CN103996474A - Manufacturing method of neodymium iron boron rare earth permanent magnetic alloy - Google Patents
Manufacturing method of neodymium iron boron rare earth permanent magnetic alloy Download PDFInfo
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Abstract
The invention discloses a manufacturing method of neodymium iron boron rare earth permanent magnetic alloy. Firstly, R-Fe-B-M raw materials are heated to be over 500 DEG C under the vacuum condition, then argon is charged, the R-Fe-B-M raw materials are continuously heated to be melted and refined to be molten alloy, T203 oxide tiny powder is added in the process, and finally the molten alloy liquid is cast on a rotating roller with water cooling through a tundish to form an alloy sheet, wherein the T203 represents one or more oxides of Dy2O3, Tb2O3, Ho2O3, Y2O3, Al2O3 and Ti2O3; the adding amount of the T203 oxide tiny powder is greater than or equal to zero but smaller than or equal to 2%.
Description
Technical field
The invention belongs to rare earth permanent magnet field, particularly relate to a kind of manufacture method of permanent-magnet rare-earth NdFeB alloy.
Background technology
Nd-Fe-B rare earth permanent magnetic material, is more and more applied with its good magnetic property, is widely used in medical Magnetic resonance imaging, computer hard disc driver, sound equipment, mobile phone etc.; Along with energy-conservation and requirement low-carbon economy, Nd-Fe-B rare earth permanent magnetic material starts again at auto parts and components, household electrical appliance, energy-conservation and control motor, hybrid vehicle, field of wind power generation application.
Nineteen eighty-three, Japan Patent 1,622, first 492 and 2,137,496 disclose Nd-Fe-B rare earth permanent magnetic material, announced characteristic, composition and the manufacture method of Nd-Fe-B rare earth permanent magnetic material, confirmed principal phase: Nd
2fe
14b phase, Grain-Boundary Phase: rich Nd phase, rich B phase and rare earth oxide impurity; US Patent No. 6,461,565; US6,491,765; US 6,537,385; US 6,527,874; US5,645,651 also disclose the manufacture method of Nd-Fe-B rare-earth permanent magnet.
US Patent No. 5,383,978 disclose the manufacture method of producing Nd-Fe-B rare-earth permanent magnet vacuum rapid hardening alloy, and this method has obviously improved the performance of rare earth permanent magnet, is widely adopted.Patent US5,690,752; CN97111284.3; CN1,671,869A; US5,908,513; US5,948,179; US5,963,774; CN1,636,074A is disclosed is all the improvement technology to Nd-Fe-B rare-earth permanent magnet vacuum rapid hardening alloy.
Summary of the invention
The present invention adds T in the time of Nd Fe B alloys melting
2o
3oxide micropowder, in the alloy rapid hardening process after fusing, T
2o
3oxide micropowder is evenly distributed in Grain-Boundary Phase, has suppressed grain growth, has obviously improved the deficiencies in the prior art:
1, reduced the consumption of heavy rare earth, heavy rare earth is scarce resource in the world, and in the Rare Earth Mine of finding at present, only in the South Ore Deposit of China, heavy rare earth content is higher, and the consumption that reduces heavy rare earth needs the application of heatproof extremely important to development rare earth permanent magnet at motor etc.In addition, heavy rare earth price is higher, and the consumption that reduces heavy rare earth is extremely important to the price of reduction rare earth permanent magnet.
2, obviously improved the magnetic energy product of magnet, orientation when crystal grain reduces to be conducive to pressing under magnetic field, has improved the magnetic energy product of magnet.
3, the decay resistance that has improved magnet, adds T
2o
3after oxide micropowder, in the time of sintering, change the distribution of structure and the rich neodymium phase of Grain-Boundary Phase, the decay resistance of magnet is improved.
Along with the expansion of the application market of Nd-Fe-B rare earth permanent magnetic material, the problem of rare earth resources shortage is more and more serious, especially at electronic devices and components, energy-conservation and control the application of motor, auto parts and components, new-energy automobile, field of wind power generation, need more heavy rare earth to improve coercive force.Therefore, how to reduce the use of rare earth, the especially use of heavy rare earth, is the important topic of pendulum in face of us.Through exploring, we have found a kind of permanent-magnet rare-earth NdFeB alloy and manufacture method.
