CN102768891B - The product of the nitrogenous magnetic preparation technology of rare earth and equipment and preparation - Google Patents
The product of the nitrogenous magnetic preparation technology of rare earth and equipment and preparation Download PDFInfo
- Publication number
- CN102768891B CN102768891B CN201110116325.2A CN201110116325A CN102768891B CN 102768891 B CN102768891 B CN 102768891B CN 201110116325 A CN201110116325 A CN 201110116325A CN 102768891 B CN102768891 B CN 102768891B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- boiler tube
- nitrogenous
- magnetic
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Hard Magnetic Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
A kind of nitrogenous magnetic preparation technology of rare earth and equipment, this equipment is made up of boiler tube (5), heating furnace (6), vacuum system (2), cooling system (3) and air supply system (1), and wherein equipment boiler tube (5) is built with lapping device (4).Quick-fried for the hydrogen of rare earth alloy process, nitrogen treatment, ball-milling treatment three critical processes concentrate in an equipment and carry out by this technique, can effectively suppress oxidation, technological process is short, efficiency is high, obtain magnetic particle capability excellent and stable.
Description
Technical field
The present invention relates to the nitrogenous magnetic one-step preparation process of rare earth and equipment thereof, and the nitrogenous magnetic of rare earth adopting this technique to prepare, belong to rare-earth magnetic functional material and preparing technical field thereof.
Background technology
Binding rare earth permanent magnet is combined by rare earth permanent-magnet powder and binding material to form, and directly injects or the various permanent magnet devices of compression molding by user's requirement.Such magnet has that dimensional accuracy is high, magnetic uniformity is good, corrosion resistance is good, rate of finished products is high, be easily processed into the advantages such as complex-shaped device, is widely used in the devices such as household electrical appliances, electrical micro-machine, automated office equipment, instrument and meter, medical device, automobile, magnetic machinery and equipment.
The key preparing bonded rare earth permanent magnetic is exactly the preparation of rare earth permanent magnet powder, and the performance of magnetic directly determines quality and the market price of bonded permanent magnet.At present, bonded rare earth permanent magnetic powder mainly comprises MQ isotropism magnetic, HDDR anisotropic powders, Th
2zn
17n
xtype anisotropic powders, TbCu
7n
xtype isotropism powder, ThMn
12n
xtype anisotropic powders, binding rare earth permanent magnet ripe on market is essentially isotropic NdFeB Bonded Magnets.In recent years, along with the development of electric motor car, wind power generation, magnetic suspension train, the serviceability temperature of rare-earth permanent magnet is had higher requirement, bonding rare earth iron boron series magnet corrosion resistance and non-oxidizability poor, and its Curie temperature is lower limits its high-temperature applications.
Research finds, interstitial atom (C, N, H) enters into rare-earth iron compound can produce larger impact to its performance, is called interstitial atom effects.Interstitial atom effects can improve the Curie temperature of compound, saturation magnetization and anisotropy field.Peking University poplar should prosperous academician patent CN90109166.9, the 92103831.3 inventions rare earth Fe-N compound R of high-curie temperature
2fe
17n
x, R
2fe
14bN
ywith R (Fe, M)
12n
zpoint out that the magnetic that this compound obtains has the advantages that corrosion resistance is high, oxidation resistance is strong, but preparation technology is long, be difficult to industrialization, Powder Oxidation wherein in preparation process, the soft magnetism phase a-Fe in the uniformity of nitrogenize, the granularity of magnetic and magnetic and Nd-rich phase are the principal elements affecting final magnetic particle capability.
Based on the problems referred to above, author has carefully studied the preparation technology of rare earth Fe-N bonding magnetic.The patent CN02159665.4 of University of Science & Technology, Beijing's application and CN03150162.1, its Patent CN02159665.4 provide a kind of method adopting vat blue RS to manufacture Sm-Fe-N permanent magnetic alloy powder.Patent CN03150162.1 provides a kind of method that Sm-Fe-N permanent magnetic material is prepared in mechanical alloying; Patent 91103836.1 and 93107808.3 each provide a kind of hydrogenation add nitrogenize method preparation (R1-xR ' x)
2(Fe1-yMy)
17n
δ; Beijing three ring patent 91110811.4 and 91110908.0 adopts the method for rapid shaping and powder metallurgy to prepare R
2(Fe1-yMy)
17x
3-δpermanent magnet.The patent CN01123172.6 that Daido Steel Co., Ltd of Japan applies in China, patent US2004144450 at U. S. application and the patent JP2004063666 in Japanese publication, JP2003173907, JP2002057017 disclose the resin-bonded magnet isotropism SmFeN powder magnet material of a kind of production, composition is SmxFe100-x-vNv, SmxFe100-x-v-yM
1yNv, SmxFe100-x-v-zM
2zNv, crystal structure is TbCu7 type, and the thickness of thin slice is 10-40um, by melt spinning molten alloy the direct nitriding in nitrogenous gas of the alloyed powder of such gained is prepared magnet powder.Sumitomo Metal Industries mine patent JP7288205, JP6188110, JP2008171868, JP2008024979, JP2007327101 etc. disclose reduction-diffusion process and prepare Sm-Fe-N magnetic, and stability, squareness, earning rate improvement etc.
