CN114346245B - Long-life rare earth molybdenum crucible and preparation method thereof - Google Patents
Long-life rare earth molybdenum crucible and preparation method thereof Download PDFInfo
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Abstract
The long-life rare earth molybdenum crucible and the preparation method thereof provided by the invention overcome the problems of short service life of the existing molybdenum crucible and high use cost of the tungsten crucible. The method can prepare a molybdenum crucible for smelting rare earth with long service life, and the molybdenum crucible prepared by the method is made of pure molybdenum-pure tungsten, molybdenum lanthanum oxide-tungsten lanthanum oxide, molybdenum cerium oxide-tungsten cerium oxide, molybdenum zirconium oxide-tungsten zirconium oxide, molybdenum yttrium oxide-tungsten yttrium oxide and other materials; and the crucible density reaches more than 94%, the purity is high, the interface connectivity is good, the interface strength is high, the grain size is tiny, be suitable for batch production, the main research content of this patent is for preparing the crucible that the oral area is tungsten material, well lower wall and bottom are molybdenum material to increase life.
Description
Technical Field
The invention belongs to the field of powder metallurgy, and particularly relates to a long-life rare earth molybdenum crucible and a preparation method thereof.
Background
Molybdenum is a refractory rare metal and has a density of 10.2g/cm 3 The melting point is 2610deg.C and the boiling point is 5560 deg.C. Molybdenum has excellent physical properties such as high melting point, good wear resistance, small thermal expansion coefficient, good heat conduction performance and the like, has high chemical stability, does not react with hydrochloric acid, hydrofluoric acid and alkali solution at normal temperature, is only dissolved in nitric acid, aqua regia or concentrated sulfuric acid, is quite stable for most liquid metal, nonmetallic slag and molten glass, and has wide application in the fields of metallurgy, glass, ceramics, military equipment, high-temperature furnaces and the like due to the excellent properties. The patent is directed to a molybdenum crucible for producing rare earth metal by reducing rare earth oxide by an electrolytic method. Molybdenum crucibles for reducing rare earths generally comprise pure molybdenum crucibles (molybdenum content greater than 99.9%) or molybdenum alloy crucibles (usually doped with small amounts of at least 1 of cerium oxide, lanthanum oxide, yttrium oxide, zirconium oxide, the total mass percentage of the doped material not being greater than 3%). The molybdenum alloy crucible is added with an oxide dispersion phase, the grain size of the molybdenum alloy crucible is reduced, the relative compactness of the molybdenum alloy crucible is increased, but the service life of the molybdenum alloy crucible is not obviously prolonged compared with that of a pure molybdenum crucible.
The crucible for melting rare earth by the electrolytic method is gradually consumed at the mouth part in normal use until the wall height is low enough to meet the use requirement. The wall thickness and bottom thickness will also be thinner when the crucible is in use, but this is not the root cause of the ultimate failure of the crucible. The consumption was found to be from the mouth down through long term use observation, as: during production, electrolyte can flow down along the wall of the crucible in the process of taking out the pouring from the electrolytic furnace, so that the mouth of the crucible is exposed to the air, the lower part is still protected by the electrolyte, the lower part is not exposed to the air, the temperature of the crucible is about 1100 ℃, the mouth of the crucible is rapidly oxidized in the air, and the middle lower part is not oxidized under the protection of the electrolyte, so that the mouth is consumed first. Therefore, it is important to strengthen the protection of the mouth and to reduce oxidation of the mouth in the air exposed to the air.
Tungsten is also a refractory rare metal with a theoretical density of 19.35g/cm 3 The melting point was 3410 ℃. Tungsten has the characteristics of high melting point, small thermal expansion coefficient, good heat conduction performance, good corrosion resistance and the like, and has stronger oxidation resistance in air than molybdenum. And through long-term use, the pure tungsten crucible has higher service life than the pure molybdenum crucible under the same use condition, the service life of the pure tungsten crucible is about 2 times that of the pure molybdenum crucible, but the density of tungsten is high, the single weight is high, the price is high, and the condition that the service life is not up to the point of replacement due to continuous updating exists during use, so that the cost performance of tungsten is not as high as that of molybdenum as a whole. Therefore, the main research content of the patent is to prepare the crucible with the tungsten material at the mouth and the molybdenum material at the middle and lower walls and the bottom, thereby prolonging the service life.
