition rate of rhenium was 0.30mm/h under the process conditions of this example, the deposition was stopped 17.5h after deposition, and the test piece was removed after cooling. The thickness of the re layer was measured to be 5.25mm, and the re crucible in a deposited state was obtained as shown in fig. 2.
Compiling a numerical control machining program according to the requirements of a design drawing, and selecting a proper hard cutter to perform mechanical finishing machining on the outer surface of the rhenium crucible in a deposition state; then, the mold core is removed by turning, and the inner profile of the crucible is polished, so that a rhenium crucible product with the inner diameter of 80mm and the thickness of 5.0mm is finally obtained, as shown in fig. 3. As a result of Transmission Electron Microscope (TEM) observation of the obtained rhenium crucible, as shown in fig. 4, it is understood from fig. 4 that the rhenium material prepared by the CVD method has a lamellar growth twin structure having a strengthening effect, and the rhenium material prepared in this example has high-temperature strength.
And carrying out related detection on the obtained rhenium crucible material. The utilization rate of the rhenium raw material is 93 percent; the relative density is 99.8 percent, and the purity is 99.95 percent; the tensile strength at 1800 ℃ is 130.9MPa, the creep strain at 1649 ℃ and the stress of 27.56MPa is 0.22 percent; the inner diameter of the crucible is 80 +/-0.028 mm, the thickness of the crucible is 5 +/-0.025 mm, and the roughness of the inner surface of the crucible is 1.6 mu m.
Example 2
Processing a graphite rod into a cylindrical mold core with the diameter of 80mm multiplied by 80mm, polishing, ultrasonically cleaning and drying the surface of the mold core, mounting the mold core to be deposited with rhenium on a rotating platform of a deposition chamber, and positioning the mold core in the middle of an induction coil.
The appropriate amount of rhenium block is put in the quartz periphery of the chlorination chamber, and the deposition system is sealed and then vacuumized to 0.8 Pa.
The chlorination chamber was heated to 900 ℃ and the deposition core was heated to 1300 ℃. Then chlorine gas is introduced into the deposition chamber for 100mL/min, and the pressure of the deposition chamber is adjusted to 1200 Pa.
The deposition rate of rhenium was 0.35mm/h under the process conditions of this example, the deposition was stopped after 15h of deposition, and the test piece was removed after cooling. The thickness of the rhenium layer was measured to be 5.25mm, and the rhenium crucible in the deposited state was obtained.
Compiling a numerical control machining program according to the requirements of a design drawing, and selecting a proper hard cutter to perform mechanical finishing machining on the outer surface of the rhenium crucible in a deposition state; and removing the mold core by using a turning method, and polishing the inner profile of the crucible to finally obtain a rhenium crucible product with the inner diameter of 80mm and the thickness of 5.0 mm.
And carrying out related detection on the obtained rhenium crucible material. The utilization rate of the rhenium raw material is 94%; the relative density is 99.6 percent, and the purity is 99.93 percent; the tensile strength at 1800 ℃ is 124.5MPa, the creep strain at 1649 ℃ and the stress of 27.56MPa is 0.23 percent; the inner diameter of the crucible is 80 +/-0.028 mm, the thickness of the crucible is 5 +/-0.025 mm, and the roughness of the inner surface of the crucible is 1.6 mu m.
Example 3
Processing a graphite rod into a cylindrical mold core with the diameter of 70mm multiplied by 70mm, polishing, ultrasonically cleaning and drying the surface of the mold core, mounting the mold core to be deposited with rhenium on a rotating platform of a deposition chamber, and positioning the mold core in the middle of an induction coil.
The appropriate amount of rhenium block is put in the quartz periphery of the chlorination chamber, and the deposition system is sealed and then vacuumized to 0.8 Pa.
The chlorination chamber was heated to 750 ℃ and the deposition core was heated to 1200 ℃. Then chlorine gas is introduced for 90mL/min, and the pressure of the deposition chamber is adjusted to 900 Pa.
The deposition rate of rhenium was 0.25mm/h under the process conditions of this example, the deposition was stopped 17h after deposition, and the test piece was removed after cooling. The thickness of the rhenium layer was measured to be 4.25mm, and the rhenium crucible in the deposited state was obtained.
A numerical control machining program is compiled according to the requirements of a design drawing, and a proper hard tool is selected to perform mechanical finishing machining on the outer molded surface of the rhenium crucible; and removing the mold core by using a turning method, and polishing the inner profile of the crucible to finally obtain a rhenium crucible product with the inner diameter of 70mm and the thickness of 4.0 mm.
And carrying out related detection on the obtained rhenium crucible material. The utilization rate of the rhenium raw material is 92%; the relative density is 99.7 percent, and the purity is 99.93 percent; the tensile strength at 1800 ℃ is 128.6MPa, the creep strain at 1649 ℃ and the stress of 27.56MPa is 0.23 percent; the inner diameter of the crucible is 70 +/-0.025 mm, the thickness is 4 +/-0.023 mm, and the roughness of the inner surface of the crucible is 1.5 mu m.
