CN111411251B - Anti-oxidation coating for rhenium spray pipe, preparation method of anti-oxidation coating and rhenium-anti-oxidation coating spray pipe - Google Patents

Anti-oxidation coating for rhenium spray pipe, preparation method of anti-oxidation coating and rhenium-anti-oxidation coating spray pipe Download PDF

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CN111411251B
CN111411251B CN202010376203.6A CN202010376203A CN111411251B CN 111411251 B CN111411251 B CN 111411251B CN 202010376203 A CN202010376203 A CN 202010376203A CN 111411251 B CN111411251 B CN 111411251B
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rhenium
coating
spray pipe
temperature
iridium
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CN111411251A (en
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胡昌义
魏燕
蔡宏中
刘俊
陈力
周利民
闻明
张诩翔
崔浩
张贵学
柳森
吴霏
汪星强
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Sino Platinum Metals Co Ltd
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Sino Platinum Metals Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C5/00Alloys based on noble metals
    • C22C5/04Alloys based on a platinum group metal
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical 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
    • C23C16/08Chemical 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
    • C23C16/14Deposition of only one other metal element

Abstract

The invention provides an anti-oxidation coating for a rhenium spray pipe, a preparation method of the anti-oxidation coating and the rhenium-anti-oxidation coating spray pipe, and belongs to the technical field of coating preparation. The oxidation resistant coating of the present invention has high compactness and component uniformity. Smelting is a commonly adopted traditional method for preparing precious metal materials, and has the advantages of high preparation speed, mature process and simple equipment. The material is further homogenized and densified through smelting prealloying, homogenizing heat treatment, hot forging and hot isostatic pressing, and a high-density coating material with the relative density of more than 99.9 percent can be obtained; the coating is prepared by machining, the thickness and the machining precision of the coating are completely machined according to the design requirements of drawings, the thickness uniformity is controllable, and the size precision can reach +/-10 microns.

Description

Anti-oxidation coating for rhenium spray pipe, preparation method of anti-oxidation coating and rhenium-anti-oxidation coating spray pipe
Technical Field
The invention relates to the technical field of coating preparation, in particular to an antioxidant coating for a rhenium spray pipe, a preparation method of the antioxidant coating and the rhenium-antioxidant coating spray pipe.
Background
The low-thrust space engine is mainly applied to attitude and orbit control of a space vehicle. The performance of the engine mainly depends on the working temperature, so that the improvement of the working temperature of the engine has great significance for the improvement of the performance of the engine, the working temperature is determined by the temperature resistance of a thrust device (spray pipe) material of the engine, along with the further development of the aerospace technology, higher requirements are put forward for the performance of the engine, and the working temperature needs to reach more than 1800 ℃. Rhenium is a high-melting-point rare metal with a close-packed hexagonal structure, has excellent comprehensive properties of high-temperature strength, good plasticity, thermal shock resistance, chemical inertness and the like, and becomes a three-generation aerospace engine nozzle matrix structure material. However, rhenium has poor oxidation resistance, and an oxidation resistant coating is required to protect rhenium when the rhenium is used in a high-temperature oxidation environment. The iridium is a noble metal with higher melting point and stronger oxidation resistance, and the thermal expansion coefficients of the iridium and rhenium are very close, so that the iridium is suitable for being used as a protective coating of a rhenium spray pipe base material. The working temperature of the rhenium-based/iridium-coated engine reaches over 1800 ℃ and can reach 2200 ℃ at most.
The preparation method of the iridium coating is mainly a deposition method, and comprises Chemical Vapor Deposition (CVD), arc deposition, fused salt electrodeposition and the like. CVD is widely used for preparing iridium coatings by utilizing the thermal decomposition reaction of precursor compounds of iridium (such as iridium acetylacetonate), and the method has the advantages that the obtained coatings have higher density, but have the defects of slow deposition rate and high cost; the electric arc deposition iridium process is a Physical Vapor Deposition (PVD) method, which has the advantages of high deposition rate, but because the iridium coating is deposited on the inner surface of the rhenium spray pipe, the coating thickness control, measurement and coating quality inspection are difficult to realize, and the deposition efficiency and the utilization rate of the iridium target are not high; fused salt electrodeposition of iridium has the advantages of high deposition rate and poor repeatability, and the deposition quality is difficult to control.