Above rare earth nitrogenous magnetic preparation method mainly comprises following step: 1. the preparation of foundry alloy; 2. annealing or Crystallizing treatment; 3. the quick-fried or HDDR process of hydrogen; 4. nitrogen treatment; 5. ball-milling treatment.This preparation technology owing to carrying out in distinct device, and need to repeat to vacuumize, change and prepare environment etc., the cycle is long, efficiency of nitridation is low, magnetic oxygen content is high, prepare magnetic particle capability instability, is not suitable for mass industrialized production.The present invention proposes that a kind of technological process is short, cost is low, efficiency is high on this basis, is applicable to preparation low, that magnetic property the is high rare earth nitrogenous magnetic one-step preparation process of suitability for industrialized production oxygen content and equipment used thereof.
Summary of the invention
Primary and foremost purpose of the present invention is to provide the equipment that the nitrogenous magnetic one-step preparation process of a kind of rare earth uses.
Second object of the present invention is to provide that a kind of technological process is short, cost is low, efficiency is high, is applicable to the one-step preparation process of the nitrogenous magnetic of preparation low, that magnetic property the is high rare earth of suitability for industrialized production oxygen content.
3rd object of the present invention is to provide the nitrogenous magnetic of rare earth prepared by above-mentioned one-step technology.
To achieve these goals, the present invention takes following technical scheme:
A kind of equipment that the one-step preparation process of the nitrogenous magnetic of rare earth of the present invention uses, is equipped with the boiler tube 5 of the driven rotation of lapping device 4, heating furnace 6, vacuum system 2, cooling system 3 and air supply system 1 and forms by inside.
Wherein, described heating furnace 6 and its built with heater and heating power supply composition heating system; Vacuum system 2 is connected with boiler tube 5; Air supply system 1 is connected with boiler tube 5; Boiler tube 5 is positioned among heating furnace 6, and water-cooling system 3 is positioned at the bottom of heating furnace 6.
Cooling system 3 adopts water-cooling pattern, can be made up of a row to the water pipe spraying running water.
Described lapping device 4 is one or more in stainless steel, pottery, agate material.
Described lapping device 4 is spherical or clavate.
In the said equipment, the semicircular structure that heating furnace is equipped with heater respectively by two inner sides forms, these two semicircular structures can close up when heating boiler tube 5 is enclosed within centre as required, can separately be exposed by boiler tube, so that boiler tube cools fast when cooling.
In the said equipment, the described rotatable boiler tube 5 with lapping device 4 is driven by motor and rotates, and its rotary speed is at 0-200r/min continuously adjustabe, and rotary speed ≠ 0.Wherein, boiler tube 5 is rotatable, and its rotary speed is at 1-100r/min continuously adjustabe.
An one-step preparation process for the nitrogenous magnetic of rare earth, this technique comprises the steps:
(1) load rare earth alloy with in the boiler tube of lapping device, vacuum system starts and vacuumizes rear air supply system to boiler tube and in boiler tube, be filled with hydrogen carry out hydrogen fragmentation to rare earth alloy and obtain rare earth alloy powder;
(2) cooling system starting is cooled to less than 150 DEG C to the rare earth alloy powder after hydrogen fragmentation in boiler tube and is greater than 0 DEG C, then under inert gas or nitrogen protection, carries out grinding to rare earth alloy powder and obtains rare earth alloy fine powder;
(3) boiler tube is vacuumized, boiler tube is heated to 400-600 DEG C by heating furnace, and then the nitrogenous gas being filled with 0.01 ~ 0.3MPa in boiler tube carries out nitrogen treatment, after nitrogenize completes to rare earth alloy fine powder, 400-600 DEG C vacuumizes and is incubated 1-10h, carries out homogenizing process;
(4) the rare earth alloy fine powder after nitrogen treatment and homogenizing process carries out being cooled to less than 150 DEG C and is greater than 0 DEG C by cooling system starting, obtains rare earth nitrogenous magnetic after grinding under inert gas shielding to the rare earth alloy powder after nitrogen treatment and homogenizing process.
In affiliated step (1), the suction hydrogen temperature of carrying out hydrogen fragmentation to rare earth alloy is 0-300 DEG C, inhale the hydrogen time is 0-10h, desorption temperature is 300-800 DEG C, dehydrogenation time is 0-10h, pass into amounts of hydrogen, suction hydrogen time and dehydrogenation time are 0 and show that in one-step technology of the present invention, hydrogen shattering process can be omitted under given conditions.
In affiliated step (1); as the original granularity of rare earth alloy processed comparatively thin (maximum particle diameter is at below 5mm); then step (1) can be saved, and namely alloy directly enters step (2) without hydrogen fragmentation under inert gas or nitrogen protection, be milled to particle mean size to rare earth alloy be 10-500 μm.
Particle mean size in step (2) and step (4) all represents with D50 in an embodiment.
Step (2) middle rare earth alloy fine powder is 10 ~ 500 μm, obtains rare earth alloy fine powder by controlling certain milling time, then takes out and carries out measurement and obtain empirical value.
Nitrogenous gas described in step (3) is N
2, NH
3, N
2+nH
3, N
2+ H
2, NH
3+ H
2, N
2+ NH
3+ H
2in any one.
Its temperature of nitrogen treatment described in step (3) is 400-600 DEG C, nitridation time is 1-100h.
Certain particle mean size described in step (4) is 1-200 μm.
