CN113604720B - Large-size deformation-resistant molybdenum alloy bar and preparation method thereof - Google Patents
Large-size deformation-resistant molybdenum alloy bar and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
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- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
- B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
Abstract
The invention provides a large-size deformation-resistant molybdenum alloy bar and a preparation method thereof. The method comprises the following steps: the method comprises the following steps of molybdenum alloy powder preparation, press forming, high-temperature sintering, forging deformation and annealing, wherein in the molybdenum alloy powder preparation, the molybdenum alloy powder preparation comprises the following components in percentage by weight: w5% -15%, ZrO20.5 to 2.5 percent of molybdenum and the balance of Mo, respectively weighing a molybdenum source, a tungsten source and a zirconium source, and mixing to obtain molybdenum alloy powder. The size of the molybdenum alloy bar prepared by the method is phi 90-phi 120mm, the longest length can reach 3000mm, the highest tensile strength at room temperature can reach 750MPa, the highest high-temperature strength at 1300 ℃ can reach 350MPa, and the highest recrystallization temperature can reach 1400 ℃.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a large-size deformation-resistant molybdenum alloy rod and a preparation method thereof.
Background
The pure molybdenum has the characteristics of excellent high-temperature strength, good electric and heat conductivity, low thermal expansion coefficient, no coloring to glass and the like, and is widely applied to the fields of glass industry and glass fiber industry as a glass melting electrode.
The specifications of the common molybdenum electrode produced in China at present are usually 50-80mm in diameter and less than or equal to 2000mm in length, the size of the common molybdenum electrode cannot meet the requirements with the large-scale development of a glass industrial kiln, and meanwhile, the common pure molybdenum electrode has the defects of low recrystallization temperature, low high-temperature strength, poor creep resistance, easy deformation and even fracture in the long-term service process and the like.
Patent CN110066952B discloses a preparation method of a zirconia reinforced molybdenum alloy rod, which comprises mixing ammonium molybdate with a zirconium nitrate solution, then ball-milling, drying, and roasting to obtain precursor powder; the precursor powder is subjected to secondary reduction in a reducing atmosphere, and then the molybdenum alloy rod is obtained by press forming, sintering and forging, but the molybdenum alloy rod prepared by the method has smaller size and cannot meet the use requirement of a molybdenum electrode of a large-size glass industrial kiln.
Patent CN109306421B discloses an anti-erosion molybdenum electrode and a manufacturing method thereof, the method is through solid-liquid doping and multi-element ball milling doping, and the electrode is composed of the following components by weight percentage: ZrO (ZrO)23～5wt％、Si 0.8～1.2wt％、B 0.1～0.5wt％、GeO20.001～3wt％、SnO20.001～3wt％、Bi2O30.001 to 3 wt%, W0 to 5 wt%, and Al2O30-4 wt%, the balance of Mo and non-removable impurities, the molybdenum alloy has more doping elements, and the uniformity of the molybdenum alloy powder is poor; and the ceramic phase zirconia has high content, the molybdenum alloy has poor plasticity, cracks are easy to appear in the subsequent deformation processing process, the production qualification rate is low, and the method is not suitable for industrial production.
Disclosure of Invention
Aiming at the defects and defects in the prior art, one of the purposes of the invention is to provide a preparation method of a large-size deformation-resistant molybdenum alloy rod, the molybdenum alloy rod prepared by the method has the excellent performances of high production yield, fine and uniform crystal grains, high-temperature strength, high recrystallization temperature and the like, the prepared molybdenum alloy rod can reach phi 90-phi 120mm, the length can reach 3000mm, and the use requirement in the field of glass fiber industry can be met.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a large-size deformation-resistant molybdenum alloy rod comprises the following steps:
the preparation method of the molybdenum alloy powder comprises the following steps: respectively weighing a molybdenum source, a tungsten source and a zirconium source according to the weight percentage, and mixing to obtain molybdenum alloy powder, wherein the molybdenum alloy powder comprises the following components in percentage by weight: w5% -15%, ZrO20.5-2.5% and the balance of Mo;
a step of press forming: filling the molybdenum alloy powder into a designed die cavity for compression molding treatment to obtain a pressed blank;
and (3) high-temperature sintering: carrying out high-temperature sintering treatment on the pressed blank in reducing atmosphere, inert gas or vacuum condition to obtain a molybdenum alloy sintered blank;
forging and deforming: carrying out forging deformation treatment on the molybdenum alloy sintered blank to obtain a forged bar blank;
and (3) annealing: and annealing the forged bar blank in a reducing atmosphere to obtain the large-size deformation-resistant molybdenum alloy bar.
