CN1296503C - Molybdenum-base alloy and its preparing method - Google Patents
Molybdenum-base alloy and its preparing method Download PDFInfo
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- CN1296503C CN1296503C CNB2005100725897A CN200510072589A CN1296503C CN 1296503 C CN1296503 C CN 1296503C CN B2005100725897 A CNB2005100725897 A CN B2005100725897A CN 200510072589 A CN200510072589 A CN 200510072589A CN 1296503 C CN1296503 C CN 1296503C
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- molybdenum
- base alloy
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Abstract
The present invention relates to a Mo-base alloy and a preparing method thereof. The Mo-base alloy comprises the components of the following weight ratio: 0.1% to 0.8% of zirconium hydride, 0.1% to 0.8% of carbon, 0.4% to 2.2% of titanium carbide whose particle size is smaller than 0.6 micrometers, 0.5% to 2.5% of rare earth oxide whose particle size is smaller than 40 nanometers, and Mo as the rest. The Mo-base alloy is prepared from the components by the procedures of homogenization, press and sintering. The Mo-base alloy can be used to strengthen a solid solution to form a dispersed carbide phase and improve the bonding strength of the crystal lattices of the solid solution.
Description
Technical field:
The present invention relates to a kind of molybdenum base alloy composition and prepare the method for said composition, particularly be suitable for occasion uses such as the axle top of pipe-mill and rare-earth smelting industry crucible molybdenum base alloy composition and prepare the method for said composition.
Background technology:
To the detection data presentation of pure molybdenum, the intensity δ B=40kg/mm of pure polonium in the time of 20 ℃
2About, the intensity in the time of 1000 ℃ is 7kg/mm
2, and the intensity in the time of 2000 ℃ only is 1.2kg/mm
2So,, pure molybdenum does not have hot strength and unique physicals such as anti-oxidant.But molybdenum is a kind ofly can keep the hot strength of its alloy and the metal of corrosion resistance nature, to be molybdenum with the form of alloy exist can possess unique physicals, for example, just can under severe environment, work with molybdenum alloy parts such as employed axle top and crucible on the molybdenum alloy making pipe-mill.
The technology of multiple composition about molybdenum alloy and preparation method thereof was once proposed in the prior art.As " a kind of method for preparing hypoxemia TZM molybdenum alloy bar base " of No. 1540017, Chinese patent bulletin with regard to an example.Adopting high-carbon molybdenum powder and titanium hydride and zircoium hydride in this method is raw material, makes the molybdenum alloy bar base through mixing and sintering.Its meaning is to make reductor with carbon, and generates CO (carbon monoxide converter) gas, simultaneously, and the recrystallization temperature of the hot strength of the zr element raising molybdenum of utilization trace and the titanium raising molybdenum of trace.To have a cost low though this kind molybdenum alloy is compared with the as cast condition molybdenum alloy, the simple relative advantages of higher of technology with the life-span, but, prepare this alloy and when batching, must control the content of carbon, because of can making the plasticity of molybdenum alloy and toughness, reduces the molybdenum carbide that is generated behind excessive carbon and the molybdenum chemical combination, and fragility strengthens, and problem such as be full of cracks occurs; In addition, because hydrogen that titanium hydride and zircoium hydride are deviate from when carbonization and the remaining more water of oxygen reaction generation, water meeting obstruction crystal boundary in exclusion process moves and forms hole, and then influences the work-ing life of molybdenum alloy.
In addition, Chinese patent also discloses the technology that name is called " a kind of preparation method of dipping molybdenum alloy " for No. 1083900.This method is to utilize molybdenum ammonium solution and rare earths salt uniform mixing to produce the doping ammonium paramolybdate earlier, then doped molybdenum is made in the ammonium paramolybdate reduction, is processed into various goods through moulding and sintering circuit again.Obviously, what this technology adopted is that liquid-liquid doping method is produced molybdenum alloy powder, so that rare earth element can be evenly distributed in the molybdenum forming composite oxides, thereby improves the comprehensive mechanical property of molybdenum materials effectively.But this kind method prepares molybdenum base alloy with powder metallurgic method and compares certain difference in addition.
