CN102041403A - Preparation method of low-oxygen MHC alloy and application of low-oxygen MHC alloy - Google Patents
Preparation method of low-oxygen MHC alloy and application of low-oxygen MHC alloy Download PDFInfo
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- CN102041403A CN102041403A CN2009103087148A CN200910308714A CN102041403A CN 102041403 A CN102041403 A CN 102041403A CN 2009103087148 A CN2009103087148 A CN 2009103087148A CN 200910308714 A CN200910308714 A CN 200910308714A CN 102041403 A CN102041403 A CN 102041403A
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Abstract
The invention provides a preparation method of a low-oxygen MHC alloy. The method comprises the following steps of: 1) selecting raw materials, namely uniformly mixing industrial molybdenum powder of which the Fisher particle size is 4 mu m to 50 mu m, hafnium-containing power of which the Fisher particle size is 3 mu m to 10 mu m and elementary carbon of which the Fisher particle size is 0.1 mu m to 3 mu m in a certain mass ratio; 2) molding the raw materials, namely treating the mixed raw materials under the pressure of 100 and 300MPa to obtain a molded blank; and 3) sintering the raw materials, namely sintering the molded blank in an environment of vacuum, hydrogen or inert gas and at the temperature of between 1,800 and 2,300 DEG C for 5 to 15 hours to obtain the low-oxygen MHC alloy. By the method, the problem that the MHC alloy prepared by a powder metallurgy method contains high oxygen is solved. The low-oxygen MHC alloy prepared by the method can be applied to the preparation of X-ray tube rotating anode targets, composite target base targets, high-temperature crucibles, hot-forged dies and high-temperature ceramic pads.
Description
Technical field
The present invention relates to method and the application of hypoxemia MHC alloy that a kind of powder metallurgy process prepares hypoxemia MHC alloy, adopt the MHC alloy of this method preparation, oxygen level can be low to moderate below the 20ppm, and optimum can reach 1ppm.
Background technology
MHC alloy (Molybdenum-Hafnium-Carbon Alloy) is a kind of high temperature molybdenum base alloy, also is a kind of important superalloy in the present commercial use.Because the MHC alloy has the good high-temperature performance, thereby is used widely in industries such as medicine equipment, aerospace, electronic industry and glass-ceramic production.
Studies show that the plasticity-brittle transition temperature of MHC alloy, recrystallization temperature, toughness are all relevant with oxygen level.Oxygen in the MHC alloy easily combines with the strengthening element hafnium, and the oxide particle of hafnium is bigger, and it is even to be difficult to disperse, and strengthening effect is poor, and easily forms formation of crack.When oxygen level is high in the MHC alloy, alloy plasticity-brittle transition temperature is raise, recrystallization temperature reduces, and directly causes alloy toughness to reduce, and workability is poor, has a strong impact on alloy property.Oxygen level is high more in the MHC alloy, and alloy property is poor more, otherwise alloy property is just good more, and therefore, oxygen is the impurity element of wanting strict control.
The main method of producing above-mentioned alloy has two kinds: smelting process and powder metallurgic method.
Smelting process is that pure molybdenum and a certain amount of hafnium, carbon are carried out the method that melting obtains the MHC alloy under vacuum.Smelting process can make in the MHC alloy oxygen level drop to 30ppm even below the 20ppm.But the above-mentioned alloy grain that smelting process is produced is thick, complex process, and yield rate is low, the cost height.
Powder metallurgic method be with molybdenum powder and hafnium powder or hydrogenation hafnium powder and carbon black powder by a certain percentage uniform mixing after static pressure shaping, sintering, rolling (forging), annealing obtain the method for MHC alloy.The MHC alloy grain that powder metallurgic method is produced is tiny, and operation and equipment are simple, and is with short production cycle, the yield rate height.But powder metallurgy technology in the past is difficult to reduce the oxygen level in the MHC alloy, and the MHC alloy oxygen level of powder metallurgic method production is all more than 200ppm usually.
If adopt hypoxemia MHC alloy material in the past, not only discharge quantity is bigger, and is difficult to so big load of carrying, and the situation of crackle even fracture easily takes place, and material property can't satisfy the service requirements of high temperature and high speed rotation.
When the MHC alloy material making high-temperature resistant container that adopts in the past, because discharge quantity is big and hot strength is low, the phenomenon that container also can occur exitting and pollute molten metal or crackle seepage metal occurs.
Equally, when employing MHC alloy material was in the past made hot forged mould and sintering high temperature ceramic backing, mould was easily cracked in the high temperature process process, and backing plate is yielding, influences the work-ing life of mould and backing plate.
Summary of the invention
The invention provides a kind of preparation method and application thereof of hypoxemia MHC alloy, the method that has mainly solved applied powder metallurgy is prepared the high problem of MHC alloy oxygen level.