The present invention is achieved through the following technical solutions:
A manufacture method for permanent-magnet rare-earth NdFeB alloy is first heated to R-Fe-B-M raw material more than 500 DEG C under vacuum condition, is filled with afterwards argon gas continuation heating and R-Fe-B-M raw material is melted and be refined into molten alloy, in this process, adds T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet;
Wherein R represents more than one in the rare earth element that comprises Nd;
One or more in M representative element Al, Co, Nb, Ga, Zr, Cu, V, Ti, Cr, Ni, Hf element;
T
2o
3represent oxide Dy
2o
3, Tb
2o
3, Ho
2o
3, Y
2o
3, Al
2o
3, Ti
2o
3in one or more;
Described T
2o
3the addition of oxide micropowder: 0≤T
2o
3≤ 2%;
Preferred T
2o
3the addition of oxide micropowder: 0 < T
2o
3≤ 0.8%;
Preferred T
2o
3oxide micropowder is Al
2o
3and Dy
2o
3in more than one;
Further preferred T
2o
3oxide micropowder is Al
2o
3;
Further preferred T again
2o
3oxide micropowder is Dy
2o
3;
The manufacture method of described permanent-magnet rare-earth NdFeB alloy, first by R-Fe-B-M raw material and T
2o
3oxide micropowder is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating R-Fe-B-M raw material is fused into alloy, after refining by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, molten alloy forms alloy sheet after rotating roller is cooling.
The manufacture method of described permanent-magnet rare-earth NdFeB alloy, first R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating R-Fe-B-M raw material is fused into alloy and carries out refining, refining temperature, at 1400-1470 DEG C, adds T
2o
3after oxide micropowder by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, transfer roller rotating speed 1-4m/s, molten alloy forms alloy sheet after rotating roller is cooling.
The manufacture method of described permanent-magnet rare-earth NdFeB alloy is first heated to R-Fe-B-M raw material more than 500 DEG C under vacuum condition, is filled with afterwards argon gas continuation heating and R-Fe-B-M heating raw materials is melted and be refined into molten alloy, in this process, adds T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet, alloy sheet leaves falls that on rotating disk, to carry out secondary cooling after rotation copper roller immediately.
The manufacture method of described permanent-magnet rare-earth NdFeB alloy is first heated to R-Fe-B-M raw material more than 500 DEG C under vacuum condition, is filled with afterwards argon gas continuation heating and R-Fe-B-M heating raw materials is melted and be refined into molten alloy, in this process, adds T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet, alloy sheet falls after leaving rotation copper roller immediately, lower backward alloy sheet carries out fragmentation, enters rewinding tank after fragmentation.
The manufacture method of described permanent-magnet rare-earth NdFeB alloy is first heated to R-Fe-B-M raw material more than 500 DEG C under vacuum condition, is filled with afterwards argon gas continuation heating and R-Fe-B-M heating raw materials is melted and be refined into molten alloy, in this process, adds T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet, alloy sheet leaves falls that on coldplate, to carry out secondary cooling after rotation copper roller immediately, the cooling rear alloy sheet of secondary carries out fragmentation, after fragmentation, be incubated, with inert gas, alloy sheet is cooling after insulation.
A kind of manufacture method of Fe-B rare-earth permanent magnet:
First R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, is filled with afterwards argon gas continuation heating and R-Fe-B-M raw material is melted and be refined into molten alloy, in this process, add T
2o
3oxide micropowder, afterwards the aluminium alloy of melting is formed to alloy sheet by trough casting to being with in water-cooled rotating roller, afterwards alloy sheet is carried out to hydrogen fragmentation, the broken laggard row airflow milling powder of hydrogen, pressing under magnetic field, sintering and timeliness operation are made Fe-B rare-earth permanent magnet, then make various rare earth permanent magnet devices through machining and surface treatment.Wherein:
R represents more than one in rare earth element;
One or more in M representative element Al, Co, Nb, Ga, Zr, Cu, V, Ti, Cr, Ni, Hf element;
T
2o
3represent oxide Dy
2o
3, Tb
2o
3, Ho
2o
3, Y
2o
3, Al
2o
3, Ti
2o
3in more than one;
HR represent Dy, Tb, Ho, Y rare earth element more than one.