After the service life is prolonged, the production cost of rare earth metal or rare earth alloy preparation can be reduced, and precious molybdenum resources can be saved for the country, so that the method has great significance.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a long-life rare earth molybdenum crucible, which comprises the following steps:
step a, powder selection: selecting raw material powder meeting the requirements;
step b, powder batch mixing: separately mixing the powder of the component A and the powder of the component B;
step c, packing: filling the powder of the component B and the powder of the component A into a sheath according to the sequence, compacting and sealing;
step d, sintering by hot isostatic pressing: placing the sheath filled with the powder into a hot isostatic pressing machine for sintering treatment to obtain a crucible blank with the sheath;
step e, machining: and turning the crucible blank on a lathe to remove the sheath to obtain a crucible, and machining the crucible to obtain a finished product.
Further, in the step b, the batch mixing method is a mechanical mixing method.
Further, the height at which the component B is provided is 1/5 of the height of the crucible.
Further, in step c, sealing the sheath includes the following steps:
step c1, welding a cover plate on the sheath;
and c2, placing the sheath in a vacuum electron beam welding cavity for vacuumizing, and welding an extraction opening on the cover plate by using the vacuum electron beam welding.
Further, the vacuum degree in the vacuum electron beam welding cavity is 1 x 10 -2 Pa, and the temperature is 300-500 ℃.
In the step d, the heating rate of the hot isostatic pressing treatment is 100-500 ℃/h, the pressure is 170-200MPa, and the heat preservation and pressure maintaining time is 1-5h.
A long life rare earth molybdenum crucible made by the method of any one of claims 1-6, the molybdenum crucible comprising a component a and a component B, wherein the component a comprises molybdenum powder and the component B comprises tungsten powder.
Further, the component A is pure molybdenum powder or the mixture of molybdenum powder and oxide powder; the component B is pure tungsten powder or the mixture of tungsten powder and oxide powder.
Further, the oxide powder is cerium oxide powder, yttrium oxide powder, zirconium oxide powder and lanthanum hydroxide powder.
Further, the granularity of the molybdenum powder is 3.0-4.0 mu m, and the granularity of the tungsten powder is 1.5-2.5 mu m.
The invention has the beneficial effects that:
(1) The purity of the raw material powder selected in the rare earth molybdenum crucible with long service life is more than 99.9 percent; the granularity of the pure molybdenum powder is preferably 3.5 mu m, the granularity of the pure tungsten powder is preferably 2 mu m, the granularity matching of the molybdenum powder and the tungsten powder is proper, and the density and the grain size of the obtained sintered blank are optimal;
(2) The preparation method of the rare earth molybdenum crucible with long service life can prepare pure molybdenum-pure tungsten and various crucibles doped with disperse phases, and has rich materials;
(3) The preparation method of the rare earth molybdenum crucible with long service life adopts a hot isostatic pressing mode for sintering, can obtain blanks with various specifications, and has good uniformity;
(4) The crucible mouth part in the long-life rare earth molybdenum crucible is made of tungsten, the middle lower wall and the bottom are made of molybdenum, so that the oxidation of the crucible exposed in the air during use is greatly reduced, the service life is prolonged, the production cost of rare earth metal or rare earth alloy during preparation can be reduced after the service life is prolonged, and precious molybdenum resources can be saved for the country, so that the long-life rare earth molybdenum crucible has great significance;
(5) The preparation method of the rare earth molybdenum crucible with long service life has the advantages of good cooperation of all steps, obvious overall synergistic effect, simple and easy operation steps and contribution to mass production.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a flow chart of a method for preparing a long-life rare earth molybdenum crucible according to a preferred embodiment of the present invention;
FIG. 2 shows a schematic view of the present invention after the package is assembled;
FIG. 3 is a diagram of a long life rare earth molybdenum crucible finished product of the present invention;
fig. 4 is a tungsten-molybdenum interface gold phase diagram of a long life rare earth molybdenum crucible of the present invention.