The rotary speed of the rotatable boiler tube described in step (1) respectively can continuously adjustabe in 0-200r/min as required in step (1), step (2), step (3), step (4), and rotary speed ≠ 0, wherein in step (1) and step (3), be preferably 1-10r/min, in step (2) and step (4), be preferably 10-60r/min.
Step (2) and the milling time described in step (4) are 10min ~ 5h, change according to different granularity requirements, milling time is less than 10min and does not have broken effect, easily causes the change of oxidation and powder phase structure after being greater than 5h.
The nitrogenous magnetic chemical formula of rare earth prepared by one-step technology of the present invention is R
a(Fe
1-xm
x)
100-a-bn
b, wherein 5≤a≤11,0≤b≤40,0≤x≤1, R represents at least one comprised in all rare earth elements of Sc and Y, and M represents at least one in Zr, Hf, Mn, Ti, Si, V, Co, Ni, Cr, Mo, Al, Nb, Ga, In, Cu, Zn.
The present invention also comprises the nitrogenous magnet of a kind of rare earth, adopts the nitrogenous magnetic of foregoing rare earth to be mixed with into binding agent.
Major advantage of the present invention has:
(1) technological process is short, efficiency is high, and the magnetic oxygen content of preparation is low, magnetic property is high;
This technique is by the several key links in nitrogenous for rare earth magnetic preparation technology: hydrogen fragmentation, Nitrizing Treatment, ball milling etc. are concentrated and completed continuously within one device, obviously can reduce the oxygen content of magnetic while shortened process.
(2) nitriding process efficiency is high, and nitrogenize is even, magnetic property is stablized;
During due to this technique Nitrizing Treatment, boiler tube slow circumvolve, adds that the stirring action of ball milling can make alloyed powder and nitrogen fully gas-solid reaction occur, nitrogenize can be made to complete within a short period of time, and efficiency of nitridation is high, the magnetic nitrogen content of preparation is even, and magnetic property is stablized.
(3) magnetic can cool fast, and production efficiency is high, be conducive to reducing magnetic oxygen content;
The equipment that one-step technology provided by the invention is used, owing to adopting two halves formula heating furnace, can close up according to the needs of heating or cooling or open.When magnetic needs to cool, burner hearth is opened, and running water directly can be sprayed to boiler tube cooling by cooling system.Therefore, cooling effectiveness is higher, significantly can shorten magnetic cooling time, and production efficiency is high, be conducive to reducing magnetic oxygen content.
Accompanying drawing illustrates:
Fig. 1 is one-step method special equipment schematic diagram of the present invention.Number in the figure is: 1 air supply system; 2 vacuum systems; 3 cooling systems; 4 lapping devices; 5 boiler tubes; 6 heating burner hearths.
Fig. 2 is that A-A heats schematic diagram.
Body of heater cross sectional representation when Fig. 3 cools.
Fig. 4 is the XRD figure before and after the nitrogenize of embodiment 1 alloyed powder.
Fig. 5 is the XRD figure before and after the nitrogenize of embodiment 9 alloyed powder.
Embodiment
As shown in Figure 1, the equipment that the one-step preparation process of the nitrogenous magnetic of rare earth of the present invention uses, is equipped with the boiler tube 5 of the driven rotation of lapping device 4, heating furnace 6, vacuum system 2, cooling system 3 and air supply system 1 and forms by inside.Wherein, vacuum system 2 is made up of equipment such as vacuum pumps, and the outlet vacuumized and the boiler tube 5 of vacuum system 2 are connected; Air supply system 1 is made up of equipment such as nitrogen cylinder, nitrogenous gas bottle, hydrogen cylinder and inert gas bottles, and outlet and the boiler tube 5 of gas cylinder are connected; Boiler tube 5 is positioned among heating furnace 6, and water-cooling system 3 is positioned at the bottom of heating furnace 6, and cooling system 3 adopts water-cooling pattern, can be made up of a row to the water pipe spraying running water.As shown in Figure 2, the semicircular structure that heating furnace 6 is equipped with heater respectively by two inner sides forms, and these two semicircular structures can close up when heating boiler tube 5 is enclosed within centre as required; When cooling, as shown in Figure 3, boiler tube 5 can separately expose by these two semicircular structures, and a drainage pipe of cooling system 3 can spray running water, cools fast to make boiler tube 5.
Embodiment 1
The rare earth alloy of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Then the heater of burner hearth 6 starts heating, within 10 minutes, be warming up to 100 DEG C, boiler tube 5 starts to rotate with the speed of 10r/min, then air-channel system 1 fills high-purity hydrogen and is incubated quick-fried 1 hour of hydrogen to 0.12MPa, inhale hydrogen saturated after is evacuated to 1Pa at 450 DEG C of dehydrogenase 12s hour, then open burner hearth 6 and utilize below cooling system 3 water-cooled boiler tube to 150 DEG C.
The above-mentioned alloy handled well is carried out ball milling nitrogen treatment, 2x10 is evacuated to boiler tube 5
-3pa, then air-channel system 1 controls to pass into 0.12MPa high pure nitrogen, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 60r/min, its granularity D50 closes up burner hearth 6 and starts heating when reaching 40 μm, within 1 hour, be warming up to 400 DEG C of insulation nitrogenize 3 hours, then be evacuated to below 1Pa homogenizing 1 hour, control boiler tube 5 while nitrogenize and rotate with the speed of 10r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, open and drive boiler tube to continue ball milling 4 hours with the speed of 60r/min, obtain the Sm that granularity D50 is 1 μm
11.5fe
88.5n
2.9magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.Before and after this magnetic nitrogenize, the change of phase as shown in Figure 4.