Particularly, the active ingredient of being added in molybdenum base alloy only accounts for about 3% of its gross weight, and active ingredient wants and molybdenum powder thorough mixing equably, and its particle diameter is an important parameters, and this parameter has determined concentration and other character of impurity on molybdenum base alloy unit's crystal boundary face.If the particle diameter of active ingredient is excessive, the concentration of impurity will increase on the unit crystal boundary face, and contains elements such as the oxygen of atomic state and carbon poly-partially on crystal boundary in the impurity, and the trend of transgranular fracture increases, and causes the intensity of alloy and other performances to reduce; Simultaneously, particle diameter can also influence intermolecular diffusion greatly, makes its alloying fully in sintering process, and has bigger pore in alloy substrate, and then is prone to crackle, seriously influences its work-ing life.
Summary of the invention:
Task of the present invention provides a kind of molybdenum base alloy, and this alloy utilizes the linkage force problem of micron and nanotechnology solution crystal boundary face impurity concentration and intergranule, to improve its hardness and intensity and to increase plasticity.
Another task of the present invention provides a kind of method for preparing above-mentioned molybdenum base alloy.
Component that molybdenum base alloy adopted and weight percent proposed by the invention are: zircoium hydride, carbon, particle are respectively 0.1%-0.8%, 0.1%-0.8%, 0.4%-2.2% less than the titanium carbide below 0.6 micron, with particle be less than the rare earth oxide 0.5%-2.5% below 40 nanometers, its surplus is a molybdenum.After adding rare earth oxide, rare earth element and oxygen reaction back generate multiple double oxide, when having fixed oxygen, also changed the form that crystal boundary impurity exists, made can not produce more water in the alloy and hinder moving of crystal boundary, and then also can not occur the large size hole in the alloy; Simultaneously, exist because titanium finally is form with titanium carbide in alloy, and titanium carbide can improve the wear resistance and the recrystallization temperature of molybdenum alloy, directly add the superfine titanium carbide among the present invention to avoid in the certain embodiments carbon content not enough or generate dimolybdenum carbide; In addition, because there are a large amount of interfaces in micron-sized titanium carbide and nano level rare earth oxide in structured material, and these interfaces provide the approach of short-range diffusion for atom, this high diffusivity makes molybdenum base alloy have unique surface effects, volume effect and quantum size effect, but be distributed in to disperse in the molybdenum matrix, can further improve hardness, intensity, density and the high-temperature behavior of molybdenum base alloy.
Described rare earth oxide can be made of cerium oxide or yttrium oxide or the mixture of the two, and when it was the mixture of the two, its weight percent was cerium oxide 0.3%-1.5%, yttrium oxide 0.2%--1.0%.Wherein, adding cerium oxide, can to suppress alloy grain long thick and assemble, and impurity concentration reduces on the unit's of making crystal boundary face, and hardness of alloy, intensity and plasticity increase, and add yttrium oxide in alloy mainly with Zr
0.4Ce
0.6O
2, Zr
3Y
4O
12Form Deng double oxide exists, and can promote the forming core of carbide to grow up, and improves the linkage force of intergranule, plays the effect that purifies crystal boundary, has particularly fixed oxygen, avoids occurring in the alloy more large size hole.
Described rare earth oxide can be made of cerium oxide or yttrium oxide or lanthanum trioxide or three's mixture, when it was three's mixture, cerium oxide, yttrium oxide, lanthanum trioxide three's weight percent was respectively 0.3%--1.2%, 0.2%--1.0%, 0%--0.3%.
The component of this molybdenum base alloy and weight percent are: the titanium carbide that zircoium hydride, carbon, particle are 0.1 to 0.6 micron is respectively 0.2%-0.6%, 0.1%-0.6%, 0.5%-2.0%, with particle be the cerium oxide 0.5%-1.5% of 10 to 40 nanometers, yttrium oxide 0.3%-0.8%, its surplus is a molybdenum.
Be used to prepare the method for above-mentioned molybdenum base alloy, may further comprise the steps:
Homogeneous: zircoium hydride, carbon dust and micron-sized titanium carbide and nano level rare earth oxide predetermined amounts are joined in the molybdenum powder matrix, and then all materials are put into the mixer thorough mixing;
Compacting: pack into the mixture of the predetermined amount behind the above-mentioned homogeneous in the gum cover and put into isostatic pressing machine together with gum cover and suppress, its force value keeps taking out at least 4 minutes between 180 to 220 MPas suppresses workpiece;
Sintering: the workpiece after will suppressing is inserted sintering in vacuum intermediate frequency furnace or the hydrogen furnace, and its sintering temperature rises between 1900 ℃ to 2000 ℃ gradually and kept 3-4 hour.