Disclosure of Invention
In view of the above, the invention aims to provide an antioxidant coating for a rhenium spray pipe, a preparation method of the antioxidant coating and the rhenium-antioxidant coating spray pipe. The preparation method provided by the invention can obtain the antioxidant coating with high compactness and uniform components.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an anti-oxidation coating for a rhenium spray pipe, which comprises the following steps:
smelting iridium to obtain a cylindrical ingot blank;
carrying out hot forging processing on the cylindrical ingot blank to obtain a bar blank, wherein the starting processing temperature of the hot forging processing is 1600-1800 ℃, the finish forging temperature is 1400-1500 ℃, and the total processing deformation is not lower than 60%;
carrying out surface treatment on the bar blank to obtain a treated bar blank;
carrying out hot isostatic pressing treatment on the treated bar blank to obtain a bar, wherein the hot isostatic pressing treatment conditions are as follows: vacuumizing, and then filling argon, wherein the temperature is 1500-1600 ℃, the pressure is 100-120 MPa, and the time is 2 hours;
and machining the bar to obtain the anti-oxidation coating for the rhenium spray pipe.
Preferably, the smelting sequentially comprises a first smelting and a second smelting, wherein the first smelting is carried out in an electric arc furnace and a vacuum argon filling environment, and the second smelting is carried out in a high-temperature ceramic crucible and adopts medium-frequency vacuum.
Preferably, the second smelting adopts a magnesium oxide crucible, and the vacuum degree is not lower than 10-2Pa。
Preferably, the iridium further comprises rhodium element.
Preferably, the mass percentage content of rhodium element in the iridium is 5-40%.
Preferably, the hot forging process further comprises the steps ofHomogenizing heat treatment with vacuum degree of not less than 5 × 10-3Pa, the temperature is 1800-2000 ℃, and the time is 2-4 h.
The invention also provides the anti-oxidation coating for the rhenium spray pipe, which is prepared by the preparation method in the technical scheme, wherein the thickness of the anti-oxidation coating for the rhenium spray pipe is 250-500 mu m, the precision is +/-10 mu m, and the relative density is more than or equal to 99.9%.
The invention also provides a rhenium-antioxidant coating spray pipe which is prepared by the method comprising the following steps:
and carrying out vacuum negative pressure deposition on the surface of the anti-oxidation coating for the rhenium spray pipe in the technical scheme to form a rhenium matrix layer.
Preferably, the temperature of the vacuum negative pressure deposition is 1100-1300 ℃, the chlorination temperature is 500-800 ℃, and the pressure is 800-1000 Pa.
Preferably, the thickness of the rhenium substrate layer is 1-3 mm.
The invention provides a preparation method of an anti-oxidation coating for a rhenium spray pipe, which comprises the following steps: smelting iridium to obtain a cylindrical ingot blank; carrying out hot forging processing on the cylindrical ingot blank to obtain a bar blank, wherein the starting processing temperature of the hot forging processing is 1600-1800 ℃, the finish forging temperature is 1400-1500 ℃, and the total processing deformation is not lower than 60%; carrying out surface treatment on the bar blank to obtain a treated bar blank; carrying out hot isostatic pressing treatment on the treated bar blank to obtain a bar, wherein the hot isostatic pressing treatment conditions are as follows: vacuumizing, and then filling argon, wherein the temperature is 1500-1600 ℃, the pressure is 100-120 MPa, and the time is 2 hours; and machining the bar to obtain the anti-oxidation coating for the rhenium spray pipe.