In the figure, 1-extraction opening, 2-welding seam, 3-cover plate, 4-sheath, 5-component A and 6-component B.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Aiming at the defects and defects of the prior art, the invention aims to provide a long-life rare earth molybdenum crucible and a preparation method thereof, and solves the problems of short service life and high use cost of the tungsten crucible in the prior molybdenum crucible. The method can prepare a molybdenum crucible for smelting rare earth with long service life, and the molybdenum crucible prepared by the method is made of pure molybdenum-pure tungsten, molybdenum lanthanum oxide-tungsten lanthanum oxide, molybdenum cerium oxide-tungsten cerium oxide, molybdenum zirconium oxide-tungsten zirconium oxide, molybdenum yttrium oxide-tungsten yttrium oxide and other materials; and the crucible density reaches more than 94%, the purity is high, the interface connectivity is good, the interface strength is high, the grain size is tiny, be suitable for batch production, the main research content of this patent is for preparing the crucible that the oral area is tungsten material, well lower wall and bottom are molybdenum material to increase life.
The preparation method of the long-life rare earth molybdenum crucible provided by the invention, as shown in figure 1, comprises the following steps:
step a, powder selection: selecting raw material powder meeting the requirements;
step b, powder batch mixing: separately mixing the powder of the component A and the powder of the component B;
step c, packing: filling the powder of the component B and the powder of the component A into a sheath according to the sequence, compacting and sealing;
step d, sintering by hot isostatic pressing: placing the sheath filled with the powder into a hot isostatic pressing machine for sintering treatment to obtain a crucible blank with the sheath;
step e, machining: and turning the crucible blank on a lathe to remove the sheath to obtain a crucible, and machining the crucible to obtain a finished product.
Preferably, the long-life rare earth molybdenum crucible prepared by the invention comprises a component A and a component B, wherein the main component of the component A is molybdenum powder, the main component of the component B is tungsten powder, and the component A is pure molybdenum powder or the mixture of the molybdenum powder and oxide powder; the component B is pure tungsten powder or the mixture of tungsten powder and oxide powder, and the oxide is cerium oxide powder, yttrium oxide powder, zirconium oxide powder and lanthanum hydroxide powder.
In the powder selecting step, the raw materials include molybdenum powder, tungsten powder, lanthanum hydroxide powder, cerium oxide powder, yttrium oxide powder, and zirconium oxide powder, and the preferable powder purities are 99.9% or more. The crucible is made of pure molybdenum-pure tungsten, molybdenum lanthanum oxide-tungsten lanthanum oxide, molybdenum cerium oxide-tungsten cerium oxide, molybdenum yttrium oxide-tungsten yttrium oxide, molybdenum zirconium oxide-tungsten zirconium oxide and the like.
In the preparation method, as a preferred embodiment, in the powder selection step, the particle size of the molybdenum powder is 3.0-4.0 μm, the particle size of the tungsten powder is 1.5-2.5 μm, and more preferably the particle size of the molybdenum powder is 3.5 μm, and the particle size of the tungsten powder is 2 μm. The optimal sintering temperature of molybdenum is lower than that of tungsten, and in theory, the smaller the powder granularity is, the easier the sintering is, the molybdenum powder with larger granularity and the tungsten powder with smaller granularity are selected to be more favorable for the consistency of the relative density of simultaneous sintering, and the subsequent sintering condition is better when the granularity of the raw material is limited in the range, and the obtained sintered blank has optimal density and grain size.
As a preferred embodiment, in the powder batch step (the mixing process of the powders obtained in the different batch production processes having the same chemical composition is referred to as batch mixing), mechanical mixing is adopted in the batch mixing method, and the batch mixing time of pure molybdenum powder is 3h, the batch mixing time of pure tungsten powder is 3h, the batch mixing time of molybdenum-doped powder is 12h, and the batch mixing time of tungsten-doped powder is 12h.
The pure molybdenum-pure tungsten crucible is formed by separately mixing pure molybdenum and pure tungsten powder; the molybdenum-doped tungsten crucible is formed by independently mixing molybdenum powder-doped material and tungsten powder-doped material.