Comparative example 1
Composition is identical with embodiment 1 with technique, but hydrogen is quick-fried, nitrogenize, ball-milling treatment are carried out respectively in different equipment, obtains Sm
11.5fe
88.5n
1.6performance and the nitrogen oxygen content of magnetic compare with embodiment 1, and result is as shown in table 1.
Embodiment 2
By clean surface rare earth alloy load inner being equipped with in the rotatable boiler tube 5 of lapping device 4, close up burner hearth 6 and boiler tube be enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Recycling burner hearth 6 starts heating, within 10 minutes, be warming up to 200 DEG C, boiler tube 5 is driven to rotate with the speed of 5r/min, then fill high-purity hydrogen and be incubated quick-fried 1 hour of hydrogen to 0.12MPa, inhale hydrogen saturated after is evacuated to 1Pa at 800 DEG C of dehydrogenase 12s hour, then open burner hearth 6 and utilize below cooling system 3 water-cooled boiler tube to 150 DEG C.
The above-mentioned alloy handled well is carried out ball milling nitrogen treatment, 2x10 is evacuated to boiler tube 5
-3pa, then 0.3MPa high pure nitrogen is passed into, boiler tube 5 rotates boiler tube ball milling 1 hour with the speed of 80r/min, its granularity D50 closes up burner hearth 6 and starts heating when reaching 20 μm, within 1 hour, be warming up to 450 DEG C of insulation nitrogenize 2 hours, then be evacuated to below 1Pa homogenizing 3 hours, while nitrogenize, utilize control boiler tube (5) to rotate with the speed of 5r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, drive boiler tube to continue ball milling 4 hours with the speed of 80r/min, obtain the Sm that granularity D50 is 2 μm
2fe
15.5(Zr
1.0nb
0.5) N
3.1magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Comparative example 2
Composition is identical with embodiment 2 with technique, but hydrogen is quick-fried, nitrogenize, ball-milling treatment are carried out respectively in different equipment, obtains Sm
2fe
15.5(Zr
1.0nb
0.5) N
1.8the performance of magnetic and oxygen content compare with embodiment 2, and result is as shown in table 1.
Embodiment 3
The rare earth alloy of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; The heating system that recycling burner hearth 6 forms starts heating, within 30 minutes, be warming up to 300 DEG C, boiler tube 5 is driven to rotate with the speed of 10r/min, then air-channel system 1 controls to fill high-purity hydrogen and is incubated quick-fried 0.5 hour of hydrogen to 0.12MPa, inhale hydrogen saturated after is evacuated to 1Pa 300 DEG C of dehydrogenations 10 hours, then open burner hearth 6 and utilize below cooling system 3 water-cooled boiler tube to 150 DEG C.
The above-mentioned alloy handled well is carried out ball milling nitrogen treatment, 2x10 is evacuated to boiler tube 5
-3pa, then passes into the N that 0.12MPa volume ratio is 1: 3
2and NH
3mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 40r/min, its granularity D50 closes up burner hearth 6 and starts heating when reaching 50 μm, within 1 hour, be warming up to 500 DEG C of insulation nitrogenize 3 hours, then below 1Pa homogenizing is evacuated to 10 hours, utilize control boiler tube 5 to rotate with the speed of 10r/min while nitrogenize, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, drive boiler tube to continue ball milling 5 hours with the speed of 40r/min, obtain the Sm that granularity D50 is 3 μm
1.4pr
0.6fe
16.1(Cu
0.03ni
0.03zn
0.03) N
5.8magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Comparative example 3
Composition is identical with embodiment 3 with technique, but hydrogen is quick-fried, nitrogenize, ball-milling treatment are carried out respectively in different equipment, obtains Sm
1.4p
r0.6fe
16.1(Cu
0.03ni
0.03zn
0.03) N
2.8performance and the nitrogen oxygen content of magnetic compare with embodiment 3, and result is as shown in table 1.
Embodiment 4
The rare earth alloy of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Sharp burner hearth 6 starts heating again, within 10 minutes, be warming up to 100 DEG C, boiler tube 5 is driven to rotate with the speed of 1r/min, then air-channel system 1 controls to fill high-purity hydrogen and is incubated quick-fried 10 hours of hydrogen to 0.12MPa, inhale hydrogen saturated after is evacuated to 1Pa at 500 DEG C of dehydrogenase 13s hour, then open burner hearth 6 and utilize below cooling system (3) water-cooled boiler tube to 150 DEG C.
The above-mentioned alloy handled well is carried out ball milling nitrogen treatment, 2x10 is evacuated to boiler tube 5
-3pa, then passes into the H that 0.02MPa volume ratio is 1: 3
2and NH
3mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 100r/min, its granularity D50 closes up burner hearth 6 and starts heating when reaching 10 μm, within 1 hour, be warming up to 450 DEG C of insulation nitrogenize 2 hours, then below 1Pa homogenizing is evacuated to 1 hour, utilize control boiler tube 5 to rotate with the speed of 1r/min while nitrogenize, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, drive boiler tube 5 to continue ball milling 2 hours with the speed of 100r/min, obtain the NdFe that granularity D50 is 1 μm
11.2co
0.8n
1.3magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Comparative example 4
Composition is identical with embodiment 4 with technique, but hydrogen is quick-fried, nitrogenize, ball-milling treatment are carried out respectively in different equipment, obtains NdFe
11.2co
0.8n
0.6the performance of magnetic and oxygen content compare with embodiment 4, and result is as shown in table 1.