Has the advantages that:
(1) the oxidation resistant coating has high compactness and component uniformity. Smelting is a commonly adopted traditional method for preparing precious metal materials, and has the advantages of high preparation speed, mature process and simple equipment. The raw material of noble metal iridium or rhodium contains certain gas, the gas can not be completely removed in the smelting process, a small amount of gas is dissolved in the solution, and defects such as pores are formed in the cast ingot in the cooling process; the hot forging processing is to heat the bar to 1600-1800 ℃, wherein the iridium or iridium-rhodium alloy is softened to a certain degree at the temperature, and then hot forging processing is utilized to extrude gas in pores, so that most of loose pores are sealed, the defects of pores, looseness and the like in cast ingots can be basically eliminated, the tissue structure and the mechanical property of the material are improved, and the density of the material is improved; the hot isostatic pressing treatment is carried out on the bar under high temperature (1500-1600 ℃) and high pressure (100-120 MPa), so that the holes in the material can be further eliminated, the material is further homogenized and densified, a high-density material with the relative density close to the theoretical density is obtained, and a high-density coating material with the relative density over 99.9 percent can be obtained.
(2) The thickness of the coating is uniform and controllable. The coating is prepared by machining, the thickness and the machining precision of the coating are completely machined according to the design requirements of drawings, the thickness uniformity is controllable, and the size precision can reach +/-10 microns.
(3) The size adaptation range is large. The size of the throat of the rhenium spray pipe coating is not particularly limited, and the machining process of the coating with the size of the throat smaller than 5mm can be completely realized.
(4) The quality can be directly checked. After the coating is processed, quality inspection including coating size, surface condition, material internal structure and the like can be directly carried out, and a rhenium substrate layer is deposited on the outer surface of the coating after the coating is qualified, so that the rhenium/iridium or rhenium/iridium-rhodium alloy spray pipe is obtained.
(5) The cost is low. The turning material produced in the coating machine processing process can be recycled, the recovery of the precious metal waste is a mature technology, and the recovery rate can reach more than 95 percent, so the method also has the advantage of low cost.
(6) The substrate and the coating are firmly combined. The temperature for depositing rhenium on the coating is as high as 1100-1300 ℃, the deposition time is 10-20 h, and after the deposition is finished, a 10-20 mu m element diffusion layer is formed on the interface of the rhenium substrate layer and the iridium or iridium-rhodium alloy coating, so that the combination is firm.
Furthermore, the iridium also comprises rhodium element, and the oxidation resistance of the iridium (Ir) can be greatly improved by adding a certain content of rhodium (Rh) element into the iridium (Ir). After the pure Ir is oxidized for 10 hours in the atmospheric environment at 1550 ℃, the oxidation weight loss rate of the pure Ir is 0.65 percent, after 15 percent of rhodium is added, the weight loss rate is 0.51 percent, which is 22 percent lower than that of the pure Ir; after 30% of rhodium is added, the weight loss rate is 0.31%, and the weight loss rate is reduced by 52% compared with that of pure Ir. Therefore, the oxidation resistance of the Ir-15Rh and the Ir-30Rh alloy is respectively improved by 22 percent and 52 percent compared with that of pure Ir.
Drawings
FIG. 1 is a schematic structural diagram of a rhenium-antioxidant coating spray pipe prepared by the invention, wherein 10 is an antioxidant coating, and 20 is a rhenium substrate layer;
FIG. 2 is a metallographic structure of the antioxidant coating for the rhenium lance of example 1;
FIG. 3 is a pictorial representation of an oxidation resistant coating for the rhenium lance of example 1;
FIG. 4 is a metallographic structure of the antioxidant coating for the rhenium lance of example 3;
fig. 5 is a pictorial view of an oxidation resistant coating for the rhenium lance of example 3.
Detailed Description
The invention provides a preparation method of an anti-oxidation coating for a rhenium spray pipe, which comprises the following steps:
smelting iridium to obtain a cylindrical ingot blank;
carrying out hot forging processing on the cylindrical ingot blank to obtain a bar blank, wherein the starting processing temperature of the hot forging processing is 1600-1800 ℃, the finish forging temperature is 1400-1500 ℃, and the total processing deformation is not lower than 60%;
carrying out surface treatment on the bar blank to remove impurities, and obtaining a treated bar blank;
carrying out hot isostatic pressing treatment on the treated bar blank to obtain a bar, wherein the hot isostatic pressing treatment conditions are as follows: vacuumizing, and then filling argon, wherein the temperature is 1500-1600 ℃, the pressure is 100-120 MPa, and the time is 2 hours;
and machining the bar to obtain the anti-oxidation coating for the rhenium spray pipe.