In the packing step, tungsten or tungsten alloy powder is firstly packed into the packing sleeve 4 according to the calculated powder packing amount, then molybdenum or molybdenum alloy powder is packed into the packing sleeve 4 according to the calculated powder packing amount, wherein the tungsten powder packing amount is calculated by taking the tungsten layer height accounting for 1/5 of the total height of the crucible as a reference when the tungsten powder is finished, the tungsten powder is packed into the packing sleeve, the tungsten powder is put into a vibrating platform for compaction, then an upper cover plate 3 and the powder packing sleeve 4 are welded, and then the packing sleeve 4 filled with the powder is put into a vacuum electron beam welding cavity for welding an extraction opening 1, wherein the vacuum degree is 1 x 10 -2 Pa, temperature 300-500 ℃ (e.g. 350 ℃, 400 ℃, 450 ℃).
Illustratively, sealing the capsule 4 comprises two steps: firstly, welding a cover plate 3 on a sheath 4, and forming a welding line 2 between the cover plate 3 and the sheath 4; and secondly, placing the sheath 4 in a vacuum electron beam welding cavity for vacuumizing, and welding an extraction opening 1 on the cover plate 3 by using the vacuum electron beam welding.
As a preferred embodiment, in the step of packing, the material of the jacket 4 is pure molybdenum, and the thickness of the jacket 4 is 1-3mm (such as 1.5mm, 2mm, 2.5 mm).
As a preferred embodiment, in the step of hot isostatic pressing, the hot isostatic pressing is performed under a non-oxidizing atmosphere; more preferably, the non-oxidizing atmosphere is at least one of a nitrogen atmosphere, a helium atmosphere, and an argon atmosphere; further preferably under an argon atmosphere. In the hot isostatic pressing step, the heating rate of the hot isostatic pressing treatment is 100-500 ℃/h (such as 150 ℃/h, 200 ℃/h, 300 ℃/h, 400 ℃/h, 450 ℃/h), the highest temperature is 1900-2000 ℃ (such as 1920 ℃, 1940 ℃, 1960 ℃, 1980 ℃), the pressure is 170-200MPa (such as 180MPa, 190 MPa), and the heat preservation and pressure maintaining time is 1-5h (such as 2h, 3h, 4 h). Argon is pumped out after the temperature is reduced to below 300 ℃ during discharging, and the obtained sintered blank has the density of more than 94 percent after opening the cover and discharging.
In a preferred embodiment, the machining step is performed mainly on a horizontal lathe.
The long-life rare earth molybdenum crucible prepared by the preparation method of the invention has the relative density of more than 94%, the outer diameter of 100-300mm (120 mm, 140mm, 160mm, 180mm, 200mm, 220mm, 240mm, 260mm, 280 mm), the height of 100-300mm (120 mm, 140mm, 160mm, 180mm, 200mm, 220mm, 240mm, 260mm, 280 mm) and the wall thickness of 6-20mm (10 mm, 12mm, 14mm, 16mm, 18 mm).
Example 1
The embodiment prepares a pure molybdenum-pure tungsten crucible with the relative density of more than 99.4 percent, and the external dimension of the crucible is
The wall thickness is 10mm, the material of the middle and lower walls and the bottom of the crucible is pure molybdenum, the material of the mouth of the crucible is pure tungsten, and the height of the pure tungsten is 30mm, and the specific steps are as follows:
step a, powder selection: selecting molybdenum powder with purity of 99.9% and granularity of 3.5 μm as a component A; the purity is 99.9 percent, and tungsten powder with granularity of 2.0 mu m is used as a component B;
step b, powder batch mixing: mechanically mixing the component A of the molybdenum powder with the granularity of 3.5 mu m for 3 hours; mechanically mixing component B of tungsten powder with granularity of 2.0 mu m for 3 hours;
step c, packing: sequentially filling powder into powder filling bags according to the sequence of filling tungsten powder (component B) and filling molybdenum powder (component A), compacting the powder filling bags on a vibrating platform, welding an upper cover plate 3 and the powder filling bags 4 to form a welding line 2, placing the bags 4 in a vacuum electron beam welding cavity, vacuumizing an extraction opening 1 on the cover plate 3 by vacuum electron beam welding to obtain a crucible blank with the bags, wherein the thickness of the bags is 1.5mm, the temperature during vacuumizing is 350 ℃, and a schematic diagram after the bags are packaged is shown in fig. 2;
step d, sintering by hot isostatic pressing: placing the sheath filled with the powder into a hot isostatic pressing machine for sintering treatment, wherein the sintering is performed under the argon atmosphere, the argon pressure is 180MPa, the heating rate of the whole temperature section is 400 ℃/h, the highest sintering temperature is 1950 ℃, and the heat preservation time is 2h, so that a pure molybdenum-pure tungsten crucible blank with the sheath is obtained;
and e, removing the sheath of the crucible blank obtained in the step d by using a horizontal lathe, and then processing the crucible blank into a finished product according to a finished product drawing shown in fig. 3.