Also comprise in the described homogenizing step zircoium hydride, carbon dust, micron-sized titanium carbide and nano level rare earth oxide are taken out predetermined amount, and then 2 times the molybdenum powder that takes out its gross weight carries out just mixing, in the material adding molybdenum powder matrix after will just mixing more at last.
The molybdenum base alloy that the present invention proposes adds the nano-scale rare earth element and can strengthen sosoloid, makes it form the dispersing carbide phase, has improved the linkage force of solid solution crystals lattices.Through to this molybdenum base alloy finished product detection, its density d 〉=9.3g/cm
3, hardness HB200-230Kg/mm
2, tensile strength δ
b〉=25Kg/mm
2(1100 ℃), the top of wearing steel tube place's consumption with the molybdenum plug of this molybdenum base alloy making is dropped to below the 0.30Kg/T by original 0.50Kg/T, and only this item just can obtain the up to ten million units of economic benefit.
Embodiment:
Embodiment 1, gets TiC powder 0.65kg, ZrH
2Powder 0.15kg, CeC
2Powder 0.5kg, Y
2O
3Powder 0.25kg, C powder 0.2kg, Mo powder 3.5kg sieve after stirring with material shovel in Stainless Steel Disc, and the little V-type blender of packing into mixed 90 minutes.Addition material after getting Mo powder 44.75kg and just mixing places mixer to mix 36 hours.To the alloy powder multidraw analysis that makes, the segregation-free phenomenon then adopts manual charging.Pack into after molybdenum alloy powder weighed in the product gum cover of top, carry out isostatic pressing after the tamping sealing.Pressing pressure 200Mpa, pressurize 5 minutes.With the rolled-up stock that density is up to the standards, be lathed the top blank of certain taper shape.2000 ℃ of vacuum intermediate frequency sintering are incubated 3 hours, obtain the molybdenum plug product of pierced billet steel alloy, stainless steel seamless pipe.
Embodiment 2: get TiH
2Powder 0.35kg, ZrH
2Powder 0.1kg, CeC
2Powder 0.25kg, Y
2O
3Powder 0.2kg, C powder 0.1kg, Mo powder 2kg give in blender and mixing 80 minutes, get Mo powder 47kg and give the blended addition material, place mixer to mix 32 hours.Behind the sampling analysis segregation-free, molybdenum alloy powder weighed pack in crucible or the electrode product gum cover, carry out isostatic pressing, pressing pressure 180Mpa, pressurize 3 minutes.1980 ℃ of turning pressed compact spare final vacuum intermediate frequency sintering are incubated 4 hours, make molybdenum alloy crucible or electrode product.
Claims (6)
1, a kind of molybdenum base alloy, it is characterized in that: the component of this molybdenum base alloy and weight percent are: zircoium hydride, carbon, particle are respectively 0.1%-0.8%, 0.1%-0.8%, 0.4%-2.2% less than the titanium carbide below 0.6 micron, with particle less than the rare earth oxide 0.5%-2.5% below 40 nanometers, its surplus is a molybdenum.
2, molybdenum base alloy according to claim 1, it is characterized in that: described rare earth oxide can be made of cerium oxide or yttrium oxide or the mixture of the two, when it was the mixture of the two, its weight percent was cerium oxide 0.3%-1.5%, yttrium oxide 0.2%-1.0%.
3, molybdenum base alloy according to claim 1, it is characterized in that: described rare earth oxide can be made of cerium oxide or yttrium oxide or lanthanum trioxide or three's mixture, when it was three's mixture, cerium oxide, yttrium oxide, lanthanum trioxide three's weight percent was respectively 0.3%-1.2%, 0.2%-1.0%, 0%-0.3%.
4, molybdenum base alloy according to claim 1, it is characterized in that: the component of this molybdenum base alloy and weight percent are: the titanium carbide that zircoium hydride, carbon, particle are 0.1 to 0.6 micron is respectively 0.2%-0.6%, 0.1%-0.6%, 0.5%-2.0%, with particle be the cerium oxide 0.5%-1.5% of 10 to 40 nanometers, yttrium oxide 0.3%-0.8%, its surplus is a molybdenum.
5, the method for preparing molybdenum base alloy described in the claim 1 is characterized in that this method may further comprise the steps:
Homogeneous: zircoium hydride, carbon dust and micron-sized titanium carbide and nano level rare earth oxide predetermined amounts are joined in the molybdenum powder matrix, and then all materials are put into the mixer thorough mixing;
Compacting: pack into the mixture of the predetermined amount behind the above-mentioned homogeneous in the gum cover and put into isostatic pressing machine together with gum cover and suppress, its force value is between 180 to 220 MPas and keep taking out at least 4 minutes the compacting workpiece;
Sintering: the workpiece after will suppressing is inserted sintering in vacuum intermediate frequency furnace or the hydrogen furnace, and its sintering temperature rises between 1900 ℃ to 2000 ℃ gradually and kept 3-4 hour.
6, method according to claim 5, it is characterized in that: also comprise in the described homogenizing step zircoium hydride, carbon dust, micron-sized titanium carbide and nano level rare earth oxide are taken out predetermined amount, and then 2 times the molybdenum powder that takes out its gross weight carries out just mixing, in the material adding molybdenum powder matrix after will just mixing more at last.
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| CNB2005100725897A CN1296503C (en) | 2005-05-15 | 2005-05-15 | Molybdenum-base alloy and its preparing method |
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| CNB2005100725897A CN1296503C (en) | 2005-05-15 | 2005-05-15 | Molybdenum-base alloy and its preparing method |
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| CN1296503C true CN1296503C (en) | 2007-01-24 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7860220B2 (en) * | 2005-10-27 | 2010-12-28 | Kabushiki Kaisha Toshiba | Molybdenum alloy; and X-ray tube rotary anode target, X-ray tube and melting crucible using the same |
| CN101423911B (en) * | 2007-10-29 | 2011-09-07 | 四平市北威钼业有限公司 | Manufacturing technology of molybdenum-based rare-earth alloy slab and equipment thereof |
| CN101397617B (en) * | 2008-10-28 | 2010-11-24 | 西安交通大学 | Method for preparing alloy nano rare-earth oxide doping molybdenum-silicium-boron alloy |
| CN102218535B (en) * | 2011-07-14 | 2014-05-14 | 金堆城钼业股份有限公司 | Sintering method for molybdenum product |
| CN103121104A (en) * | 2011-11-21 | 2013-05-29 | 高殿斌 | Production method used for vacuum crystallization furnace heat preservation assembly materials |
| CN102990054B (en) * | 2012-04-01 | 2016-05-25 | 鹤山市沃得钨钼实业有限公司 | Rare earth molybdenum crucible blank and utilize this blank to manufacture the method for rare earth molybdenum crucible |
| CN103170621B (en) * | 2013-03-26 | 2014-12-24 | 金堆城钼业股份有限公司 | Preparation method of large molybdenum rod blank |
| CN103320634B (en) * | 2013-06-08 | 2015-07-29 | 金堆城钼业股份有限公司 | A kind of preparation method of TZM alloy material |
| CN103386487B (en) * | 2013-08-16 | 2016-07-06 | 苏州艾默特材料技术有限公司 | A kind of preparation method of carbide reinforced molybdenum alloy |
| CN103421969B (en) * | 2013-09-06 | 2015-04-15 | 金堆城钼业股份有限公司 | Preparation method of molybdenum alloys for isothermal forging die |
| CN104525948B (en) * | 2014-12-23 | 2017-03-15 | 金堆城钼业股份有限公司 | A kind of preparation method of molybdenum alloy electrode |
| CN107099716B (en) * | 2017-03-02 | 2019-01-08 | 中广核研究院有限公司 | Interface enhancing molybdenum alloy and preparation method thereof |
| CN109852917B (en) * | 2019-01-31 | 2021-04-13 | 航天材料及工艺研究所 | Vacuum plasma spraying forming preparation method of molybdenum titanium zirconium member on surface of C/C, C/SiC composite material |
| CN110184519B (en) * | 2019-06-10 | 2020-03-24 | 中国兵器工业第五九研究所 | Preparation method of large-diameter special-shaped thin-wall tubular molybdenum-based alloy part |
| CN114951639B (en) * | 2022-05-10 | 2023-11-14 | 厦门虹鹭钨钼工业有限公司 | High-density fine-grain structure molybdenum alloy plug and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4952705A (en) * | 1972-09-22 | 1974-05-22 | ||
| CN1540017A (en) * | 2003-10-29 | 2004-10-27 | 西部金属材料股份有限公司 | Method for preparing rod billets of mionectic T2M molybdenum alloy |
-
2005
- 2005-05-15 CN CNB2005100725897A patent/CN1296503C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4952705A (en) * | 1972-09-22 | 1974-05-22 | ||
| CN1540017A (en) * | 2003-10-29 | 2004-10-27 | 西部金属材料股份有限公司 | Method for preparing rod billets of mionectic T2M molybdenum alloy |
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