Technical solution of the present invention is as follows:
The preparation method of this hypoxemia MHC alloy may further comprise the steps:
1) raw material is chosen
Choosing Fisher particle size is the industrial molybdenum powder of 4 μ m～50 μ m, Fisher particle size is that hafnium powder, hydrogenation hafnium powder or the hafnium powder of 3 μ m～10 μ m mixes with arbitrary proportion with the hydrogenation hafnium powder, Fisher particle size is the carbon simple substance powder of 0.1 μ m～3 μ m, described industrial molybdenum powder, hafnium powder or hydrogenation hafnium powder and carbon simple substance powder mixes is even, form mixing raw material, or industrial molybdenum powder, hafnium powder and hydrogenation hafnium powder is even with mixture and the carbon simple substance powder mixes that arbitrary proportion is mixed and made into, form mixing raw material; Described mixing raw material is by mass ratio, contain the mixture that 0.1%～2.0% hafnium powder, hydrogenation hafnium powder or hafnium powder and hydrogenation hafnium powder are mixed and made into arbitrary proportion, 0.01%～0.15% carbon simple substance powder and 97.85%～99.89% industrial molybdenum powder; Theoretically, the molybdenum powder powder Fisher particle size of choosing is big more, and the MHC alloy oxygen level that obtains is low more, but the Fisher particle size of powder is big more, and the powder process difficulty is big more, and the powder process cost is high more, and moulding is difficult more, the sintering temperature height, and the time is long;
2) material forming
The raw material that mixes through step 1) is carried out static pressure or mold pressing obtains shaping blank, and the pressure size of choosing is relevant with the powder size size, chooses 100MPa～300MPa usually, preferably 220MPa～300Mpa;
3) raw material sintering
In vacuum, hydrogen or inert gas environment, shaping blank is carried out sintering, sintering temperature is 1800 ℃～2300 ℃, and sintering time is relevant with the size and the powder size of base to be sintered with sintering temperature, and powder size is big more, sintering temperature is high more, and sintering time is 5～15 hours usually.
Above-described carbon simple substance powder is that carbon black, graphite or carbon dust are arbitrary or arbitrarily multiplely mix with arbitrary proportion; When the powder Fisher particle size was excessive, tooling cost will significantly promote.The preferable range that factors such as cost that therefore, comprehensive powder process, moulding, sintering are required and material performance consider to draw the molybdenum powder granularity is 10 μ m～30 μ m.
Use the hypoxemia MHC alloy of method for preparing, be used for the preparation of X ray tube rotary anode target, composition target base target, high-temperature crucibles, hot forged mould and pyroceramic pad.
The invention has the advantages that:
1, the hypoxemia MHC alloy that utilizes the preparation method of hypoxemia MHC alloy provided by the invention to prepare, its oxygen level can be reduced to and be lower than 20ppm, oxygen level impurity is few in the alloy, prevented that the strengthening element hafnium from forming oxide compound, and the disperse that causes because of oxide particle is thick is inhomogeneous, defective such as easily cracks.
2, utilize the preparation method of hypoxemia MHC alloy provided by the invention to prepare the strengthening element hafnium carburet of hypoxemia MHC alloy inside after particle tiny, particle diameter is less than 1 μ m, disperse is even, strengthening effect is remarkable.
3, hypoxemia MHC alloy plasticity-brittle transition temperature of utilizing the preparation method of hypoxemia MHC alloy provided by the invention to prepare is low, and normal temperature toughness is strong, and workability is strong, the lumber recovery height, and production technique is simple, and cost is low.
4, the hypoxemia MHC alloy recrystallization temperature height that utilizes the preparation method of hypoxemia MHC alloy provided by the invention to prepare, excellent property and stable under the high temperature.
Embodiment
Embodiment a:
1) raw material is chosen
Get the industrial molybdenum powder that Fisher particle size is respectively 5 μ m, 7 μ m, 9 μ m, 11 μ m, 13 μ m, 15 μ m, 18 μ m, 24 μ m, 30 μ m, 40 μ m, 50 μ m, the hydrogenation hafnium powder of Fisher particle size 3 μ m～10 μ m, and Fisher particle size is 0.1 μ m～3 μ m carbon blacks.It is 1.20% that the hydrogenation hafnium powder adds quality, and the interpolation quality of carbon black powder is 0.15%, and all the other are molybdenum powder.Molybdenum powder after choosing, hydrogenation hafnium powder and carbon black powder are mixed.
2) material forming
The raw material that mixes through step 1) is carried out hydrostatic profile obtain blank under 220MPa～300MPa pressure, billet size is Φ 120mm * 130mm.