Embodiment 5
The rare earth alloy of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Recycling burner hearth 6 starts heating, within 10 minutes, be warming up to 100 DEG C, boiler tube 5 is driven to rotate with the speed of 10r/min, then pass into high-purity hydrogen by air supply system 1 and be incubated quick-fried 2 hours of hydrogen to 0.01MPa, inhale hydrogen saturated after is evacuated to 1Pa at 450 DEG C of dehydrogenase 34s hour, then open burner hearth 6 and utilize below cooling system 3 water-cooled boiler tube to 150 DEG C.
The above-mentioned alloy handled well is carried out ball milling nitrogen treatment, 2x10 is evacuated to boiler tube 5
-3pa, then passes into the N that 0.2MPa volume ratio is 1: 1: 3
2, H
2and NH
3mist, boiler tube 5 is driven to rotate boiler tube ball milling 0.5 hour with the speed of 200r/min, its granularity D50 closes up burner hearth 6 and starts heating when reaching 10 μm, within 1 hour, be warming up to 500 DEG C of insulation nitrogenize 3 hours, then below 1Pa homogenizing is evacuated to 2 hours, utilize control boiler tube 5 to rotate with the speed of 10r/min while nitrogenize, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, be filled with inert gas and do protective atmosphere after its cooling, open and drive boiler tube to continue ball milling 1 hour with the speed of 200r/min, obtain granularity D50 at the Sm of 1 μm
1.9gd
0.05la
0.025ce
0.025fe
16.7co
0.3n
4magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Embodiment 6
The rare earth alloy of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; The heating system that recycling burner hearth 6 forms starts heating, within 10 minutes, be warming up to 100 DEG C, open and drive boiler tube 5 to rotate with the speed of 10r/min, then pass into high-purity hydrogen by air supply system 1 and be incubated quick-fried 1 hour of hydrogen to 0.05MPa, inhale hydrogen saturated after is evacuated to below 1Pa at 500 DEG C of dehydrogenase 35s hour, then open burner hearth 6 and utilize below cooling system 3 water-cooled boiler tube to 150 DEG C.
The above-mentioned alloy handled well is carried out ball milling nitrogen treatment, 2x10 is evacuated to boiler tube 5
-3pa, then passes into the NH of 0.12MPa
3open and drive boiler tube 5 to rotate boiler tube ball milling 2 hours with the speed of 10r/min, its granularity D50 closes up burner hearth 6 and starts heating when reaching 100 μm, within 1 hour, be warming up to 500 DEG C of insulation nitrogenize 1 hour, then 1Pa homogenizing is evacuated to 1 hour, utilize control boiler tube 5 to rotate with the speed of 10r/min while nitrogenize, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, open and drive boiler tube 5 to continue ball milling 5 hours with the speed of 10r/min, obtain the Nd that granularity D50 is 5 μm
0.8dy
0.2tiFe
10vN
3.8magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Embodiment 7
The rare earth alloy of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; The heating system that recycling burner hearth 6 forms starts heating, within 10 minutes, be warming up to 150 DEG C, open and drive boiler tube 5 to rotate with the speed of 6r/min, then utilize air supply system (1) to pass into high-purity hydrogen and be incubated quick-fried 6 hours of hydrogen to 0.08MPa, inhale hydrogen saturated after is evacuated to below 1Pa 600 DEG C of dehydrogenations 10 hours, then open burner hearth 6 and utilize below cooling system 3 water-cooled boiler tube to 150 DEG C.
The above-mentioned alloy handled well is carried out ball milling nitrogen treatment, 2x10 is evacuated to boiler tube 5
-3pa, then passes into the N that 0.08MPa volume ratio is 1: 3
2and H
2mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 120r/min, its granularity D50 reach 10 μm close up burner hearth 6 start heating, within 1 hour, be warming up to 600 DEG C of insulation nitrogenize 3 hours, then 1Pa homogenizing is evacuated to 5 hours, utilize control boiler tube 5 to rotate with the speed of 6r/min while nitrogenize, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, be filled with inert gas and do protective atmosphere after its cooling, drive boiler tube to continue ball milling 3 hours with the speed of 120r/min, obtain granularity D50 at the Nd of 2 μm
0.8pr
0.2tiFe
10moN
4.2magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Embodiment 8
The rare earth alloy of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa, passes into the H of 0MPa
2, hydrogen quick-fried and desorption temperature time is 0; Then the N that 0.15MPa volume ratio is 1: 3 is passed into
2and NH
3mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 60r/min, its granularity D50 closes up burner hearth 6 when reaching 20 μm, the heating system that recycling burner hearth 6 forms starts heating, within 1 hour, be warming up to 450 DEG C of insulation nitrogenize 6 hours, then be evacuated to below 1Pa homogenizing 2 hours, while nitrogenize, utilize control boiler tube 5 to rotate with the speed of 10r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, open and drive boiler tube 5 to continue ball milling 2 hours with the speed of 60r/min, obtain the Sm that granularity D50 is 2 μm
1.98tb
0.01dy
0.01fe
17n
3.6magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Embodiment 9
The rare-earth alloy casting slice of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Then the H that 0.2MPa volume ratio is 1: 3 is passed into
2and NH
3mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 30r/min, its granularity D50 closes up burner hearth 6 when reaching 200 μm, the heating system that recycling burner hearth 6 forms starts heating, within 1 hour, be warming up to 450 DEG C of insulation nitrogenize 40 hours, then be evacuated to below 1Pa homogenizing 5 hours, control boiler tube 5 while nitrogenize and rotate with the speed of 3r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, open and drive boiler tube to continue ball milling 1 hour with the speed of 30r/min, obtain the Sm that granularity D50 is 20 μm
7.2fe
76.8co
3.2zr
0.8n
12magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.Before and after this magnetic nitrogenize, the change of phase as shown in Figure 5.