The method provided by the invention is used for smelting iridium to obtain a cylindrical ingot blank. The form of iridium in the present invention is not particularly limited, and the iridium may be a powder, a sheet or a block, and the purity of iridium is preferably not less than 99.95%. In the present invention, the melting mainly melts raw materials in different states to form an integral structure.
In the present invention, the iridium preferably further includes rhodium element, that is, iridium-rhodium alloy is used as a raw material. In the invention, the mass percentage of rhodium element in iridium is preferably 5-40%, and more preferably 15% or 30%. When iridium-rhodium alloy is used, the smelting can fuse different elements and distribute the elements uniformly.
In the invention, the smelting preferably sequentially comprises a first smelting and a second smelting, wherein the first smelting is preferably carried out in an electric arc furnace and a vacuum argon-filled environment, and the second smelting is preferably carried out in a high-temperature ceramic crucible and adopts medium-frequency vacuum. The invention has no special limitation on the smelting temperature and time, and can ensure that the raw materials are uniformly melted.
The invention has no special limitation on the specific parameters of the electric arc furnace and the vacuum argon filling environment, and can obtain ingot blanks.
In the invention, the second melting is preferably performed by using a magnesia crucible, and the degree of vacuum is preferably not less than 10-2Pa。
After the second smelting is finished, the cylindrical ingot blank is obtained by bottom leakage casting. The invention preferably sizes the diameter of the cylindrical ingot according to the requirements of the bar stock used for preparing the coating layer on the total working deformation of hot forging, in a specific embodiment of the invention the diameter Φ of the cylindrical ingot is preferably 18mm, 46mm or 78 mm.
After obtaining the cylindrical ingot blank, carrying out hot forging processing on the cylindrical ingot blank to obtain a bar blank, wherein the starting processing temperature of the hot forging processing is 1600-1800 ℃, the preferred temperature is 1700 ℃, the finishing processing temperature is 1400-1500 ℃, and the total processing deformation is not less than 60%, the preferred temperature is 63%, 65% or 66%. In the present invention, the strain per pass is preferably within 15%, more preferably 10%. In the invention, the hot forging process is used for eliminating defects such as holes in the alloy and improving the structure of the alloy. In the present invention, the Φ of the bar is preferably 11mm, 27mm or 46 mm.
In the present invention, when the raw material is an iridium-rhodium alloy, the heat is generatedThe forging process preferably further comprises a homogenization heat treatment, and the degree of vacuum of the homogenization heat treatment is preferably not less than 5X 10-3Pa, the temperature is preferably 1800-2000 ℃, and the time is preferably 2-4 h. In the present invention, the homogenization heat treatment is preferably performed in a high-temperature vacuum tungsten wire furnace, and the purpose of the homogenization heat treatment is to more uniformly distribute iridium and rhodium in the alloy structure.
After the bar billet is obtained, the invention carries out surface treatment on the bar billet to remove impurities, and the treated bar billet is obtained. In the present invention, the surface treatment is preferably an acid pickling and/or a lathing method. The pickling and turning method of the present invention is not particularly limited, and may be performed in a manner known to those skilled in the art.
After the processed bar billet is obtained, carrying out hot isostatic pressing treatment on the processed bar billet to obtain a bar material, wherein the hot isostatic pressing treatment conditions are as follows: and (3) vacuumizing, and then filling argon, wherein the temperature is 1500-1600 ℃, the preferable temperature is 1550 ℃, the pressure is 100-120 MPa, and the time is 2 h. In the invention, the hot isostatic pressing temperature has the greatest influence on the density of the material, and the hot isostatic pressing temperature is controlled to be 1500-1600 ℃, so that the relative density (density) of the material can reach 99.9-100.9% of the theoretical density; the influence of pressure on the compactness is relatively small. In the present invention, the argon gas is preferably a high purity argon gas.