In the above method for preparing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the step for preparing the molybdenum alloy powder, the molybdenum source is molybdenum powder, the tungsten source is tungsten powder, the zirconium source is nano-zirconia powder, the fisher particle size of the molybdenum powder is 2.0 to 4.0 μm, the fisher particle size of the tungsten powder is 2.5 to 4.5 μm, and the particle size of the nano-zirconia powder is 20 to 60 nm.
In the application, tungsten is introduced into a molybdenum matrix, and the tungsten and molybdenum can form a solid solution to play a role in solid solution strengthening; the nano-grade zirconia is added, so that the zirconia can be uniformly distributed among the molybdenum matrix grains, the growth speed of high-temperature grains is greatly reduced, and the dispersion strengthening effect can be achieved, so that the recrystallization temperature and the creep resistance of the molybdenum alloy are improved; the molybdenum alloy has the advantages that the added tungsten element and the added nano zirconia have too high content, so that the pressure processing performance of the molybdenum alloy is deteriorated due to solid solution strengthening and second phase dispersion strengthening, cracks are easily induced to form, the material is invalid, the content of the added tungsten element and the nano zirconia is low, and the performance of the molybdenum alloy is not obviously improved; in addition, in the molybdenum alloy, when the second phase particles of nano zirconia are moderate in quantity and are dispersed in the molybdenum alloy in fine particles, the performance of the molybdenum alloy can be improved, when the zirconia particles are too large, the strengthening effect is poor, and when the zirconia particles are too small, agglomeration is easy to form.
In the above method for manufacturing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the step of press forming, the diameter of the green compact is 200 to 300mm (for example, 220mm, 240mm, 260mm, 280mm, 300 mm).
In the above method for producing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the high-temperature sintering step, the maximum sintering temperature of the high-temperature sintering treatment is 2000-2200 ℃ (such as 2020 ℃, 2060 ℃, 2100 ℃, 2150 ℃ and 2200 ℃), and the temperature is kept for 4-8 hours (such as 4.5 hours, 5 hours, 6 hours, 7 hours and 7.5 hours) under the condition of the maximum sintering temperature; preferably, the high-temperature sintering treatment is a step-by-step heating sintering, and a plurality of heat preservation steps are arranged before the highest sintering temperature is reached so as to remove impurities; in the application, the density of the sintered blank is insufficient when the highest sintering temperature is too low, so that the subsequent forging deformation processing is not facilitated, crystal grains are easy to grow up and the product cost is increased sharply when the highest sintering temperature is too high.
In the above method for manufacturing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the high-temperature sintering step, the diameter of the molybdenum alloy sintered compact is 180 to 250mm (e.g., 190mm, 210mm, 230mm, 250 mm).