10 pure molybdenum-pure tungsten crucibles prepared by the method of the example, the average value of the actual density measured by a still water weighing method is 11.37g/cm 3 The relative density averages 96.9%. The purity of the obtained crucible material is more than 99.9%, the interface connectivity is good, the connection is tight, no obvious transition layer exists, the metallographic phase at the interface is shown in figure 4, wherein the lower left corner is molybdenum Mo, the upper right corner is tungsten W, the interface strength is higher, one side of the tungsten is broken when the tensile strength at normal temperature is tested, the fracture is not at the interface, the tensile strength is 160MPa, the average service life of the crucible is 3.8 months, and the service life of the crucible is 1.9 times that of the pure molybdenum crucible.
Example two
The embodiment prepares a molybdenum yttrium oxide-tungsten yttrium oxide crucible with the relative density of more than 99.4 percent, and the external dimension of the crucible is
The wall thickness is 15mm, the material of the lower wall and the bottom of the crucible is molybdenum yttrium oxide, the material of the mouth of the crucible is tungsten yttrium oxide, and the height of the tungsten yttrium oxide is 50mm, and the specific steps are as follows.
Step a, powder selection: selecting yttrium oxide powder with purity of 99.9% and granularity of 3.5 mu m, wherein the doped mass fraction of the yttrium oxide powder is 1% as a component A; the purity is 99.9 percent, and yttrium oxide powder with the granularity of 2.0 mu m and 1 percent of doped mass fraction is used as a component B;
step b, powder batch mixing: mechanically mixing the component A of the molybdenum yttrium oxide mixed powder for 12 hours; mechanically mixing the component B of the tungsten yttrium oxide mixed powder for 12 hours;
step c, packing: sequentially filling powder into powder filling bags according to the sequence of filling tungsten yttrium oxide mixed powder (component B) and molybdenum yttrium oxide mixed powder (component A), compacting the powder filling bags on a vibrating platform, welding an upper cover plate 3 and the powder filling bags 4 to form welding seams 2, putting the powder filling bags into a hot isostatic pressing machine for sintering treatment, placing the bags 4 into a vacuum electron beam welding cavity for vacuumizing, and welding an extraction opening 1 on the cover plate 3 by vacuum electron beam welding to obtain a crucible blank with the bags, wherein the thickness of the bags is 2.5mm, and the temperature during vacuumizing is 450 ℃;
step d, sintering by hot isostatic pressing: placing the sheath filled with the powder into a hot isostatic pressing machine for sintering treatment, wherein the sintering is performed under the argon atmosphere, the argon pressure is 190MPa, the heating rate of the whole temperature section is 200 ℃/h, the highest sintering temperature is 1990 ℃, and the heat preservation time is 4h, so as to obtain a molybdenum-doped tungsten-doped crucible blank with the sheath;
and e, removing the sheath of the crucible blank obtained in the step d by using a horizontal lathe, and then processing the crucible blank into a finished product according to a finished product drawing.
10 molybdenum yttrium oxide-tungsten yttrium oxide crucibles prepared by the method of the example, the average value of the actual density measured by a still water weighing method is 11.45g/cm 3 The relative density averages 97.8%. The obtained crucible material has the purity of more than 99.9 percent, good interface connectivity and higher interface strength, when the tensile strength at normal temperature is tested, one side of tungsten is firstly broken, the fracture is not at the interface, the tensile strength is 260MPa, the average service life of the crucible is 4 months, and the service life of the crucible is about 2 times of that of a pure molybdenum crucible.
In order to more intuitively observe the molybdenum crucible effect prepared by the preparation method of the rare earth molybdenum crucible with long service life, a comparative example is also provided in the embodiment of the invention.
Comparative example 1
The embodiment prepares a pure molybdenum crucible with the relative density of more than 99.4 percent, and the external dimension of the crucible is
The wall thickness is 10mm, and the crucible is made of pure molybdenum.