First described hydrogen fragmentation packs alloy sheet into hydrogen crushing furnace, after vacuumizing, be filled with hydrogen by absorption hydrogen, keep inhaling hydrogen temperature 80-300 DEG C, inhale hydrogen and finish rear heating and vacuumize dehydrogenation, desorption temperature 300-900 DEG C, dehydrogenation finishes rear involutory gold plaque and carries out cooling.
The broken broken equipment of continuous hydrogen that adopts of described hydrogen, the material frame of RE permanent magnetic alloy sheet is housed, under the driving of transmission device, order is by suction hydrogen chamber, Heating Dehydrogenation chamber, the cooling chamber of the broken equipment of continuous hydrogen, enter discharge chamber by outlet valve, alloy sheet after hydrogen is broken is derived from material frame, falls into the storage tank of discharge chamber bottom, under nitrogen protection, storage tank is encapsulated, material frame shifts out from the discharge door of discharge chamber, again circular flow after charging; The suction hydrogen temperature 50-350 DEG C of described suction hydrogen chamber, described Heating Dehydrogenation chamber is more than one, desorption temperature 600-900 DEG C, described cooling hydrogen chamber is more than one.
The described broken equipment of continuous hydrogen has two Heating Dehydrogenation chambers, and material frame stops two Heating Dehydrogenation chambers successively, in time of staying of single Heating Dehydrogenation chamber at 2-6 hour; The broken equipment of described continuous hydrogen has two cooling chambers, and material frame stops at two cooling chambers successively, in time of staying of single cooling chamber at 2-6 hour.
Before described airflow milling powder, the alloy sheet after hydrogen fragmentation is joined to batch mixer and carries out front batch mixing, when front batch mixing, add antioxidant and lubricant more than one.
Before described airflow milling powder, the alloy sheet after hydrogen fragmentation is joined to batch mixer and carries out front batch mixing, when front batch mixing, add oxide micropowder more than one.
Described airflow milling powder, adopt nitrogen protection airflow milling powder, first broken the hydrogen after batch mixing powder is packed into the hopper of feeder, by feeder, powder is joined to mill chamber, utilize the high velocity air of nozzle ejection to carry out grinding, powder after grinding enters centrifugal separation polling powder with air-flow, the meal that does not reach powder process granularity turns back to mill chamber and continues grinding under the effect of centrifugal force, the fine powder that reaches granularity enters cyclone collector after by separation wheel sorting and collects, a small amount of fine powder can be discharged along with the air-flow of cyclone collector blast pipe, entering rear cyclone collector collects again, the gas that rear cyclone collector is discharged enters into the air inlet pipe of nozzle after cooling again through compressor compresses and cooler, nitrogen circulation is used.
The described powder that enters cyclone collector collection is collected in by the valve of alternation switch in the mixed powder machine of cyclone collector bottom, the powder that enters rear cyclone collector collection is also collected in the mixed powder machine of cyclone collector bottom by the valve of alternation switch, and powder packs rewinding tank into after mixing in mixed powder machine.
The powder that the powder that described cyclone collector is collected and rear cyclone collector are collected imports in rewinding tank by collector.
The described powder that enters rear cyclone collector collection is collected by the rear cyclone collector of 2-6 in parallel.
The described powder that enters rear cyclone collector collection is collected by the rear cyclone collector of 4 in parallel.
After described airflow milling powder, be sent to and on batch mixer, carry out rear batch mixing, the powder mean particle sizes 1.6-2.9 μ m after rear batch mixing.
After described airflow milling powder, be sent to and on batch mixer, carry out rear batch mixing, the powder mean particle sizes 2.1-2.8 μ m after rear batch mixing.
Described pressing under magnetic field method, under nitrogen protection, pack the permanent-magnet rare-earth NdFeB alloy powder of preorder into nitrogen protection lutation magnetic field presser, under nitrogen protection, in lutation magnetic field presser, the material of weighing is put into the mould cavity after assembling, pack seaming chuck into die cavity afterwards, then mould is sent into the orientation space of electromagnet, in alignment magnetic field interval, the alloy powder in mould is pressurizeed and pressurize, then magnetic patch is demagnetized, after demagnetization, hydraulic cylinder resets, afterwards mould is withdrawn into dress powder position, opening mould packs magnetic patch taking-up plastics or gum cover by magnetic patch, and then mould is assembled, cycling, magnetic patch after packaging is put into charging tray and is taken out from lutation magnetic field presser in batches, send into isostatic pressing machine and wait static pressure.