Embodiment 10
The rare-earth alloy casting slice of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Then the N that 0.12MPa volume ratio is 1: 3: 1 is passed into
2, H
2and NH
3mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 20r/min, its granularity D50 closes up burner hearth 6 when reaching 500 μm, the heating system that recycling burner hearth 6 forms starts heating, within 1 hour, be warming up to 400 DEG C of insulation nitrogenize 100 hours, then be evacuated to below 1Pa homogenizing 10 hours, control boiler tube 5 while nitrogenize and rotate with the speed of 1r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, drive boiler tube 5 to continue ball milling 2 hours with the speed of 20r/min, obtain the Nd that granularity D50 is 15 μm
0.2sm
6.2zr
3.0co
4.3ti
0.3b
0.9fe
70.6n
14.5magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Embodiment 11
The rare-earth alloy casting slice of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube 5 is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Then the high-purity N that 0.02MPa volume ratio is 1: 3 is passed into
2and H
2mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 50r/min, its granularity D50 close up when reaching 30 μm burner hearth 6 recycle the heating system be made up of the heater of heating power supply and burner hearth 6 start heating, within 1 hour, be warming up to 450 DEG C of insulation nitrogenize 3 hours, then below 1Pa homogenizing is evacuated to 1 hour, control boiler tube 5 while nitrogenize to rotate with the speed of 10r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, drive boiler tube 5 to continue ball milling 1 hour with the speed of 50r/min, obtain the Pr that granularity D50 is 8 μm
0.2sm
6.2zr
3.0cu
0.05zn
0.9co
4.3fe
72.85n
12.5magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Embodiment 12
The rare-earth alloy casting slice of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube 5 is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Pass into the high-purity N that 0.12MPa volume ratio is 1: 3
2and H
2mist, boiler tube 5 is driven to rotate boiler tube ball milling 0.5 hour with the speed of 20r/min, its granularity D50 closes up burner hearth 6 when reaching 300 μm, the heating system that recycling burner hearth 6 forms starts heating, within 1 hour, be warming up to 450 DEG C of insulation nitrogenize 4 hours, then be evacuated to below 1Pa homogenizing 1 hour, control boiler tube 5 while nitrogenize and rotate with the speed of 5r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, obtain the Dy that mean particle size D 50 is 200 μm
0.2sm
6.8zr
3.0co
4.3febalN
14.5magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
Embodiment 13
The rare-earth alloy casting slice of clean surface is loaded inner being equipped with in the rotatable boiler tube 5 of lapping device 4, closes up burner hearth 6 and boiler tube 5 is enclosed within centre; Then vacuum system 2 pairs of boiler tubes 5 are utilized to be evacuated to 2x10
-3below Pa; Then the high-purity N that 0.12MPa volume ratio is 1: 3 is passed into
2and H
2mist, boiler tube 5 is driven to rotate boiler tube ball milling 1 hour with the speed of 30r/min, its granularity D50 closes up burner hearth 6 when reaching 200 μm, the heating system that recycling burner hearth 6 forms starts heating, within 1 hour, be warming up to 480 DEG C of insulation nitrogenize 3 hours, then be evacuated to below 1Pa homogenizing 1 hour, control boiler tube 5 while nitrogenize and rotate with the speed of 5r/min, improve efficiency of nitridation and promote that nitrogenize is even.
Open burner hearth 6, utilize the above-mentioned nitrogenize powder handled well of cooling system 3 water-cooled, after its cooling, be filled with inert gas do protective atmosphere, drive boiler tube to continue ball milling with the speed of 20r/min and within 1 hour, obtain the Sm that mean particle size D 50 is 100 μm
6.8zr
1.8co
4si
0.6fe
73.9n
13.5magnetic, tests its magnetic property and nitrogen oxygen content is as shown in table 1.