After the bar is obtained, the bar is machined to obtain the anti-oxidation coating for the rhenium spray pipe. In the present invention, the machining is preferably performed using numerically controlled machines (turning, grinding, milling) and special precision machining devices.
The invention also provides the anti-oxidation coating for the rhenium spray pipe, which is prepared by the preparation method in the technical scheme, wherein the thickness of the anti-oxidation coating for the rhenium spray pipe is 250-500 mu m, the precision is +/-10 mu m, and the relative density is more than or equal to 99.9%.
The invention also provides a rhenium-antioxidant coating spray pipe which is prepared by the method comprising the following steps:
and carrying out vacuum negative pressure deposition on the surface of the anti-oxidation coating for the rhenium spray pipe in the technical scheme to form a rhenium matrix layer.
In the invention, the temperature of the vacuum negative pressure deposition is preferably 1100-1300 ℃, more preferably 1200 ℃, the chlorination temperature is preferably 500-800 ℃, more preferably 700 ℃, and the pressure is preferably 800-1000 Pa. In a specific embodiment of the present invention, the specific process of the vacuum negative pressure deposition is preferably:
introduction of Cl2Reacts with the raw material Re to generate ReCl5Gas, Recl5The gas is transported to the oxidation-resistant coating for the rhenium spray pipe which is heated to the deposition temperature, the thermal decomposition reaction is carried out on the surface of the coating, Re atoms are separated out, and the Re atoms are continuously accumulated to form a rhenium substrate layer.
In the invention, an element diffusion layer with the thickness of 10-20 mu m is preferably formed on the interface of the rhenium substrate layer and the rhenium anti-oxidation coating for the spray pipe.
In the present invention, the thickness of the rhenium substrate layer is preferably 1 to 3 mm. In the invention, the relative density of the rhenium spray pipe is more than or equal to 99.9%, the room-temperature ultimate tensile strength is preferably 685-782 MPa, and the elongation is preferably 30-38%.
Fig. 1 is a schematic structural diagram of a rhenium-antioxidant coating nozzle, wherein 10 is an antioxidant coating for the rhenium nozzle, and 20 is a rhenium substrate layer.
To further illustrate the present invention, the oxidation resistant coating for rhenium nozzles and the method of making the same, and the rhenium-oxidation resistant coated nozzle provided by the present invention are described in detail below with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of an anti-oxidation coating (iridium-rhodium alloy coating) for a rhenium spray pipe comprises the following steps:
(1) the preparation method comprises the steps of preparing 150g of Ir-30Rh alloy, and uniformly dividing the mixture into 5 parts of 30g each. Smelting each part of the ingredients into small ingots by using an electric arc furnace, putting 5 small ingots into a medium frequency furnace for vacuum smelting, and casting into cylindrical ingots with phi of 18 mm;
(2) putting Ir-30Rh alloy ingot blank into a high-temperature vacuum tungsten filament furnace, and pumping the vacuum degree of the system to 2 multiplied by 10-3Pa starts to rise, and after homogenizing heat treatment for 2h at 1800℃, the temperature is reducedWarming;
(3) the Ir-30Rh alloy ingot blank is put into a magnesium oxide crucible, the ingot blank is forged when being heated to 1700 ℃ by using oxygen-acetylene, the alloy ingot blank is hot forged by a circular die, and the forging is stopped when the temperature of the bar is reduced to 1400 ℃. The pass processing amount is controlled to be 10%, an alloy bar with the diameter of 11mm is obtained through multiple times of hot forging, and the total processing deformation amount is 63%. Carrying out surface treatment on the alloy rod by adopting an acid pickling and turning method;
(4) putting the Ir-30Rh alloy bar into a hot isostatic pressing furnace molybdenum crucible, vacuumizing the system, filling high-purity argon, heating to 1500 ℃, continuously filling the high-purity argon to the pressure of 100MPa, maintaining the pressure for 2 hours, and then releasing the pressure and reducing the temperature. The relative density of the obtained alloy bar is 99.9%, the metallographic structure of the alloy is shown in fig. 2, and the fact that the Ir-30Rh alloy bar prepared in the embodiment has high density is illustrated.