3) raw material sintering
In hydrogen shield atmosphere shaping blank is carried out sintering, sintering temperature is as shown in the table, and the billet size behind the sintering is Φ 100mm * 120mm.
4) blank behind the sintering is forged, forging the back sample size is Φ 230mm * 18mm.
Embodiment b:
1) raw material is chosen
Get the industrial molybdenum powder that Fisher particle size is respectively 5 μ m, 7 μ m, 9 μ m, 11 μ m, 13 μ m, 15 μ m, 18 μ m, 24 μ m, 30 μ m, 40 μ m, 50 μ m, the hydrogenation hafnium powder of Fisher particle size 3 μ m～10 μ m, and Fisher particle size is 0.1 μ m～3 μ m carbon blacks.It is 1.00% that the hydrogenation hafnium powder adds quality, and the interpolation quality of carbon black powder is 0.13%, and all the other are molybdenum powder.Molybdenum powder after choosing, hydrogenation hafnium powder and carbon black powder are mixed.
2) material forming
The raw material that mixes through step 1) is carried out hydrostatic profile obtain blank under 220MPa～300MPa pressure, billet size is Φ 120mm * 130mm.
3) raw material sintering
In hydrogen shield atmosphere shaping blank is carried out sintering, sintering temperature is as shown in the table, and the billet size behind the sintering is Φ 100mm * 120mm.
4) blank behind the sintering is forged, forging the back sample size is Φ 230mm * 18mm.
Embodiment c:
1) raw material is chosen
Get the industrial molybdenum powder that Fisher particle size is respectively 5 μ m, 7 μ m, 9 μ m, 11 μ m, 13 μ m, 15 μ m, 18 μ m, 24 μ m, 30 μ m, 40 μ m, 50 μ m, the hydrogenation hafnium powder of Fisher particle size 3 μ m～10 μ m, and Fisher particle size is 0.1 μ m～3 μ m carbon blacks.It is 0.62% that the hydrogenation hafnium powder adds quality, and the interpolation quality of carbon black powder is 0.10%, and all the other are molybdenum powder.Molybdenum powder after choosing, hydrogenation hafnium powder and carbon black powder are mixed.
2) material forming
The raw material that mixes through step 1) is carried out hydrostatic profile obtain blank under 220MPa～300MPa pressure, billet size is Φ 120mm * 130mm.
3) raw material sintering
In hydrogen shield atmosphere shaping blank is carried out sintering, sintering temperature is as shown in the table, and the billet size behind the sintering is Φ 100mm * 120mm.
4) blank behind the sintering is forged, forging the back sample size is Φ 230mm * 18mm.
Composition and performance to sample are tested, and test for tensile strength carries out under 1400 ℃.Testing data such as following table:
Annotate 1: the hardness value of sample is for forging back 1400 ℃ of hardness that timeliness recorded under the room temperature after 1 hour
Use the hypoxemia MHC alloy that preparation method provided by the invention prepares, can be used to process the bar that uses under X ray tube rotary anode target, compound x-ray target base material, high-temperature resistant container, hot forged mould, sintering high temperature ceramic backing and the hot conditions, sheet material, shaped piece etc.
Wherein, the X ray tube rotary anode target is mainly used in non-destructive testing apparatus such as medical CT examination device, luggage and articles inspection and metal, equipment flaw detection etc.For make inspection units can high output, high-definition, rotating anode target is just gradually to large scale development, general diameter even reaches about 260mm more than 100mm.
The hypoxemia MHC alloy oxygen level that the method for preparing hypoxemia MHC alloy provided by the invention is prepared can reach below the 20ppm, so discharge quantity is extremely low, and the lower limit indefinite of MHC alloy oxygen level, under the low more hot conditions of oxygen level in the use gas emit few more, high-temperature behavior is good more, can satisfy the working conditions of high temperature purposes members such as X ray tube rotary anode target, high-temperature crucibles, hot forged mould and sintering high temperature ceramic backing.
Claims (5)
1. the preparation method of a hypoxemia MHC alloy is characterized in that, may further comprise the steps:
1) raw material is chosen
Choosing Fisher particle size is the industrial molybdenum powder of 4 μ m～50 μ m, Fisher particle size is that hafnium powder, hydrogenation hafnium powder or the hafnium powder of 3 μ m～10 μ m mixes with the hydrogenation hafnium powder, Fisher particle size is the carbon simple substance powder of 0.1 μ m～3 μ m, described industrial molybdenum powder, hafnium powder or hydrogenation hafnium powder and carbon simple substance powder mixes are evenly formed mixing raw material, or mixture and the carbon simple substance powder mixes that industrial molybdenum powder, hafnium powder and hydrogenation hafnium powder are mixed and made into evenly formed mixing raw material; Described mixing raw material is by mass ratio, contains the mixture that 0.1%～2.0% hafnium powder, hydrogenation hafnium powder or hafnium powder and hydrogenation hafnium powder are mixed and made into, 0.01%～0.15% carbon containing simple substance powder and 97.85%～99.89% industrial molybdenum powder;
2) material forming
Mixing raw material is carried out static pressure or mold pressing processing, obtain shaping blank; It is 100MPa～300Mpa that the pressure of choosing is handled in described static pressure or mold pressing;
3) raw material sintering
In vacuum, hydrogen or inert gas environment shaping blank is carried out sintering, sintering temperature is 1800 ℃～2300 ℃, and sintering time is 5～15 hours, obtains hypoxemia MHC alloy after sintering is finished.