In the above method for producing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the forging deformation step, a rapid forging deformation treatment is adopted, wherein the initial forging temperature is 1400 to 1550 ℃ (such as 1420 ℃, 1450 ℃, 1470 ℃, 1520 ℃, 1540 ℃), the final forging temperature is not lower than 1100 ℃, the total deformation amount of the rapid forging deformation treatment is more than 70%, and the rapid forging deformation treatment comprises more than two times of forging treatment; preferably, the finish forging temperature is 1150-; in the application, if the finish forging temperature is too high, crystal grains are easy to be coarse, so that the performance is reduced, and if the finish forging temperature is lower than 1100 ℃, cracks are easy to generate in the forging process; in the present application, the deformation amount is (sectional area before deformation-sectional area after deformation)/sectional area before deformation; preferably, the heating time before the start of the rapid forging deformation treatment is 2 to 4 hours; more preferably, the forging speed is 80-108 mm/s (such as 82mm/s, 85mm/s, 88mm/s, 92mm/s, 95mm/s, 98mm/s, 102 mm/s); if the forging speed is too low, the temperature of the blank is reduced rapidly in the forging process, and the plasticity of the material is not facilitated; however, if the forging speed is too high, the energy consumption is large, and the cost is increased; further preferably, the forging deformation process is performed by a rapid forging machine with a nominal pressure of 1000T or more.
In the above method for producing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the forging deformation step, the forging deformation treatment includes two-fire forging treatments, and the heating treatment and the rapid forging treatment are sequentially performed for each fire forging treatment; preferably, in the first hot forging treatment, the heating temperature of the heating treatment is 1400-1550 ℃ (such as 1420 ℃, 1450 ℃, 1470 ℃, 1520 ℃ and 1540 ℃), and the heat preservation time is 1-2 h (such as 1.2h, 1.5h and 1.8h), the first hot forging treatment at the heating temperature and the heat preservation time can fully heat the blank, the temperature of the edge and the center are uniform, the plasticity of the material is improved, the high-temperature deformation resistance is reduced, and further the production efficiency and the internal quality of the forge piece are improved; the forging deformation of the rapid forging treatment is 40-60% (such as 42%, 45%, 48%, 50%, 52%, 54%, 58%), if the forging deformation is too small, the center of the blank is not deformed, and if the forging deformation is too large, cracks are easy to generate, and the yield is reduced; the forging speed is 80-108 mm/s (such as 82mm/s, 85mm/s, 88mm/s, 92mm/s, 95mm/s, 98mm/s and 102 mm/s).
Preferably, in the second hot forging treatment, the heating temperature of the heating treatment is 1250-1350 ℃ (such as 1250 ℃, 1280 ℃, 1300 ℃, 1320 ℃, 1340 ℃) and the heat preservation time is 0.5-1.5 h (such as 0.7h, 1h, 1.2h, 1.4h), the forging deformation amount of the fast forging treatment is 30-50% (such as 32%, 35%, 38%, 40%, 42%, 44%, 48%), and the forging speed is 80-108 mm/s (such as 82mm/s, 85mm/s, 88mm/s, 92mm/s, 95mm/s, 98mm/s, 102 mm/s); in the application, the heating temperature (namely the forging temperature) of the second heating treatment is lower than that of the first heating treatment, so that recrystallization in the forging process is avoided, but the forging temperature cannot be too low, and cracks can be generated when the forging temperature is too low; in the application, if the second heat deformation is too large, the blank is cracked, so the forging deformation is controlled to be 30-50%, compared with the two heat forging treatment, if the one heat forging treatment is carried out, cracks are easily generated due to too large deformation, and the capability of a quick forging device is challenged.
In this application, through the forging of the big deflection that quick forging deformation equipment realized molybdenum alloy rod, the forging number of times is no longer than two to reduce the thermal cycle number in the deformation processing, avoid the emergence of the recrystallization action in the thermal deformation processing.
In the above-described method for producing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the step of forging and deforming, the diameter of the forged rod blank is 90 to 120mm (e.g., 95mm, 100mm, 110mm, 120 mm).