(5) And (4) compiling a numerical control machining program according to the design drawing requirements, and selecting a proper hard cutter to perform coating machining. An Ir-30Rh alloy coating having the shape of the inner surface of the nozzle was obtained as shown in fig. 3. The thickness of the coating is 250 mu m, the aperture in the throat part is 3.10mm, the inner diameter of the body part is 10.00mm, and the size precision is +/-10 mu m; the coating is suitable for being used as an anti-oxidation protective coating of a rhenium spray pipe of a 10N thrust attitude control engine;
(6) the spray pipe-shaped Ir-30Rh alloy coating is placed on a rotating table of a chemical vapor deposition chamber, and a proper amount of rhenium sheet raw material is placed in a chlorination chamber. The deposition system is pumped down to 3 × 10-1Pa, heating the alloy coating of rhenium to be deposited to 1100 ℃, and heating the chlorination chamber to 500 ℃. Then chlorine gas is introduced into the deposition chamber for 100mL/min, and the pressure of the deposition chamber is adjusted to 800 Pa. The thickness of the deposited rhenium layer is 1.5mm by controlling the deposition time, the relative density of the rhenium material is 99.90 percent, the room temperature ultimate tensile strength is 685MPa, and the elongation is 30 percent. And processing the outer surface of the rhenium layer to finally obtain the rhenium/iridium-rhodium alloy spray pipe, namely the rhenium-antioxidant coating spray pipe.
After the pure Ir is oxidized for 10 hours in the atmospheric environment at 1550 ℃, the oxidation weight loss rate of the pure Ir is 0.65 percent, after 30 percent of Rh (mass percent) is added, the weight loss rate is reduced to 0.31 percent and is reduced by 52 percent compared with the pure Ir, namely the oxidation resistance of the Ir-30Rh alloy coating is improved by 52 percent compared with the pure Ir.
Example 2
A preparation method of an anti-oxidation coating (iridium-rhodium alloy coating) for a rhenium spray pipe comprises the following steps:
(1) the method comprises the steps of proportioning 1000g of Ir-15Rh alloy, and uniformly dividing the mixture into 10 parts, wherein each part is 100 g. Smelting each part of the ingredients into small ingots by using an electric arc furnace, putting 10 small ingots into a medium-frequency furnace for vacuum smelting, and casting into cylindrical ingots with phi of 46 mm;
(2) putting Ir-15Rh alloy ingot blank into a high-temperature vacuum tungsten filament furnace, and pumping the vacuum degree of the system to 2 multiplied by 10-3Pa, starting to heat up, carrying out homogenization heat treatment at 2000 ℃ for 4h, and then cooling;
(3) the Ir-15Rh alloy ingot blank is put into a magnesium oxide crucible, the ingot blank is heated to 1800 ℃ by using oxygen-acetylene to start forging, the alloy ingot blank is subjected to hot forging processing by using a circular die, and the forging is stopped when the temperature of the bar is reduced to 1400 ℃. The pass processing amount is controlled to be 10%, and the alloy bar with the diameter of 27mm is obtained through multiple hot forging, and the total processing deformation amount is 66%. Carrying out surface treatment on the alloy rod by adopting an acid pickling and turning method;
(4) putting the Ir-15Rh alloy bar into a hot isostatic pressing furnace molybdenum crucible, vacuumizing the system, filling high-purity argon, heating to 1550 ℃, continuously filling the high-purity argon to the pressure of 100MPa, and relieving the pressure and reducing the temperature after the pressure maintaining time is 2 hours. The relative density of the obtained alloy bar is 100.9%, which shows that the Ir-15Rh alloy bar prepared in the embodiment has high density.