Described semi-automatic pressing under magnetic field, first the batch can that permanent-magnet rare-earth NdFeB alloy powder is housed is docked with the charging aperture of nitrogen protection alignment magnetic field mo(u)ldenpress, after docking by after the Bas Discharged between the charging aperture valve of batch can and semi-automatic press, open the hopper that material inlet valve imports the powder in batch can weighing device, after weighing, powder is sent in the die cavity of mould automatically, after dust feeder leaves, cylinder pressure on press is moved down, enter after die cavity the powder orientation that magnetizes, under magnetic field to powder extrusion forming, afterwards the magnetic patch of moulding is demagnetized and magnetic patch is ejected from die cavity, then magnetic patch is taken out to the material platform of putting into nitrogen protection alignment magnetic field mo(u)ldenpress, magnetic patch is packed with plastics or gum cover by gloves, packaged magnetic patch is put into charging tray and is taken out in batches, send into isostatic pressing machine and wait static pressure.
Described static pressure such as grade is packaged magnetic patch to be placed in to isostatic pressing machine have in a high-pressure chamber, and in cavity, remaining space is full of with hydraulic oil, and after sealing, to hydraulic oil pressurization in cavity, pressurization maximum pressure scope 150-300MPa, after pressure release takes out magnetic patch.
Described isostatic pressing machine has two high-pressure chambers, a cavity is enclosed within the outside of another cavity, form an inner chamber body and an outer chamber, pack into wrapped magnetic patch in the inner chamber body of isostatic pressing machine, in inner chamber body, remaining space is full of liquid medium, the outer chamber of isostatic pressing machine is filled with hydraulic oil, be connected with the device that produces high pressure, the hydraulic fluid pressure of outer chamber by and inner chamber body between spacer pass to inner chamber body, inner chamber body also produces high pressure, the pressure limit 150-300MPa of inner chamber body thereupon.
Described automatic pressing under magnetic field method, first the batch can that permanent-magnet rare-earth NdFeB alloy powder is housed is docked with the charging aperture of nitrogen protection alignment magnetic field mo(u)ldenpress, after docking by after the Bas Discharged between the charging aperture valve of batch can and mo(u)ldenpress, open the hopper that material inlet valve imports the powder in batch can weighing device, after weighing, powder is sent in the die cavity of mould automatically, after dust feeder leaves, cylinder pressure on press is moved down, enter after die cavity the powder orientation that magnetizes, then to powder extrusion forming, afterwards the magnetic patch of moulding is demagnetized and magnetic patch is ejected from die cavity, then magnetic patch is taken out to the magazine of putting into nitrogen protection alignment magnetic field mo(u)ldenpress, magazine after filling closes the lid magazine, again magazine is put on charging tray, after charging tray is filled, the charging tray of filling magazine under nitrogen protection, is sent to transmission stuffing box by the discharge valve of opening nitrogen protection sealing magnetic field mo(u)ldenpress, then under nitrogen protection, dock with the protection material feeding box of vacuum sintering furnace transmitting stuffing box, the charging tray of filling magazine is sent into the protection material feeding box of vacuum sintering furnace.
Electromagnet pole and the field coil of described nitrogen protection lutation magnetic field presser are connected with coolant, and coolant is water, oil or cold-producing medium, and the space temperature of the placement mould being made up of electromagnet pole and field coil when moulding is lower than 25 DEG C.
Described coolant is water, oil or cold-producing medium, the space temperature of the placement mould being formed by electromagnet pole and field coil when moulding lower than 5 DEG C higher than-10 DEG C.Described to powder extrusion forming, briquetting pressure scope 100-300MPa.
Described sintering is magnetic patch to be sent into continuous vacuum sintering furnace under nitrogen protection to carry out sintering, under the drive of transmission device, the bin that magnetic patch is housed enters the preparation room of continuous vacuum sintering furnace successively, preheating degreasing chamber, the first degas chamber, the second degas chamber, presintering chamber, agglomerating chamber, timeliness chamber and cooling chamber carry out preheating and slough organic impurities, and then Heating Dehydrogenation is degassed, presintering, sintering, timeliness and cooling, after cooling, from continuous vacuum sintering furnace, take out to be sent to again and in vacuum aging stove, carry out secondary ageing, secondary ageing temperature 450-650 DEG C, rapid cooling after secondary ageing, make sintered NdFeB rear-earth permanent magnet, sintered NdFeB rear-earth permanent magnet is made Nd-Fe-B rare-earth permanent magnet device through machining and surface treatment again.