In the above method for manufacturing a large-size deformation-resistant molybdenum alloy rod, as a preferred embodiment, in the annealing step, the annealing temperature of the annealing treatment is 1050 to 1150 ℃ (such as 1080 ℃, 1110 ℃ and 1140 ℃), and the heat preservation time is 60 to 120min (such as 70min, 80min, 90min, 100min and 110 min); the annealing treatment mainly aims at removing internal stress caused by forging deformation, the stress can not be eliminated when the temperature is too low, and crystal grains are easy to grow when the temperature is too high; the method and the device carry out annealing treatment in a reducing atmosphere, and prevent the molybdenum alloy from being oxidized at a high temperature.
The second aspect of the invention provides a large-size deformation-resistant molybdenum alloy rod, which is prepared by adopting the preparation method; preferably, the size of the molybdenum alloy rod is phi 90-phi 120mm, the longest length can reach 3000mm, the highest tensile strength at room temperature can reach 750MPa, the highest high-temperature strength at 1300 ℃ can reach 350MPa, and the highest recrystallization temperature can reach 1400 ℃.
Compared with the prior art, the invention has the following positive effects:
(1) the preparation method provided by the invention has the advantages that the process is simple, the qualification rate of the produced molybdenum alloy rod is high, and the industrial production is easy to realize;
(2) the invention adds W and ZrO during the preparation process2By solid solution strengthening of W and ZrO2And dispersion strengthening, wherein the nano-ceramic zirconia powder is uniformly dispersed and distributed among the molybdenum matrix grains, so that the growth speed of the grains at high temperature is greatly reduced, and the recrystallization temperature and the creep resistance of the molybdenum alloy are improved.
(3) The molybdenum alloy rod prepared by the method has the excellent performances of fine and uniform grain structure, high-temperature strength, high recrystallization temperature and the like, the production specification can be expanded to phi 90-phi 120mm, and the longest length can reach 3000 mm; the tensile strength at room temperature can reach 750MPa, the high-temperature strength at 1300 ℃ can reach 350MPa, and the use requirements in the field of glass fiber industry can be met.
(4) The invention has the advantages of large total deformation amount of forging, less forging pass, fine and uniform grain structure of the obtained product, high recrystallization temperature, good high-temperature mechanical property and excellent high-temperature deformation resistance.
Drawings
For a more clear description of the invention, reference is made herein to the accompanying drawings, which form a further part hereof. Wherein:
FIG. 1 is a cross-sectional metallographic structure photograph of a large-size deformation-resistant molybdenum alloy rod prepared in example 1;
FIG. 2 is a longitudinal cross-sectional metallographic structure photograph of the large-size deformation-resistant molybdenum alloy rod prepared in example 1;
FIG. 3 is a cross-sectional metallographic structure photograph of the large-size deformation-resistant molybdenum alloy rod prepared in comparative example 1;
FIG. 4 is a cross-sectional metallographic structure photograph of the large-size deformation-resistant molybdenum alloy rod prepared in comparative example 2;
FIG. 5 is a cross-sectional metallographic structure photograph of a large-size deformation-resistant molybdenum alloy rod prepared in comparative example 3;
fig. 6 is a cross-sectional metallographic structure photograph of the large-size deformation-resistant molybdenum alloy rod prepared in comparative example 4.
Detailed Description
The large-size deformation-resistant molybdenum alloy rod and the preparation method thereof according to the present invention will be described with reference to the accompanying drawings and examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by one skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the invention as defined by the appended claims.
The starting materials used in the examples below are all commercially available. The equipment used for the forging deformation treatment is a quick forging machine, and the manufacturer is a blue stone heavy industry Co., Ltd, and the model is a 10MN quick forging machine. The purity of the molybdenum powder, tungsten powder and zirconia powder used in the following examples was 99.9% or more.