Step a, powder selection: selecting molybdenum powder with purity of 99.9% and granularity of 3.5 μm;
step b, powder batch mixing: mechanically mixing the molybdenum powder for 3 hours;
step c, packing: filling molybdenum powder into a powder filling sheath, compacting the powder filling sheath on a vibrating platform, welding an upper cover plate 3 and the powder filling sheath 4 to form a welding line 2, placing the sheath 4 in a vacuum electron beam welding cavity, vacuumizing the vacuum electron beam welding cavity, and welding an extraction opening 1 on the cover plate 3 to obtain a crucible blank with the sheath, wherein the thickness of the sheath is 1.5mm, and the temperature during vacuumizing is 350 ℃;
step d, sintering by hot isostatic pressing: placing the sheath filled with the powder into a hot isostatic pressing machine for sintering treatment, wherein the sintering is performed under the argon atmosphere, the argon pressure is 180MPa, the heating rate of the whole temperature section is 400 ℃/h, the highest sintering temperature is 1950 ℃, and the heat preservation time is 2h, so that a pure molybdenum crucible blank with the sheath is obtained;
and e, removing the sheath of the crucible blank obtained in the step d by using a horizontal lathe, and then processing the crucible blank into a finished product according to a finished product drawing.
10 pure molybdenum crucibles prepared by the method of the example have an average value of 9.95g/cm of actual density measured by a still water weighing method 3 The relative density averages 97.5%. The purity of the obtained crucible material is more than 99.9%, the tensile strength at the test normal temperature is 350MPa, and the average service life of the crucible is 2 months.
Example 1 compared with comparative example 1, the average density of the pure molybdenum-pure tungsten crucible in example 1 was greater than that of the pure molybdenum crucible, and the average crucible life was 3.8 months, which was 1.9 times that of the pure molybdenum crucible.
Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing a rare earth molybdenum crucible, which is characterized by comprising the following steps:
step a, powder selection: selecting raw material powder meeting the requirements;
step b, powder batch mixing: separately mixing the powder of the component A and the powder of the component B, wherein the component A is pure molybdenum powder or the mixture of the molybdenum powder and oxide powder; the component B is pure tungsten powder or the mixture of tungsten powder and oxide powder;
step c, packing: sequentially filling the powder of the component B and the powder of the component A into a sheath, compacting, and sealing, wherein the mouth part of a crucible in a molybdenum crucible is made of tungsten, and the middle lower wall and the bottom are made of molybdenum;
step d, sintering by hot isostatic pressing: placing the sheath filled with the powder into a hot isostatic pressing machine for sintering treatment to obtain a crucible blank with the sheath;
step e, machining: and turning the crucible blank on a lathe to remove the sheath to obtain a crucible, and machining the crucible to obtain a finished product.
2. The method for preparing a rare earth molybdenum crucible according to claim 1, wherein in the step b, the batch mixing method is a mechanical mixing method.
3. The method for producing a rare earth molybdenum crucible according to claim 1, wherein the height at which the component B is provided is 1/5 of the crucible height.
4. The method of preparing a rare earth molybdenum crucible as defined in claim 1, wherein in step c, sealing the sheath comprises the steps of:
step c1, welding a cover plate on the sheath;
and c2, placing the sheath in a vacuum electron beam welding cavity for vacuumizing, and welding an extraction opening on the cover plate by using the vacuum electron beam welding.
5. The method of claim 4, wherein the vacuum degree in the vacuum electron beam welding chamber is 1 x 10 -2 Pa, and the temperature is 300-500 ℃.
6. The method for preparing a rare earth molybdenum crucible according to claim 1, wherein in the step d, the heating rate of the hot isostatic pressing treatment is 100-500 ℃/h, the pressure is 170-200MPa, and the holding time is 1-5h.
7. The method for producing a rare earth molybdenum crucible according to claim 1, wherein the oxide powder is cerium oxide powder, yttrium oxide powder, zirconium oxide powder or lanthanum hydroxide powder.
8. The method for producing a rare earth molybdenum crucible according to claim 1, wherein the particle size of the molybdenum powder is 3.0 to 4.0 μm and the particle size of the tungsten powder is 1.5 to 2.5 μm.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307261A (en) * | 1987-06-05 | 1988-12-14 | Mitsubishi Electric Corp | Thin film forming device |
| JPH0625855A (en) * | 1992-07-13 | 1994-02-01 | Tokyo Tungsten Co Ltd | Crucible and its production |
| CN202465907U (en) * | 2012-03-14 | 2012-10-03 | 江西南方稀土高技术股份有限公司 | 10,000 ampere rare earth molten salt electrolytic bath crucible |
| CN104213096A (en) * | 2014-08-12 | 2014-12-17 | 厦门虹鹭钨钼工业有限公司 | Preparation method of crucible with tungsten coating |
| CN104470658A (en) * | 2012-05-29 | 2015-03-25 | H·C·施塔克公司 | Metallic crucibles and methods of forming the same |
| WO2015099010A1 (en) * | 2013-12-26 | 2015-07-02 | 株式会社アライドマテリアル | Sapphire single-crystal growth crucible, method for growing sapphire single crystal, and method for manufacturing sapphire single-crystal growth cruciblegrowing sapphire single crystal |
| CN206266721U (en) * | 2016-12-09 | 2017-06-20 | 株洲硬质合金集团有限公司 | A kind of molybdenum crucible |
| CN108772558A (en) * | 2018-06-15 | 2018-11-09 | 赣州有色冶金研究所 | A kind of compound tungsten crucible of multielement rare earth and its preparation method and application |
| CN109321870A (en) * | 2018-12-13 | 2019-02-12 | 株洲硬质合金集团有限公司 | A kind of compound molybdenum crucible and its preparation method and application |
| CN111015105A (en) * | 2019-12-17 | 2020-04-17 | 有研亿金新材料有限公司 | Manufacturing method of tungsten iridium crucible |
| CN111036916A (en) * | 2019-12-13 | 2020-04-21 | 安泰天龙钨钼科技有限公司 | Preparation method of rhenium alloy crucible |
| CN210952339U (en) * | 2019-11-08 | 2020-07-07 | 洛阳聚晶钨钼科技有限公司 | Anti-drop tungsten molybdenum crucible |
-
2020
- 2020-09-27 CN CN202011031112.5A patent/CN114346245B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307261A (en) * | 1987-06-05 | 1988-12-14 | Mitsubishi Electric Corp | Thin film forming device |
| JPH0625855A (en) * | 1992-07-13 | 1994-02-01 | Tokyo Tungsten Co Ltd | Crucible and its production |
| CN202465907U (en) * | 2012-03-14 | 2012-10-03 | 江西南方稀土高技术股份有限公司 | 10,000 ampere rare earth molten salt electrolytic bath crucible |
| CN104470658A (en) * | 2012-05-29 | 2015-03-25 | H·C·施塔克公司 | Metallic crucibles and methods of forming the same |
| WO2015099010A1 (en) * | 2013-12-26 | 2015-07-02 | 株式会社アライドマテリアル | Sapphire single-crystal growth crucible, method for growing sapphire single crystal, and method for manufacturing sapphire single-crystal growth cruciblegrowing sapphire single crystal |
| CN104213096A (en) * | 2014-08-12 | 2014-12-17 | 厦门虹鹭钨钼工业有限公司 | Preparation method of crucible with tungsten coating |
| CN206266721U (en) * | 2016-12-09 | 2017-06-20 | 株洲硬质合金集团有限公司 | A kind of molybdenum crucible |
| CN108772558A (en) * | 2018-06-15 | 2018-11-09 | 赣州有色冶金研究所 | A kind of compound tungsten crucible of multielement rare earth and its preparation method and application |
| CN109321870A (en) * | 2018-12-13 | 2019-02-12 | 株洲硬质合金集团有限公司 | A kind of compound molybdenum crucible and its preparation method and application |
| CN210952339U (en) * | 2019-11-08 | 2020-07-07 | 洛阳聚晶钨钼科技有限公司 | Anti-drop tungsten molybdenum crucible |
| CN111036916A (en) * | 2019-12-13 | 2020-04-21 | 安泰天龙钨钼科技有限公司 | Preparation method of rhenium alloy crucible |
| CN111015105A (en) * | 2019-12-17 | 2020-04-17 | 有研亿金新材料有限公司 | Manufacturing method of tungsten iridium crucible |
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