The oxygen content of the nitrogenous magnetic of table 1 rare earth and magnetic property
Claims (8)
1. the nitrogenous magnetic preparation technology of rare earth, it is characterized in that, this technique comprises the steps:
(1) load rare earth alloy with in the boiler tube of lapping device, vacuum system starts and vacuumizes rear air supply system to boiler tube and in boiler tube, be filled with hydrogen carry out hydrogen fragmentation to rare earth alloy and obtain rare earth alloy powder;
(2) cooling system starting is cooled to less than 150 DEG C to the rare earth alloy powder after hydrogen fragmentation in boiler tube and is greater than 0 DEG C, then under inert gas or nitrogen protection, carries out grinding to rare earth alloy powder and obtains rare earth alloy fine powder;
(3) boiler tube is vacuumized, boiler tube is heated to 400-600 DEG C by heating furnace, and then the nitrogenous gas being filled with 0.01-0.3MPa in boiler tube carries out nitrogen treatment, after nitrogenize completes to rare earth alloy fine powder, 400-600 DEG C vacuumizes and is incubated 1-10h, carries out homogenizing process;
(4) the rare earth alloy fine powder after nitrogen treatment and homogenizing process is cooled to less than 150 DEG C and is greater than 0 DEG C by cooling system starting, obtains rare earth nitrogenous magnetic after grinding under inert gas shielding to the rare earth alloy powder after nitrogen treatment and homogenizing process.
2. the nitrogenous magnetic preparation technology of rare earth according to claim 1, it is characterized in that: in described step (1), the described Hydrogen Vapor Pressure that is filled with is 0-0.2MPa, the suction hydrogen temperature of carrying out hydrogen fragmentation to rare earth alloy is 0-300 DEG C, inhale the hydrogen time is 0-10h, and desorption temperature is 300-800 DEG C, dehydrogenation time is 0-10h.
3. the nitrogenous magnetic preparation technology of rare earth according to claim 1, is characterized in that: the nitrogenous gas described in step (3) is N
2, NH
3, N
2+ NH
3, N
2+ H
2, NH
3+ H
2, N
2+ NH
3+ H
2in at least one.
4. the nitrogenous magnetic preparation technology of rare earth according to claim 1, is characterized in that: the temperature of the nitrogen treatment described in step (3) is 400-600 DEG C, nitridation time is 1-100h.
5. the nitrogenous magnetic preparation technology of rare earth according to claim 1, is characterized in that: the nitrogenous magnetic particle mean size of the rare earth described in step (4) is 1-200 μm.
6. the nitrogenous magnetic preparation technology of rare earth according to claim 1, it is characterized in that: described in step (1), boiler tube is rotatable, boiler tube rotary speed respectively can continuously adjustabe in 0-100r/min as required in step (1), step (2), step (3), step (4), and rotary speed ≠ 0.
7. the nitrogenous magnetic preparation technology of rare earth according to claim 6, it is characterized in that: wherein in step (1) and step (3), boiler tube rotary speed is 1-10r/min, in step (2) and step (4), boiler tube rotary speed is 10-60r/min.
8. the nitrogenous magnetic preparation technology of rare earth according to claim 1, is characterized in that: step (2) and the milling time described in step (4) are 10min-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110116325.2A CN102768891B (en) | 2011-05-06 | 2011-05-06 | The product of the nitrogenous magnetic preparation technology of rare earth and equipment and preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110116325.2A CN102768891B (en) | 2011-05-06 | 2011-05-06 | The product of the nitrogenous magnetic preparation technology of rare earth and equipment and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102768891A CN102768891A (en) | 2012-11-07 |
| CN102768891B true CN102768891B (en) | 2015-11-04 |
Family
ID=47096256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110116325.2A Active CN102768891B (en) | 2011-05-06 | 2011-05-06 | The product of the nitrogenous magnetic preparation technology of rare earth and equipment and preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102768891B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205543B (en) * | 2013-05-05 | 2014-12-03 | 沈阳中北真空磁电科技有限公司 | Vacuum heat treatment method and equipment for permanent NdFeB rare earth magnet device |
| CN104347215A (en) * | 2013-07-23 | 2015-02-11 | 有研稀土新材料股份有限公司 | Method for preparing rare-earth permanent magnet powder |
| CN105081335B (en) * | 2015-09-18 | 2017-04-26 | 苏州萨伯工业设计有限公司 | Energy-saving hydrogen decrepitation device for production of rare earth magnetic materials |
| CN108766701B (en) * | 2018-04-26 | 2020-08-21 | 安徽省瀚海新材料股份有限公司 | Crushing process of neodymium iron boron melt-spun piece |
| CN109332709A (en) * | 2018-10-31 | 2019-02-15 | 西安嘉业航空科技有限公司 | A kind of preparation of hypoxemia metal powder all-in-one machine and preparation method |
| CN111180160A (en) * | 2020-01-17 | 2020-05-19 | 杭州史宾纳科技有限公司 | Process for reducing and diffusing isotropic samarium-iron-nitrogen powder and magnet |
| CN112712956B (en) * | 2020-12-16 | 2022-05-31 | 横店集团东磁股份有限公司 | Nitriding method of rare earth magnet and nitrided rare earth magnet |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105503A (en) * | 2000-07-24 | 2002-04-10 | Kinya Adachi | Method for manufacturing magnetic material, and magnetic material powder with rust preventive layer thereon and bonded magnet using it |