Example 1
(1) Preparing molybdenum alloy powder: according to Mo-6% W-1% ZrO2(i.e., ZrO in the molybdenum alloy powder in terms of weight percent)21 percent, W6 percent and the balance of Mo) are respectively weighed to obtain molybdenum powder and molybdenum powder with Fisher grain size of 3.2 mu mMixing tungsten powder with the particle size of 2.5 mu m and zirconia powder with the particle size of 20-40nm in a mixer to obtain molybdenum alloy powder;
(2) cold isostatic pressing: putting the molybdenum alloy powder obtained in the step (1) into a die, and maintaining the pressure for 6 minutes under the pressure of 150MPa to obtain a pressed blank with the diameter of 280 mm;
(3) and (3) high-temperature sintering: putting the pressed blank obtained in the step (2) into a medium-frequency high-temperature hydrogen sintering furnace for sintering: heating to 1200 ℃ at the speed of 80 ℃/h, preserving heat for 6h, then continuously heating to 2050 ℃ at the speed of 120 ℃/h, preserving heat for 4h, and obtaining a sintered blank with the diameter of 240 mm;
(4) forging deformation: carrying out quick forging deformation treatment on the sintered blank obtained in the step (3) for two times; wherein the first heating temperature is 1450 ℃, the heat preservation time is 1h, the diameter is 160mm after forging, the forging deformation is 55%, and the forging speed is 95 mm/s; the heating temperature of the second heating is 1300 ℃, the heat preservation time is 0.8h, the forging deformation is 44%, the forging speed is 90mm/s, the finish forging temperature is 1150 ℃, a forging bar blank with the diameter of 120mm and the length of 3000mm is finally obtained, and the total deformation of the forging deformation treatment is 75%;
(5) annealing: and (4) placing the forged bar blank obtained in the step (4) in a hydrogen protection heating furnace for annealing treatment, wherein the annealing temperature is 1100 ℃, and the temperature is kept for 60 min.
Fig. 1 is a cross-sectional metallographic structure photograph of the molybdenum alloy rod prepared in example 1, and fig. 2 is a longitudinal-sectional metallographic structure photograph of the molybdenum alloy rod prepared in example 1, and it can be seen that the molybdenum alloy rod prepared in example 1 has fine and uniform crystal grains.
In the embodiment, the recrystallization temperature is obtained by observing the grain structure change of the prepared molybdenum alloy rod at different temperatures, and the molybdenum alloy rod prepared in the embodiment 1 has the recrystallization temperature of 1300 ℃ and the room-temperature tensile strength of 660MPa through a tensile test (a room-temperature tensile test is carried out according to GB/T228.1-2010 part 1 room-temperature test method of a metal material tensile test, and a high-temperature tensile test is carried out according to GB/T4338-2006 part 1 high-temperature tensile test method); the high-temperature strength at 1300 ℃ reaches 260 MPa; example 13 molybdenum rods were prepared with a pass rate of 100%.
Example 2
(1) Preparing molybdenum alloy powder: according to Mo-10% W-1.5% ZrO2(i.e., ZrO in the molybdenum alloy powder in terms of weight percent)21.5 percent, W10 percent and the balance of Mo), respectively weighing molybdenum powder with Fisher granularity of 3.2 mu m, tungsten powder with Fisher granularity of 2.5 mu m and zirconia powder with the grain diameter of 20-40nm, and mixing in a mixer to obtain molybdenum alloy powder;
(2) cold isostatic pressing: putting the molybdenum alloy powder obtained in the step (1) into a die, and maintaining the pressure for 8 minutes under the pressure of 180MPa to obtain a pressed compact with the diameter of 280 mm;
(3) and (3) high-temperature sintering: putting the pressed blank obtained in the step (2) into a medium-frequency high-temperature hydrogen sintering furnace for sintering: heating to 1200 ℃ at the speed of 70 ℃/h, preserving heat for 8h, then continuously heating to 2100 ℃ at the speed of 110 ℃/h, preserving heat for 5h, and obtaining a sintered blank with the diameter of 240 mm;
(4) forging deformation: carrying out quick forging deformation treatment on the sintered blank obtained in the step (3) for two times; wherein the first heating temperature is 1500 ℃, the heat preservation time is 1.5h, the diameter is 160mm after forging, the forging deformation is 55%, and the forging speed is 100 mm/s; the heating temperature of the second heating is 1350 ℃, the heat preservation time is 1h, the forging deformation is 44%, the forging speed is 95mm/s, the finish forging temperature is 1150 ℃, a forged bar blank with the diameter of 120mm and the length of 3000mm is finally obtained, and the total deformation of the forging deformation treatment is 75%;
(5) annealing: and (4) placing the forged bar blank obtained in the step (4) in a hydrogen protection heating furnace for annealing treatment, wherein the annealing temperature is 1150 ℃, and the temperature is kept for 100 min.