Described bin is introduced into charging chamber entering before the preparation room of continuous vacuum sintering furnace, in charging chamber, remove packaging Deng the magnetic patch after static pressure, pack magazine into, then magazine is contained on bin, under actuator drives, by valve, bin is sent into preparation room afterwards.
Described vacuum presintering is to carry out at continous vacuum pre-burning freezing of a furnace, the magazine that magnetic patch after moulding is housed is contained on sintering bin, under the drive of transmission device, sintering bin enters the preparation room of continous vacuum pre-burning freezing of a furnace successively, degreasing chamber, the first degas chamber, the second degas chamber, the 3rd degas chamber, the first presintering chamber, the second presintering chamber and cooling chamber carry out preheating degreasing, Heating Dehydrogenation is degassed, presintering and cooling, cooling employing argon gas, cooling rear sintering bin takes out and magazine is installed to timeliness bin again from continous vacuum pre-burning freezing of a furnace, timeliness bin plays and sends into the preheating chamber of continous vacuum sintering aging furnace, heating chamber, agglomerating chamber, high-temperature aging chamber, fore-cooling room, low temperature aging chamber and cooling chamber carry out sintering, high-temperature aging, pre-cooled, low temperature aging and air cooling fast.
Described preheating skimming temp scope is at 200-400 DEG C, the degassed temperature range of Heating Dehydrogenation is at 400-900 DEG C, pre-sintering temperature scope is at 900-1050 DEG C, sintering range is at 1010-1085 DEG C, high-temperature aging temperature range is at 800-950 DEG C, low temperature aging temperature range, at 450-650 DEG C, is sent into cooling chamber argon gas or nitrogen rapid cooling after insulation.
Described preheating skimming temp scope is at 200-400 DEG C, the degassed temperature range of Heating Dehydrogenation is at 550-850 DEG C, pre-sintering temperature scope is at 960-1025 DEG C, sintering range is at 1030-1070 DEG C, high-temperature aging temperature range is at 860-940 DEG C, low temperature aging temperature range, at 460-640 DEG C, is sent into cooling chamber argon gas or nitrogen rapid cooling after insulation.
Described presintering vacuum degree is higher than 5 × 10
-1pa, sintering vacuum degree is 5 × 10
-1pa to 5 × 10
-3within the scope of Pa.
Described presintering vacuum degree is higher than 5Pa, and sintering vacuum degree, in 500Pa to 5000Pa scope, is filled with argon gas when sintering.
The effective width 400-800mm of described sintering bin, the effective width 300-400mm of timeliness bin,
The magnet density scope of described presintering is at 7.2-7.5g/cm
3, the magnet density scope of sintering is at 7.5-7.7g/cm
3
The structure of described Nd-Fe-B permanent magnet has at R
2(Fe
1-xco
x)
14the surrounding of B crystal grain surrounds heavy rare earth content higher than R
2(Fe
1-xco
x)
14the ZR of B phase
2(Fe
1-xco
x)
14the structure of B phase, ZR
2(Fe
1-xco
x)
14b phase and PR
2(Fe
1-xco
x)
14between B without Grain-Boundary Phase, ZR
2(Fe
1-xco
x)
14between B phase, connect by Grain-Boundary Phase; In literary composition, ZR is illustrated in crystalline phase heavy rare earth HR content higher than average heavy rare earth content, and R represents that the content of heavy rare earth HR in rare-earth phase is lower than the content of average heavy rare earth HR; 0≤x≤0.5.
More than two ZR in the structure of described Nd-Fe-B permanent magnet
2(Fe
1-xco
x)
14in the Grain-Boundary Phase of the intersection of B phase crystal grain, there is small Nd
2o
3particulate.
The hydrogen fragmentation of described alloy, first the alloy sheet of preorder is packed in swing roller, after vacuumizing, be filled with hydrogen by absorption hydrogen, keep absorption hydrogen temperature 30-300 DEG C, inhale hydrogen and finish to start to heat and vacuumize dehydrogenation, dehydrogenation holding temperature 350-900 DEG C, temperature retention time 3-15 hour, insulation stops heating after finishing, it is cooling to cylinder to withdraw heating furnace, and continues swing roller and vacuumize, temperature is lower than after 300 DEG C, cooling to cylinder water spray.
Analyze and find, part T
2o
3oxide micropowder enters in the powder of filter collection, the T in the powder that filter is collected
2o
3oxide micropowder content is apparently higher than T in the powder of collecting in cyclone collector
2o
3oxide micropowder content, T
2o
3oxide micropowder has protective effect to superfine powder, has obviously improved the oxidation resistance of the superfine powder of filter collection, and for this reason, the superfine powder that the powder that cyclone collector can be collected is collected with filter be mixed, and mixed powder is for next procedure.
Beneficial effect of the present invention:
1, in the time of alloy melting, T
2o
3oxide micropowder enters Grain-Boundary Phase, has suppressed grain growth, and rich neodymium is evenly distributed mutually, is conducive to improve magnetic property and the decay resistance of magnet.
2, when airflow milling powder, part T
2o
3oxide micropowder enters in the superfine powder of filter collection, has improved the oxidation resistance of superfine powder, and superfine powder can be mixed with the powder that cyclone collector is collected, and has not only improved stock utilization, has also improved the performance of magnet.
3, in the time of sintering, there is rare earth diffusion and displacement reaction, be distributed in R
2(Fe
1-xco
x)
14b phase T around
2o
3heavy rare earth element in oxide powder and R
2(Fe
1-xco
x)
14the B mutually Nd of periphery replaces, and forms the higher ZR of heavy rare earth content
2(Fe
1-xco
x)
14b phase, ZR
2(Fe
1-xco
x)
14b is enclosed in R mutually
2(Fe
1-xco
x)
14the periphery of B phase, forms ZR
2(Fe
1-xco
x)
14b surrounds R mutually
2(Fe
1-xco
x)
14the new construction principal phase of B phase; Nd is preferentially combined with O after entering crystal boundary, forms small Nd
2o
3particulate, Nd
2o
3particulate effectively suppresses ZR in crystal boundary
2(Fe
1-xco
x)
14growing up of B phase, especially Nd
2o
3when particle is positioned at the intersection of more than two crystal grain, effectively suppressing the fusion of crystal grain, limit the abnormal growth of crystal grain, obviously improved the coercive force of magnet, there is Nd in the crystal boundary intersection that therefore a distinguishing feature of the present invention is crystal grain more than two
2o
3particulate.
Embodiment
Further illustrate remarkable result of the present invention below by the contrast of embodiment.
Embodiment 1
Choose magnet composition Nd
30dy
1co
1.2cu
0.1b
0.9al
0.1fe
surplusalloy raw material is heated to more than 500 DEG C under vacuum condition, is filled with afterwards argon gas continuation heating and R-Fe-B-M raw material is melted and be refined into molten alloy, in this process, adds T
2o
3oxide micropowder, T
2o
3oxide micropowder is Dy
2o
3, Tb
2o
3,the content of oxide micropowder is in table 1, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet, use continous vacuum hydrogen crushing furnace hydrogen broken, first alloy sheet is packed into the charging basket playing, order is sent into the suction hydrogen chamber of continuous hydrogen crushing furnace, Heating Dehydrogenation chamber, cooling chamber is inhaled respectively hydrogen, Heating Dehydrogenation and cooling, then the alloy after hydrogen is broken under protective atmosphere packs storage tank into, after hydrogen fragmentation, carry out batch mixing, the laggard row airflow milling of batch mixing, under nitrogen protection with delivering to pressing under magnetic field press-molding of the present invention after batch mixer batch mixing, oxygen content 150ppm in guard box, alignment magnetic field 1.8T, 3 DEG C of mould cavity temperatures, magnetic patch size 62 × 52 × 42mm, direction of orientation is 42 dimensional directions, after shaping, in guard box, encapsulate, taking-up waits static pressure, hydrostatic pressure 200MPa, magnetic patch is sent into afterwards to continuous vacuum sintering furnace under nitrogen protection and carried out sintering, under the drive of transmission device, the bin that magnetic patch is housed enters the preparation room of continuous vacuum sintering furnace successively, preheating degreasing chamber, the first degas chamber, the second degas chamber, presintering chamber, agglomerating chamber, timeliness chamber and cooling chamber carry out preheating and slough organic impurities, and then Heating Dehydrogenation is degassed, presintering, sintering, timeliness and cooling, after cooling, from continuous vacuum sintering furnace, take out to be sent to again and in vacuum aging stove, carry out secondary ageing, secondary ageing temperature 450-650 DEG C, rapid cooling after secondary ageing, make sintered NdFeB rear-earth permanent magnet, sintered NdFeB rear-earth permanent magnet is made Nd-Fe-B rare-earth permanent magnet device through machining and surface treatment again.; Can find out Dy by table 1
2o
3, Tb
2o
3content is within the scope of 0.01-1.4%, and magnet performance obviously improves, Dy
2o
3, Tb
2o
3content is within the scope of 0.1-0.8%, and magnet performance significantly improves, Dy
2o
3, Tb
2o
3content is within the scope of 0.1-0.4%, and magnet performance is best.