(5) And (4) compiling a numerical control machining program according to the design drawing requirements, and selecting a proper hard cutter to perform coating machining. Obtaining the Ir-15Rh alloy coating with the shape of the inner surface of the spray pipe. The thickness of the coating is 350 mu m, the aperture in the throat part is 11.70mm, the inner diameter of the body part is 26.00mm, and the size precision is +/-10 mu m; the coating is suitable for being used as an anti-oxidation protective coating of a rhenium spray pipe of a posture control engine with 150N thrust;
(6) the spray pipe-shaped Ir-15Rh alloy coating is placed on a rotating table of a chemical vapor deposition chamber, and a proper amount of rhenium sheet raw material is placed in a chlorination chamber. The deposition system is pumped down to 3 × 10-1Pa, heating the alloy coating of rhenium to be depositedTo 1200 ℃, the chlorination chamber is heated to 700 ℃. 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 time is controlled to obtain that the thickness of the deposited rhenium layer is 2.0mm, the relative density of the rhenium material is 99.92%, the room-temperature ultimate tensile strength is 753MPa, and the elongation is 33%. And processing the outer surface of the rhenium layer to finally obtain the rhenium/iridium-rhodium alloy spray pipe, namely the rhenium-antioxidant coating spray pipe.
After the Ir-15Rh is oxidized for 10 hours in the atmospheric environment at 1550 ℃, the oxidation weight loss rate of the Ir-15Rh is 0.51 percent and is reduced by 22 percent compared with pure Ir, namely the oxidation resistance of the Ir-15Rh alloy coating is improved by 22 percent compared with the pure Ir.
Example 3
A preparation method of an anti-oxidation coating (iridium coating) for a rhenium spray pipe comprises the following steps:
(1) 3600g of iridium raw material (the purity is not lower than 99.95%) is prepared and evenly divided into 18 parts, and each part is 200 g. Smelting each part of ingredients into small ingots by using an electric arc furnace, putting 18 small ingots into a medium-frequency furnace for vacuum smelting, and casting into cylindrical ingots with phi of 78 mm;
(2) and (3) putting the iridium ingot blank into a magnesium oxide crucible, heating the ingot blank to 1600 ℃ by using oxygen-acetylene, starting forging, performing hot forging processing on the iridium ingot by using a circular die, and stopping forging when the temperature of the bar is reduced to 1500 ℃. The pass processing amount is controlled within 10 percent, and alloy bars with the diameter of 46mm are obtained through multiple hot forging, and the total processing deformation amount is 65 percent. Carrying out surface treatment on the iridium rod by adopting an acid pickling and turning method;
(3) and putting the iridium rod into a molybdenum crucible of a hot isostatic pressing furnace, vacuumizing the system, filling high-purity argon, heating to 1600 ℃, continuously filling the high-purity argon to a pressure of 120MPa, and relieving the pressure and reducing the temperature after the pressure is maintained for 2 hours. The relative density of the obtained iridium bar is 99.98%, and the metallographic structure of iridium is shown in fig. 4, which illustrates that the iridium bar prepared in this example has high density.
(4) And compiling a numerical control machining program according to a design drawing, and selecting a proper hard tool for machining the iridium coating. An iridium coating having the shape of the inner surface of the nozzle was obtained as shown in fig. 5. The thickness of the coating is 500 mu m, the aperture in the throat part is 18.00mm, the inner diameter of the body part is 45.00mm, and the size precision is +/-10 mu m; the anti-oxidation protective coating is suitable for being used as an anti-oxidation protective coating of a rhenium spray pipe of a track control engine with 490N thrust;
(5) the spray pipe-shaped iridium coating is placed on a rotating table of a chemical vapor deposition chamber, and a proper amount of rhenium sheets as raw materials are placed in a quartz tube of a chlorination chamber. The deposition system is pumped down to 3 × 10-1Pa, the iridium coating of rhenium to be deposited is heated to 1300 ℃ and the chlorination chamber to 800 ℃. 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 thickness of the deposited rhenium layer is 3.0mm by controlling the deposition time, the relative density of the rhenium material is 99.98 percent, the room-temperature ultimate tensile strength is 782MPa, and the elongation is 38 percent. And processing the outer surface of the rhenium layer to finally obtain the rhenium/iridium spray pipe, namely the rhenium-oxidation resistant coating spray pipe.