| CN1483538A (en) * | 2003-08-12 | 2004-03-24 | 北京科技大学 | Method and apparatus for peparing hydrogen induced rareearth magnetic-like anisotropic magnetic powder |
| CN1937111A (en) * | 2006-09-19 | 2007-03-28 | 北京大学 | Method for preparing rolling anisotropic magnetic powder and magnet |
| CN101239387A (en) * | 2007-02-08 | 2008-08-13 | 有研稀土新材料股份有限公司 | Heat-resisting oxidation-resistance nitrogen-containing anisotropic rare earth permanent magnet alloy powder and preparation thereof |
| CN101512036A (en) * | 2006-09-11 | 2009-08-19 | 株式会社爱发科 | Vacuum evaporation processing equipment |
| CN101546642A (en) * | 2008-03-26 | 2009-09-30 | 有研稀土新材料股份有限公司 | Nitrogen-containing rare-earth magnetic powder and preparation method thereof |
| CN101599329A (en) * | 2008-06-04 | 2009-12-09 | 有研稀土新材料股份有限公司 | A kind of nitrogenous rare-earth magnetic and preparation method thereof |
-
2011
- 2011-05-06 CN CN201110116325.2A patent/CN102768891B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105503A (en) * | 2000-07-24 | 2002-04-10 | Kinya Adachi | Method for manufacturing magnetic material, and magnetic material powder with rust preventive layer thereon and bonded magnet using it |
| CN1483538A (en) * | 2003-08-12 | 2004-03-24 | 北京科技大学 | Method and apparatus for peparing hydrogen induced rareearth magnetic-like anisotropic magnetic powder |
| CN101512036A (en) * | 2006-09-11 | 2009-08-19 | 株式会社爱发科 | Vacuum evaporation processing equipment |
| CN1937111A (en) * | 2006-09-19 | 2007-03-28 | 北京大学 | Method for preparing rolling anisotropic magnetic powder and magnet |
| CN101239387A (en) * | 2007-02-08 | 2008-08-13 | 有研稀土新材料股份有限公司 | Heat-resisting oxidation-resistance nitrogen-containing anisotropic rare earth permanent magnet alloy powder and preparation thereof |
| CN101546642A (en) * | 2008-03-26 | 2009-09-30 | 有研稀土新材料股份有限公司 | Nitrogen-containing rare-earth magnetic powder and preparation method thereof |
| CN101599329A (en) * | 2008-06-04 | 2009-12-09 | 有研稀土新材料股份有限公司 | A kind of nitrogenous rare-earth magnetic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102768891A (en) | 2012-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102768891B (en) | The product of the nitrogenous magnetic preparation technology of rare earth and equipment and preparation | |
| CN103056370B (en) | Method of improving coercivity of sintering Nd-Fe-B magnetic material | |
| CN104700973B (en) | A kind of rare-earth permanent magnet being made up of the common association raw ore mischmetal of Bayan Obo and preparation method thereof | |
| CN107275027B (en) | Using the cerium-rich rare earth permanent magnet and preparation method thereof of yttrium | |
| CN102969112B (en) | Rare earth permanent magnet powder and preparation method thereof and magnet prepared therefrom and magnetic device | |
| CN101767200B (en) | Minute spherical Nd-Fe-B powder preparation method | |
| CN106158203B (en) | A kind of preparation method of high-coercive force high-stability neodymium iron boron magnet | |
| CN101826386A (en) | Components and manufacturing process of rare earth permanent magnet material | |
| CN103093916A (en) | Neodymium iron boron magnetic materials and preparation method of the same | |
| CN105355412A (en) | Method for obtaining high-magnetism sintered NdFeB through sulfidizing | |
| CN111968819A (en) | Low-heavy rare earth high-performance sintered neodymium-iron-boron magnet and preparation method thereof | |
| CN101786163B (en) | Preparation method of high-performance room-temperature magnetic refrigeration nano bulk material | |
| CN102360909B (en) | Preparation method for neodymium iron boron magnet | |
| CN103624248A (en) | Preparation method for rare earth permanent magnet powder | |
| CN103280288A (en) | Manufacturing method of high-coercivity samarium-cobalt-based permanent magnet materials | |
| CN104252937B (en) | A kind of regulate and control the sintered NdFeB permanent magnet ferrum of particulate combinations and manufacture method | |
| CN103000324A (en) | Sintered rare earth permanent magnetic material and preparation method thereof | |
| CN105374488A (en) | High-temperature-resistant high-performance rare earth permanent magnet material | |
| CN112216460A (en) | Nanocrystalline neodymium-iron-boron magnet and preparation method thereof | |
| CN104392818A (en) | Method for increasing magnetic performance of sintered Nd-Fe-B permanent magnet material | |
| CN105702406A (en) | MnAlC-based high coercive force permanent magnetic material and preparation method thereof | |
| CN101719406B (en) | Method for preparing Nd-Fe-B permanent magnet material by adding Gd-Fe alloy | |
| CN103537705A (en) | Hydrogen decrepitation process for sintered Nd-Fe-B permanent magnets | |
| CN102296228A (en) | Permanent magnet alloy block added with carbon and preparation method for permanent magnet alloy block | |
| CN105374489A (en) | Heat-resistant rare-earth permanent magnetic material for motor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: GRIREM ADVANCED MATERIALS CO., LTD. Effective date: 20130812 Owner name: GRIREM ADVANCED MATERIALS CO., LTD. Free format text: FORMER OWNER: BEIJING CENTRAL INST.OF THE NONFERROUS METAL Effective date: 20130812 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20130812 Address after: 100088 Beijing city Xicheng District Xinjiekou Avenue No. 2 Applicant after: Grirem Advanced Materials Co., Ltd. Address before: 100088 Beijing city Xicheng District Xinjiekou Avenue No. 2 Applicant before: General Research Institute for Nonferrous Metals Applicant before: Grirem Advanced Materials Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |