CN101353735B - Method for preparing composite nanoparticle strongly toughened sintering molybdenum material - Google Patents
Method for preparing composite nanoparticle strongly toughened sintering molybdenum material Download PDFInfo
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- CN101353735B CN101353735B CN2008101431396A CN200810143139A CN101353735B CN 101353735 B CN101353735 B CN 101353735B CN 2008101431396 A CN2008101431396 A CN 2008101431396A CN 200810143139 A CN200810143139 A CN 200810143139A CN 101353735 B CN101353735 B CN 101353735B
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Abstract
The invention discloses a method for preparing compound nano particle tenacious sintering molybdenum material, which is characterized in that the strengthening and toughening phase of the molybdenum material is La2O3/Mo5Si3 compound nano particle, wherein, the Mo5Sio3 is added in the form of nano MoSi2, and the Mo5Si3 is generated by utilizing the in-situ reaction of MoSi2 and Mo under high temperature, while the La2O3 is added in the form of La2O3 nano particles. The preparation method related by the invention organically combines the low temperature toughening of rare earth oxide and the high temperature strengthening of the Mo5Si3, thus playing the double roles of toughening and strengthening, and effectively improving the high temperature resistance and the low temperature toughness of the molybdenum material.
Description
Technical field
The invention belongs to metallurgical technology field, relate to a kind of method for preparing composite nano microparticle strongly toughened sintering molybdenum material, be specifically related to a kind of preparation method of the copper alloy overflow mould of high heat conduction, low bulk that be used to prepare with composite nano microparticle strongly toughened sintering molybdenum material.
Background technology
The sintering molybdenum is as a kind of mmaterial of using in the high temperature engineering field, have characteristics such as fusing point height, density is moderate, thermal conductivity good, thermal expansivity is low, erosion resistance is superior, except boat and backing plate, also can be used as crucible, head piece and the electrode of glass melting, the thermoscreen of High Temperature Furnaces Heating Apparatus, the top of perforation stainless steel tube, nozzle, iron and steel die casting and the copper alloy extruding tool and mould etc. of rocket launcher as silicon controlled rectifier substrate, powder of uranium dioxide, pottery, rare earth magnet.Continuous development along with modern industry and science and technology, the Application Areas of sintering molybdenum also constantly enlarges, people have exceeded performance requriements required in existing or the conventional use in many aspects to its performance requirement, when pushing as the White Copper Tubes of extrusion temperature about 1200 ℃, common extruding mould steel will soon softening transform under this temperature, ceramic embedded material is as core rod in die steel, it is easy to crack to exist under the rapid heat cycle condition stupalith again, the problem that calibrating strap subsides, adopt the sintering molybdenum as tool and mould, require molybdenum not only to have good high-temperature intensity and low-temperature flexibility, but also has high thermal conductivity, thermostability and low thermal expansivity are really realized the structure-function integration of sintering Mo.But at present sintering molybdenum ubiquity resistance to elevated temperatures difference and embrittlement, the few quality of quantity is low, kind is incomplete yet, low, the many special-shaped specialty products of processed finished products rate are in great shortage and the very high shortcoming of cost.
For the high-performance Mo, successively develop carbide reinforced type molybdenum alloy (as TZM, Mo-0.5Ti, MHC and ZHC), solution strengthening-carbide reinforced type molybdenum alloy both at home and abroad (as M
25WH
1, M
25WH
2And M
25WZH
3), rare earth oxide intensified type molybdenum alloy (mixes La
2O
3, Sm
2O
3, Nd
2O
3, Tb
2O
3Deng), rare earth oxide-carbide multiple strengthening type molybdenum alloy and high temperature molybdenum (mixing elements such as Si, Al, K), and successfully molybdenum alloys such as TZM, ZHC, MHC are applied to push the tool and mould industry, this type of material still has higher heat resistance under the high temperature more than 1000 ℃.
Publication 200610162008.3 provides a kind of preparation method of reinforced molybdenum alloy, relate to TiC is strengthening phase, be used for copper and alloy thereof, ferrous metal die casting, insert and the molybdenum alloy of extrusion mould, publication 200610165737.4 provides a kind of method for preparing molybdenum-lanthanum alloy, relate to rare earth modified molybdenum alloy, European patent EP 080618A1 provides a kind of work in-process of the molybdenum alloy that contains intermetallic compound and the preparation method of finished product, intermetallic compound is preferably molybdenum silicide and silicon molybdenum boride, also can be molybdenum boride.
Above-mentioned patent does not all relate to and is used to prepare the preparation method of the copper alloy overflow mould of high heat conduction, low bulk with composite nano microparticle strongly toughened sintering molybdenum material.
Summary of the invention
Technical problem to be solved of the present invention is: a kind of method for preparing composite nano microparticle strongly toughened sintering molybdenum material is provided, prepared material is compared with sintering Mo in the past, when keeping high thermal conductivity and low bulk, its resistance to elevated temperatures and low-temperature flexibility effectively improve.
A kind of method for preparing composite nano microparticle strongly toughened sintering molybdenum material is characterized in that: may further comprise the steps:
1) preparation of molybdenum powder
With purity 99.8～99.9% MoO
2Powder reduces in 950～1100 ℃ and to obtain molybdenum powder under the protective atmosphere condition;
2) MoSi
2The preparation of powder
Molybdenum powder that step 1) is prepared and silica flour are by atomic ratio Mo:Si=1:(2～2.1) carry out thorough mixing, ball milling is prepared MoSi
2Powder;
3) La
2O
3/ MoSi
2The preparation of composite nanometre powder
With mass ratio is the MoSi of 1～1:1.5
2And La
2O
3The powder thorough mixing, ball milling is prepared the La that granularity is 60～80nm
2O
3/ MoSi
2Composite particles;
4) La
2O
3/ Mo
5Si
3The preparation of composite nano microparticle strongly toughened sintering molybdenum material
With La
2O
3/ MoSi
2Composite nanometre powder joins thorough mixing in the Mo powder, La
2O
3/ MoSi
2Composite nano particle be Mo quality 0.2%～2.0%; With the compacting of gained mixed powder, obtain the bar of Φ 15～55mm; Bar at 1800～1900 ℃ of sintering temperatures, is prepared La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material.
Protection gas in the described step 1) is hydrogen, and flow is 25～35dm
3Min
-1
Described step 2) the silica flour purity in is 99.8～99.9%, granularity 0～48 μ m.
Described step 2) the abrading-ball process in is: mixed powder is put into ball grinder, and ball-milling medium is a Stainless Steel Ball, and the Stainless Steel Ball specification is Φ 20mm and Φ 10mm, and its ratio is 1:(2～2.5), the weight ratio of Stainless Steel Ball and powder is (20～30): 1; Earlier ball grinder is vacuumized before the ball milling, feed argon gas then, to guarantee that mechanical milling process carries out all the time under argon shield, ball grinder seals with O type ring; Ball milling carries out in planetary ball mill, and rotating speed is 250～400r/min, and the ball milling time is 20～30 hours.
Abrading-ball process in the described step 3) is: mixed powder is put into ball grinder, ball-milling medium is a Stainless Steel Ball, the Stainless Steel Ball specification is Φ 20mm and Φ 10mm, its ratio is 1:(2～2.5), the weight ratio of Stainless Steel Ball and powder is (20～30): 1, ball milling carries out in planetary ball mill, and 25～35 hours ball milling time, rotating speed is 350～400r/min.
Pressing process in the described step 4) is: mixed powder is evenly packed in the rubber mold, suppress on cold isostatic press, pressing pressure is 180～300MPa, be 22～24min pressure rising time, dwell time is 7～9min, and the step-down time is 2～4min, obtains the bar of Φ 15～55mm.
In the described step 4), pass to hydrogen protection during the whole sintering, prevent that blank is oxidized.
The beneficial effect that the present invention had has:
La involved in the present invention
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material is that the low temperature malleableize of rare earth oxide and the High-Temperature Strengthening of three silication, five molybdenums are organically combined, and plays toughened and reinforced dual function, can improve the resistance to elevated temperatures and the low-temperature flexibility of Mo effectively.The prepared material of the present invention is compared with sintering Mo in the past, and when keeping high thermal conductivity and low bulk, its resistance to elevated temperatures and low-temperature flexibility effectively improve, and the over-all properties data of its material are seen embodiment 2～6.Overcome resistance to elevated temperatures difference that existing sintering Mo had and embrittlement, the few quality of quantity is low, low, the many special-shaped specialty products of processed finished products rate are in great shortage, the very high shortcoming of cost.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1: the preparation method of composite nano microparticle strongly toughened sintering molybdenum material mainly comprises:
1) preparation of molybdenum powder
With purity 99.9% MoO
2Powder reduces in 950～1100 ℃ under hydrogen shield, and the recovery time is 90～120min, and hydrogen flowing quantity is 30dm
3Min
-1
2) MoSi
2The preparation of powder
Molybdenum powder that step 1) is prepared and purity are 99.9%, granularity is carried out thorough mixing less than the silica flour of 48 μ m by atomic ratio Mo:Si=1:2, then the powder that mixes is put into stainless cylinder of steel and carry out ball milling, ball-milling medium is a Stainless Steel Ball, the Stainless Steel Ball specification is Φ 20mm and Φ 10mm, its ratio is 1:2, and the weight ratio of Stainless Steel Ball and powder is 20:1.Earlier ball grinder is vacuumized before the ball milling, feed the argon gas of certain pressure then, to guarantee that mechanical milling process carries out all the time under argon shield, ball grinder seals with O type ring.Ball milling carries out in planetary ball mill, and rotating speed is 390r/min, and ball milling was prepared MoSi after 24 hours
2Powder.
3) La
2O
3/ MoSi
2The preparation of composite nanometre powder
With mass ratio is the MoSi of 1:1
2And La
2O
3(analytical pure) powder thorough mixing is then with the powder that mixes set by step 2) condition put into the planetary ball mill ball milling 30 hours, the weight ratio of Stainless Steel Ball and powder is 20:1, rotating speed is 390r/min, prepares the La that granularity is 60～80nm
2O
3/ MoSi
2Composite particles.
4) La
2O
3/ Mo
5Si
3The preparation of composite nano microparticle strongly toughened sintering molybdenum material
The La that step 3) is made
2O
3/ MoSi
2Composite nanometre powder joins in the Mo powder, La
2O
3/ MoSi
2Composite nano particle be Mo quality 0.2%～2.0%.With conical mixer under normal pressure with mixed powder thorough mixing 10 hours.Powder after mixing is evenly packed in the rubber mold, suppresses on cold isostatic press, and pressing pressure is 200MPa, and be 22～24min pressure rising time, and the dwell time is 7～9min, and the step-down time is 2～4min, obtains the bar of Φ 17mm.The bar that suppresses is carried out sintering in intermediate frequency furnace, sintering temperature is 1840 ℃, is incubated 5～8 hours, prepares La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material passes to hydrogen protection during the whole sintering, prevents that blank is oxidized.
Embodiment 2
Prepare molybdenum powder by the step 1) described in " embodiment 2 ", with step 2) in ratio of grinding media to material be decided to be 20:1, rotating speed is decided to be 390r/min, prepares MoSi
2Powder, set by step 3) prepare La
2O
3/ MoSi
2Composite nano particle is with the La in the step 4)
2O
3/ MoSi
2Composite nano particle be decided to be Mo quality 0.5%, be incubated 7 hours, prepare La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material, its over-all properties data are as shown in table 1.
Table 1 present embodiment material property data
Embodiment 3
Prepare molybdenum powder by the step 1) described in " embodiment 2 ", with step 2) in ratio of grinding media to material be decided to be 20:1, rotating speed is decided to be 390r/min, prepares MoSi
2Powder, set by step 3) prepare La
2O
3/ MoSi
2Composite nano particle is with the La in the step 4)
2O
3/ MoSi
2Composite nano particle be decided to be Mo quality 0.5%, be incubated 5 hours, prepare La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material, its over-all properties data are as shown in table 2.
Table 2 present embodiment material property data
Embodiment 4
Prepare molybdenum powder by the step 1) described in " embodiment 2 ", with step 2) in ratio of grinding media to material be decided to be 20:1, rotating speed is decided to be 390r/min, prepares MoSi
2Powder, set by step 3) prepare La
2O
3/ MoSi
2Composite nano particle is with the La in the step 4)
2O
3/ MoSi
2Composite nano particle be decided to be Mo quality 1.0%, be incubated 7 hours, prepare La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material, its over-all properties data are as shown in table 3.
Table 3 present embodiment material property data
Embodiment 5
Prepare molybdenum powder by the step 1) described in " embodiment 2 ", with step 2) in ratio of grinding media to material be decided to be 30:1, rotating speed is decided to be 390r/min, prepares MoSi
2Powder, set by step 3) prepare La
2O
3/ MoSi
2Composite nano particle is with the La in the step 4)
2O
3/ MoSi
2Composite nano particle be Mo quality 0.5%, be incubated 7 hours, prepare La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material, its over-all properties data are as shown in table 4.
Table 4 present embodiment material property data
Embodiment 6
Prepare molybdenum powder by the step 1) described in " summary of the invention ", with step 2) in ratio of grinding media to material be decided to be 20:1, rotating speed is decided to be 270r/min, prepares MoSi
2Powder, set by step 3) prepare La
2O
3/ MoSi
2Composite nano particle is with the La in the step 4)
2O
3/ MoSi
2Composite nano particle be decided to be Mo quality 0.5%, be incubated 7 hours, prepare La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material, its over-all properties data are as shown in table 5.