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. The preparation method of the anti-oxidation coating for the rhenium spray pipe is characterized by comprising the following steps of:
smelting iridium to obtain a cylindrical ingot blank;
carrying out hot forging processing on the cylindrical ingot blank to obtain a bar blank, wherein the starting processing temperature of the hot forging processing is 1600-1800 ℃, the finish forging temperature is 1400-1500 ℃, and the total processing deformation is not lower than 60%;
carrying out surface treatment on the bar blank to obtain a treated bar blank;
carrying out hot isostatic pressing treatment on the treated bar blank to obtain a bar, wherein the hot isostatic pressing treatment conditions are as follows: vacuumizing, and then filling argon, wherein the temperature is 1500-1600 ℃, the pressure is 100-120 MPa, and the time is 2 hours;
and machining the bar to obtain the anti-oxidation coating for the rhenium spray pipe.
2. The method of claim 1, wherein the melting comprises, in sequence, a first melting and a second melting, the first melting being performed in an electric arc furnace, in a vacuum argon-filled environment, and the second melting being performed in a high temperature ceramic crucible, using a medium frequency vacuum.
3. The production method according to claim 2, wherein the second melting is performed using a magnesium oxide crucible having a degree of vacuum of not less than 10-2Pa。
4. The production method according to claim 1, characterized in that the iridium is replaced with an iridium-rhodium alloy.
5. The preparation method of claim 4, wherein the mass percentage of rhodium in the iridium-rhodium alloy is 5-40%.
6. The method according to claim 4, characterized by further comprising a homogenization heat treatment before the hot forging process, wherein the degree of vacuum of the homogenization heat treatment is not less than 5 x 10-3Pa, the temperature is 1800-2000 ℃, and the time is 2-4 h.
7. The anti-oxidation coating for the rhenium spray pipe prepared by the preparation method of any one of claims 1 to 6 is characterized in that the thickness of the anti-oxidation coating for the rhenium spray pipe is 250-500 μm, the precision is +/-10 μm, and the relative density is greater than or equal to 99.9%.
8. A rhenium-antioxidant coating nozzle, characterized by being prepared by a method comprising the steps of:
vacuum negative pressure deposition of a rhenium matrix layer on the surface of the rhenium spray tube oxidation resistant coating of claim 7.
9. The rhenium-antioxidant coating nozzle according to claim 8, wherein the temperature of the vacuum negative pressure deposition is 1100-1300 ℃, the chlorination temperature is 500-800 ℃, and the pressure is 800-1000 Pa.
10. The rhenium-antioxidant coating lance of claim 8, wherein the rhenium substrate layer has a thickness of 1 to 3 mm.
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CN101733641A (en) * 2009-12-18 2010-06-16 西北有色金属研究院 Manufacturing method of large-calibre seamless titanium alloy barrel body
CN104190933A (en) * 2014-09-10 2014-12-10 太仓派欧技术咨询服务有限公司 Method for preparing laser rapid forming rhenium spraying pipe
CN106001554B (en) * 2016-06-29 2018-06-01 航天材料及工艺研究所 A kind of preparation method of rhenium iridium combustion chamber

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JP2001353505A (en) * 2000-06-12 2001-12-25 Ishifuku Metal Ind Co Ltd METHOD FOR MANUFACTURING METAL PLATE OF Ir AND Ir ALLOY AND BASE TOCK CHIP
CN101376206A (en) * 2008-10-09 2009-03-04 贵研铂业股份有限公司 Method for high-density iridium fusion casting and preparing products
CN101733641A (en) * 2009-12-18 2010-06-16 西北有色金属研究院 Manufacturing method of large-calibre seamless titanium alloy barrel body
CN104190933A (en) * 2014-09-10 2014-12-10 太仓派欧技术咨询服务有限公司 Method for preparing laser rapid forming rhenium spraying pipe
CN106001554B (en) * 2016-06-29 2018-06-01 航天材料及工艺研究所 A kind of preparation method of rhenium iridium combustion chamber

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