The metallographic structure of the transverse section and the metallographic structure of the longitudinal section of the molybdenum alloy rod prepared in example 2 were similar to those of the molybdenum alloy rod prepared in example 1, and the grain size of the molybdenum alloy rod was small and uniform.
The recrystallization temperature of the molybdenum alloy rod prepared in the example 2 is 1350 ℃, and the room-temperature tensile strength of the molybdenum alloy rod reaches 710 MPa; the strength reaches 310MPa at 1300 ℃; example 23 molybdenum rods were prepared with a pass rate of 100%.
Example 3
(1) Preparing molybdenum alloy powder: according to Mo-14% W-2.2% ZrO2(i.e., ZrO in the molybdenum alloy powder in terms of weight percent)22.2 percent, W14 percent and the balance of Mo), molybdenum powder with Fisher granularity of 3.2 mu m, tungsten powder with Fisher granularity of 2.5 mu m and zirconia powder with the grain diameter of 20-40nm are respectively weighed and mixed in a mixer to obtain molybdenum alloy powder.
(2) Cold isostatic pressing: putting the molybdenum alloy powder obtained in the step (1) into a die, and maintaining the pressure for 10 minutes under the pressure of 200MPa to obtain a pressed compact with the diameter of 280 mm;
(3) and (3) high-temperature sintering: putting the pressed blank obtained in the step (2) into a medium-frequency high-temperature hydrogen sintering furnace for sintering: heating to 1200 ℃ at the speed of 60 ℃/h, preserving heat for 10h, then continuously heating to 2150 ℃ at the speed of 100 ℃/h, and preserving heat for 6h to obtain a sintered blank with the diameter of 240 mm;
(4) forging deformation: carrying out quick forging deformation treatment on the sintered blank obtained in the step (3) for two times; wherein the first heating temperature is 1520 ℃, the heat preservation time is 2 hours, the diameter is 160mm after forging, the forging deformation is 55%, and the forging speed is 105 mm/s; the heating temperature of the second heating is 1350 ℃, the heat preservation time is 1h, the forging deformation is 44%, the forging speed is 100mm/s, the finish forging temperature is 1200 ℃, a forging bar blank with the diameter of 120mm and the length of 3000mm is finally obtained, and the total deformation of the forging deformation treatment is 75%;
(5) annealing: and (4) placing the forged bar blank obtained in the step (4) in a hydrogen protection heating furnace for annealing treatment, wherein the annealing temperature is 1150 ℃, and the temperature is kept for 90 min.
The metallographic structure of the transverse section and the metallographic structure of the longitudinal section of the molybdenum alloy rod obtained in example 3 were similar to those of the molybdenum alloy rod obtained in example 1, and the grain size of the molybdenum alloy rod was small and uniform.
The recrystallization temperature of the molybdenum alloy rod prepared in the example 3 is 1400 ℃, and the room-temperature tensile strength of the molybdenum alloy rod reaches 750 MPa; the high-temperature strength at 1300 ℃ reaches 350 MPa; example 3 molybdenum rods were prepared with a pass rate of 100%.
Comparative example 1
Comparative example 1 the molybdenum alloy powder obtained in step (1) was the same as in example 1, except that the molybdenum alloy powder obtained in step (1) was changed to Mo-6% W (i.e., 6% W in the molybdenum alloy powder, and the balance Mo).
The recrystallization temperature of the molybdenum alloy rod prepared in the comparative example 1 is 1250 ℃, and the room-temperature tensile strength reaches 620 MPa; the strength reaches 230MPa at 1300 ℃; comparative example 13 molybdenum rods were prepared, and the yield was 100%.
Comparative example 2
Comparative example 2 ZrO 2 in terms of Mo-1% except in step (1)2(i.e., ZrO in the molybdenum alloy powder in terms of weight percent21% with the balance being Mo) was carried out in the same manner as in example 1 except that the molybdenum alloy powder obtained in example 1 was different from the molybdenum alloy powder obtained in example 1.
The recrystallization temperature of the molybdenum alloy rod prepared in the comparative example 2 is 1200 ℃, and the room-temperature tensile strength of the molybdenum alloy rod reaches 600 MPa; the strength reaches 180MPa at 1300 ℃; comparative example 13 molybdenum rods were prepared, and the yield was 100%.
Comparative example 3
Comparative example 3 Mo-6% W-1% ZrO in accordance with the procedure in step (1)2(i.e., W6% in the molybdenum alloy powder, ZrO in terms of weight percent)21% with the balance being Mo), molybdenum powder having a Fisher size of 3.2. mu.m, tungsten powder having a Fisher size of 2.5 μm, and zirconia powder having a particle size of 60 to 100nm were weighed to obtain molybdenum alloy powder, and the procedure was carried out in the same manner as in example 1 except that the molybdenum alloy powder was used in example 1.
The recrystallization temperature of the molybdenum alloy rod prepared in the comparative example 3 is 1300 ℃, and the room-temperature tensile strength reaches 650 MP; the high-temperature strength at 1300 ℃ reaches 245 MPa; comparative example 13 molybdenum rods were prepared, and the yield was 100%.
Comparative example 4
Comparative example 4 the same as example 3 except that the finish forging temperature in step (4) was 1350 ℃.
The recrystallization temperature of the molybdenum alloy rod prepared in the comparative example 4 is 1400 ℃, and the room-temperature tensile strength of the molybdenum alloy rod reaches 680 MP; the high-temperature strength at 1300 ℃ reaches 330 MPa; comparative example 43 molybdenum rods were prepared, and the yield was 100%.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The preparation method of the large-size deformation-resistant molybdenum alloy rod is characterized by comprising the following steps of:
the preparation method of the molybdenum alloy powder comprises the following steps: the molybdenum alloy powder comprises the following components in percentage by weight: w5% -15%, ZrO20.5-2.5% and the balance of Mo; respectively weighing a molybdenum source, a tungsten source and a zirconium source according to the weight percentage, and mixing to obtain molybdenum alloy powder, wherein in the preparation step of the molybdenum alloy powder, the molybdenum source is molybdenum powder, and the tungsten source is tungsten powder; the zirconium source is nano-zirconia powder, and the particle size of the nano-zirconia powder is 20-60 nm;
a pressing and forming step: filling the molybdenum alloy powder into a designed die cavity for compression molding treatment to obtain a pressed blank;
and (3) high-temperature sintering: carrying out high-temperature sintering treatment on the pressed blank in reducing atmosphere, inert gas or vacuum condition to obtain a molybdenum alloy sintered blank; in the high-temperature sintering step, the highest sintering temperature of the high-temperature sintering treatment is 2000-2200 ℃, and the heat is preserved for 4-8 hours under the condition of the highest sintering temperature;
forging and deforming: carrying out forging deformation treatment on the molybdenum alloy sintered blank to obtain a forged bar blank; in the forging deformation step, rapid forging deformation treatment is adopted, the initial forging temperature is 1400-1550 ℃, the final forging temperature is 1150-; in the second hot forging treatment, the heating temperature of the heating treatment is 1250-1350 ℃, the heat preservation time is 0.5-1.5 h, the forging deformation of the fast forging treatment is 30-50%, and the forging speed is 80-108 mm/s;
and (3) annealing: annealing the forged bar blank in a reducing atmosphere to obtain the large-size deformation-resistant molybdenum alloy bar; in the annealing step, the annealing temperature of the annealing treatment is 1050-1150 ℃, and the heat preservation time is 60-120 min; the large-size deformation-resistant molybdenum alloy rod has the size of phi 90-phi 120mm, the longest length of 3000mm, the highest room-temperature tensile strength of 750MPa, the highest 1300-temperature high-temperature strength of 350MPa and the highest recrystallization temperature of 1400 ℃.