2. according to the preparation method of the described hypoxemia MHC of claim 1 alloy, it is characterized in that: described carbon simple substance powder is that carbon black, graphite or carbon dust are arbitrary or arbitrarily multiplely mix with arbitrary proportion.
3. according to the preparation method of claim 1 or 2 described hypoxemia MHC alloys, it is characterized in that: the Fisher particle size of described industrial molybdenum powder is 10 μ m～30 μ m.
4. according to the preparation method of the described hypoxemia MHC of claim 3 alloy, it is characterized in that: the pressure that described static pressure or mold pressing are handled is 220MPa～300Mpa.
5. a hypoxemia MHC alloy that uses the arbitrary described method preparation of claim 1-4 is used for the preparation of X ray tube rotary anode target, composition target base target, high-temperature crucibles, hot forged mould and pyroceramic pad.
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| CN105714169A (en) * | 2016-04-27 | 2016-06-29 | 西北有色金属研究院 | Mo-Si-B-Hf-Al alloy bar and preparation method thereof |
| CN106531599A (en) * | 2016-10-28 | 2017-03-22 | 安泰天龙钨钼科技有限公司 | Tungsten-rhenium-molybdenum alloy rotary anode target material for X-ray tube and preparation method thereof |
| CN109055843A (en) * | 2018-08-08 | 2018-12-21 | 金堆城钼业股份有限公司 | A kind of preparation method of molybdenum hafnium zirconium titanium carbon alloy |
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| CN111074126A (en) * | 2019-12-19 | 2020-04-28 | 厦门钨业股份有限公司 | Low-oxygen carbide reinforced tungsten alloy and preparation method thereof |
| CN113046618A (en) * | 2021-02-08 | 2021-06-29 | 北京理工大学重庆创新中心 | Method for preparing carbon simple substance in matrix or on surface |
| CN114523100A (en) * | 2022-03-08 | 2022-05-24 | 西北有色金属研究院 | High-pressure reduction preparation method of molybdenum-hafnium-carbon alloy powder containing hafnium hydride |
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| CN105714169A (en) * | 2016-04-27 | 2016-06-29 | 西北有色金属研究院 | Mo-Si-B-Hf-Al alloy bar and preparation method thereof |
| CN106531599A (en) * | 2016-10-28 | 2017-03-22 | 安泰天龙钨钼科技有限公司 | Tungsten-rhenium-molybdenum alloy rotary anode target material for X-ray tube and preparation method thereof |
| CN106531599B (en) * | 2016-10-28 | 2018-04-17 | 安泰天龙钨钼科技有限公司 | A kind of X-ray tube W-Re molybdenum alloy rotary anode target and preparation method thereof |
| CN109055843A (en) * | 2018-08-08 | 2018-12-21 | 金堆城钼业股份有限公司 | A kind of preparation method of molybdenum hafnium zirconium titanium carbon alloy |
| CN110157930A (en) * | 2019-06-03 | 2019-08-23 | 东睦新材料集团股份有限公司 | A kind of powder metallurgy alumina-base material and preparation method thereof |
| CN111041316A (en) * | 2019-12-18 | 2020-04-21 | 合肥工业大学 | High-strength Mo-Hf-CNT molybdenum-based composite material and preparation method thereof |
| CN111074126A (en) * | 2019-12-19 | 2020-04-28 | 厦门钨业股份有限公司 | Low-oxygen carbide reinforced tungsten alloy and preparation method thereof |
| CN113046618A (en) * | 2021-02-08 | 2021-06-29 | 北京理工大学重庆创新中心 | Method for preparing carbon simple substance in matrix or on surface |
| CN114523100A (en) * | 2022-03-08 | 2022-05-24 | 西北有色金属研究院 | High-pressure reduction preparation method of molybdenum-hafnium-carbon alloy powder containing hafnium hydride |
| CN114523100B (en) * | 2022-03-08 | 2022-10-28 | 西北有色金属研究院 | High-pressure reduction preparation method of molybdenum-hafnium-carbon alloy powder containing hafnium hydride |
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Application publication date: 20110504 |