Table 5 present embodiment material property data
Claims (6)
1. method for preparing composite nano microparticle strongly toughened sintering molybdenum material is characterized in that: may further comprise the steps:
1) preparation of molybdenum powder
With purity 99.8～99.9% MoO
2Powder reduces in 950～1100 ℃ and to obtain molybdenum powder under the protective atmosphere condition;
2) MoSi
2The preparation of powder
Molybdenum powder that step 1) is prepared and silica flour are by atomic ratio Mo: Si=1: (2～2.1) carry out thorough mixing, and ball milling is prepared MoSi
2Powder; Silica flour purity is 99.8～99.9%, granularity 0～48 μ m;
3) La
2O
3/ MoSi
2The preparation of composite nanometre powder
With mass ratio 1: 1～1: 1.5 MoSi
2And La
2O
3The powder thorough mixing, ball milling is prepared the La that granularity is 60～80nm
2O
3/ MoSi
2Composite particles;
4) La
2O
3/ Mo
5Si
3The preparation of composite nano microparticle strongly toughened sintering molybdenum material
With La
2O
3/ MoSi
2Composite nanometre powder joins thorough mixing in the Mo powder, La
2O
3/ MoSi
2Composite nano particle be Mo quality 0.2%～2.0%; With the compacting of gained mixed powder, obtain the bar of Φ 15～55mm; Bar at 1800～1900 ℃ of sintering temperatures, is prepared La
2O
3/ Mo
5Si
3Composite nano microparticle strongly toughened sintering molybdenum material.
2. the method for preparing composite nano microparticle strongly toughened sintering molybdenum material as claimed in claim 1 is characterized in that: the protective atmosphere in the described step 1) is a hydrogen atmosphere, and flow is 25～35dm
3Min
-1
3. the method for preparing composite nano microparticle strongly toughened sintering molybdenum material as claimed in claim 1, it is characterized in that: the mechanical milling process described step 2) is: mixed powder is put into ball grinder, ball-milling medium is a Stainless Steel Ball, the Stainless Steel Ball specification is Φ 20mm and Φ 10mm, its ratio is 1: (2～2.5), the weight ratio of Stainless Steel Ball and powder are (20～30): 1; Earlier ball grinder is vacuumized before the ball milling, feed argon gas then, to guarantee that mechanical milling process carries out all the time under argon shield, ball grinder seals with O type ring; Ball milling carries out in planetary ball mill, and rotating speed is 250～400r/min, and the ball milling time is 20～30 hours.
4. the method for preparing composite nano microparticle strongly toughened sintering molybdenum material as claimed in claim 1, it is characterized in that: the mechanical milling process in the described step 3) is: mixed powder is put into ball grinder, ball-milling medium is a Stainless Steel Ball, the Stainless Steel Ball specification is Φ 20mm and Φ 10mm, its ratio is 1: (2～2.5), the weight ratio of Stainless Steel Ball and powder are (20～30): 1, and ball milling carries out in planetary ball mill, 25～35 hours ball milling time, rotating speed is 350～400r/min.
5. the method for preparing composite nano microparticle strongly toughened sintering molybdenum material as claimed in claim 1, it is characterized in that: the pressing process in the described step 4) is: mixed powder is evenly packed in the rubber mold, on cold isostatic press, suppress, pressing pressure is 180～300MPa, be 22～24min pressure rising time, dwell time is 7～9min, and the step-down time is 2～4min, obtains the bar of Φ 15～55mm.
6. as each described method for preparing composite nano microparticle strongly toughened sintering molybdenum material of claim 1～5, it is characterized in that: in the described step 4), pass to hydrogen protection during the whole sintering, prevent that blank is oxidized.
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|---|---|---|---|
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| CN101353735B true CN101353735B (en) | 2011-08-03 |
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| CN101935793A (en) * | 2010-10-13 | 2011-01-05 | 中南大学 | High-strength Mo-doped sheet and preparation method thereof |
| CN102274969B (en) * | 2011-07-07 | 2013-03-13 | 西安交通大学 | Preparation method of molybdenum alloy electrode material doped with nano rare earth oxides |
| CN105887029A (en) * | 2016-06-26 | 2016-08-24 | 苏州思创源博电子科技有限公司 | Preparation method of molybdenum alloy plate with hard nitrogen-yttrium-zirconium coating |
| CN108975918A (en) * | 2018-08-13 | 2018-12-11 | 四川大学 | A kind of high tenacity high-temperature structural material MoSi2-Mo5Si3The preparation of composite ceramics |
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Non-Patent Citations (1)
| Title |
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| 程仕平.中南大学博士学位论文.《高性能钼粉与烧结钼的制备及机理研究》.2007,13-17. * |
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Application publication date: 20090128 Assignee: Jiangsu Star Limited company of tungsten and molybdenum Assignor: Central South University Contract record no.: 2013320000434 Denomination of invention: Method for preparing composite nanoparticle strongly toughened sintering molybdenum material Granted publication date: 20110803 License type: Exclusive License Record date: 20130520 |
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