2. The method for preparing a large-sized deformation-resistant molybdenum alloy rod according to claim 1, wherein in the step of preparing the molybdenum alloy powder, the fisher's particle size of the molybdenum powder is 2.0 to 4.0 μm, and the fisher particle size of the tungsten powder is 2.5 to 4.5 μm.
3. The method for manufacturing a large-sized deformation-resistant molybdenum alloy rod according to claim 1 or 2, wherein in the press-forming step, the diameter of a compact is 200 to 300 mm.
4. The method for preparing a large-sized deformation-resistant molybdenum alloy rod according to claim 1, wherein the high-temperature sintering process is a step-wise temperature-rising sintering process, and a plurality of heat-insulating steps are provided before the maximum sintering temperature is reached to remove impurities.
5. The method for preparing a large-size deformation-resistant molybdenum alloy rod according to claim 4, wherein in the high-temperature sintering step, the diameter of the molybdenum alloy sintered compact is 180-250 mm.
6. The method for preparing a large-size deformation-resistant molybdenum alloy rod according to claim 1, wherein the forging deformation treatment is performed by using a rapid forging machine with a nominal pressure of 1000 tons or more.
7. The method for producing a large-size deformation-resistant molybdenum alloy rod according to claim 1, wherein in the step of forging deformation, the diameter of the forged rod blank is 90 to 120 mm.
8. A large-sized deformation-resistant molybdenum alloy rod, characterized by being produced by the production method according to any one of claims 1 to 7.
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| CN110722152A (en) * | 2019-10-29 | 2020-01-24 | 安泰天龙钨钼科技有限公司 | Large-size fine-grain molybdenum rod and preparation method thereof |
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| US7255757B2 (en) * | 2003-12-22 | 2007-08-14 | General Electric Company | Nano particle-reinforced Mo alloys for x-ray targets and method to make |
| CN102875147B (en) * | 2012-10-17 | 2013-11-20 | 安泰科技股份有限公司 | Zirconia ceramic material and preparation method thereof |
| CN109306421B (en) * | 2018-09-18 | 2019-09-17 | 厦门虹鹭钨钼工业有限公司 | A kind of anti-erosion molybdenum alloy electrode and its manufacturing method |
| CN110453127B (en) * | 2019-09-09 | 2020-07-10 | 安泰天龙钨钼科技有限公司 | Multi-element composite reinforced molybdenum alloy and preparation method thereof |
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| CN104439236A (en) * | 2014-12-23 | 2015-03-25 | 金堆城钼业股份有限公司 | Preparing method of zirconium oxide molybdenum alloy electrode |
| EP3118339A1 (en) * | 2015-07-17 | 2017-01-18 | Gesellschaft für Wolfram Industrie mbH | Molybdenum alloy, electrode comprising a molybdenum alloy, and use of an electrode |
| CN106591613A (en) * | 2016-11-10 | 2017-04-26 | 洛阳科威钨钼有限公司 | Method for preparing tungsten-molybdenum alloy by doping beneficial elements |
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| CN110722152A (en) * | 2019-10-29 | 2020-01-24 | 安泰天龙钨钼科技有限公司 | Large-size fine-grain molybdenum rod and preparation method thereof |
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