Example 4
Processing a metal molybdenum rod into a cylindrical mold core with the diameter of 50mm multiplied by 50mm, polishing, ultrasonically cleaning and drying the surface of the mold core, mounting the mold core to be deposited with rhenium on a rotating platform of a deposition chamber, and positioning the mold core in the middle of an induction coil.
The appropriate amount of rhenium block is put in the quartz periphery of the chlorination chamber, and the deposition system is sealed and then vacuumized to 0.8 Pa.
The chlorination chamber was heated to 700 ℃ and the deposition core was heated to 1150 ℃. Then chlorine gas is introduced into the chamber at a rate of 80mL/min, and the pressure in the deposition chamber is adjusted to 1000 Pa.
The deposition rate of rhenium was 0.23mm/h under the process conditions of this example, the deposition was stopped after 13.5h of deposition, and the test piece was removed after cooling. The thickness of the rhenium layer was measured to be 3.10mm, and the rhenium crucible in the deposited state was obtained.
A numerical control machining program is compiled according to the requirements of a design drawing, and a proper hard tool is selected to perform mechanical finishing machining on the outer molded surface of the rhenium crucible; and removing the mold core by using a turning method, and polishing the inner profile of the crucible to finally obtain a rhenium crucible product with the inner diameter of 50mm and the thickness of 3.0 mm.
And carrying out related detection on the obtained rhenium crucible material. The utilization rate of the rhenium raw material is 91 percent; the relative density is 99.6 percent, and the purity is 99.91 percent; the tensile strength at 1800 ℃ is 122.5MPa, the creep strain at 1649 ℃ and the stress of 27.56MPa is 0.24 percent; the inner diameter of the crucible is 50 +/-0.022 mm, the thickness of the crucible is 3 +/-0.022 mm, and the roughness of the inner surface of the crucible is 1.3 mu m.
Example 5
Processing a metal niobium rod into a cylindrical mold core with the diameter of 50mm multiplied by 50mm, polishing, ultrasonically cleaning and drying the surface of the mold core, mounting the mold core to be deposited with rhenium on a rotating platform of a deposition chamber, and positioning the mold core in the middle of an induction coil.
The appropriate amount of rhenium block is put in the quartz periphery of the chlorination chamber, and the deposition system is sealed and then vacuumized to 0.8 Pa.
The chlorination chamber was heated to 600 ℃ and the deposition core was heated to 1100 ℃. Then chlorine gas is introduced for 60mL/min, and the pressure of the deposition chamber is adjusted to 800 Pa.
The deposition rate of rhenium was 0.21mm/h under the process conditions of this example, the deposition was stopped after 15h of deposition, and the test piece was removed after cooling. The thickness of the rhenium layer was measured to be 3.15mm, and the rhenium crucible in the deposited state was obtained.
A numerical control machining program is compiled according to the requirements of a design drawing, and a proper hard tool is selected to perform mechanical finishing machining on the outer molded surface of the rhenium crucible; and removing the mold core by using a turning method, and polishing the inner profile of the crucible to finally obtain a rhenium crucible product with the inner diameter of 50mm and the thickness of 3.0 mm.
And carrying out related detection on the obtained rhenium crucible material. The utilization rate of the rhenium raw material is 91 percent; the relative density is 99.5 percent, and the purity is 99.90 percent; the tensile strength at 1800 ℃ is 123.3MPa, the creep strain at 1649 ℃ and the stress of 27.56MPa is 0.24 percent; the inner diameter of the crucible is 50 +/-0.022 mm, the thickness of the crucible is 3 +/-0.022 mm, and the roughness of the inner surface of the crucible is 1.3 mu m.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. A preparation method of a rhenium crucible is characterized by comprising the following steps;
under the vacuum condition, rhenium and chlorine are subjected to chlorination reaction to obtain ReCl5A gas;
processing the matrix to obtain a die core for the rhenium deposition crucible;
preheating the die core for the rhenium deposition crucible to obtain the die core for the preheated rhenium deposition crucible;
subjecting the ReCl5And conveying the gas to the surface of the die core for preheating and depositing the rhenium crucible for chemical vapor deposition to obtain the rhenium crucible.
2. The method of claim 1, wherein the molar ratio of rhenium to chlorine gas is 2: 5.
3. The method according to claim 1 or 2, wherein the flow rate of the chlorine gas is 50 to 100 mL/min.
4. The method according to claim 1, wherein the substrate is made of graphite or a metal rod.
5. The production method according to claim 4, wherein the metal rod is a molybdenum rod, a niobium rod, a molybdenum alloy rod, or a niobium alloy rod.
6. The method according to claim 1, wherein the temperature of the preheating is 1100 to 1300 ℃.
7. The method according to claim 1, wherein the temperature of the chemical vapor deposition is 1100 to 1300 ℃ and the pressure is 800 to 1200 Pa.
8. The method according to claim 1, wherein the chlorination reaction is carried out at a temperature of 600 to 900 ℃.
9. A rhenium crucible obtained by the production method according to any one of claims 1 to 8.
10. Use of the rhenium crucible of claim 9 in the preparation of a rare earth refractory oxide crystal.
CN202110771475.0A 2021-07-08 2021-07-08 Rhenium crucible and preparation method and application thereof Pending CN113512713A (en)

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