Comparative example 1
Choose the magnet composition Nd identical with embodiment 1
30dy
1co
1.2cu
0.1b
0.9al
0.1fe
surplusalloy raw material, adopt conventional method of smelting to make alloy sheet, and then adopt conventional technique to carry out hydrogen fragmentation, airflow milling powder, pressing under magnetic field, sintering and timeliness to make magnet, the performance of magnet is also listed table 1 in, can find out technological progress of the present invention by contrast.
The content of table 1 oxide micropowder and magnet performance
Embodiment 2
Choose magnet composition (Pr
0.2nd
0.8)
22.5dy
2.5co
1.2cu
0.3b
0.9al
0.2fe
surplusalloy raw material and T
2o
3oxide micropowder is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating R-Fe-B-M raw material is fused into alloy, after refining by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, molten alloy forms alloy sheet, T after rotating roller is cooling
2o
3oxide micropowder is Al
2o
3, Y
2o
3,the content of oxide micropowder and magnet performance are in table 2, use continous vacuum hydrogen crushing furnace hydrogen broken, first alloy sheet is packed into the charging basket playing, order is sent into the suction hydrogen chamber of continuous hydrogen crushing furnace, Heating Dehydrogenation chamber, cooling chamber is inhaled respectively hydrogen, Heating Dehydrogenation and cooling, then the alloy after hydrogen is broken under protective atmosphere packs storage tank into, after hydrogen fragmentation, carry out batch mixing, after batch mixing, carry out nitrogen protection airflow milling powder, first broken the hydrogen after batch mixing powder is packed into the hopper of feeder, by feeder, powder is joined to mill chamber, utilize the high velocity air of nozzle ejection to carry out grinding, powder after grinding enters centrifugal separation polling powder with air-flow, the fine powder that reaches granularity enters cyclone collector after by separation wheel sorting and collects, a small amount of fine powder can be discharged along with the air-flow of cyclone collector blast pipe, entering rear cyclone collector collects again, the powder that the powder that cyclone collector is collected and rear cyclone collector are collected imports in rewinding tank by collector.Under nitrogen protection with adopting automatic pressing under magnetic field method of the present invention moulding after batch mixer batch mixing, oxygen content 150ppm in guard box, alignment magnetic field 1.8T, 3 DEG C of mould cavity temperatures, magnetic patch size 62 × 52 × 42mm, direction of orientation is 42 dimensional directions, sends into continous vacuum pre-burning freezing of a furnace and carry out presintering after shaping, sends into continous vacuum sintering aging furnace and carry out sintering, high-temperature aging, pre-cooled, low temperature aging after presintering; Can find out Al by table 2
2o
3, Y
2o
3content is within the scope of 0.01-0.9%, and magnet performance obviously improves, Al
2o
3, Y
2o
3content is within the scope of 0.01-0.6%, and magnet performance significantly improves, Al
2o
3, Y
2o
3content is within the scope of 0.1-0.3%, and magnet performance is best.
Comparative example 2
Choose the magnet composition Nd identical with embodiment 1
30dy
1co
1.2cu
0.1b
0.9al
0.1fe
surplusalloy raw material, adopt conventional method of smelting to make alloy sheet, and then adopt conventional technique to carry out hydrogen fragmentation, airflow milling powder, pressing under magnetic field, sintering and timeliness to make magnet, the performance of magnet is also listed table 2 in, can find out technological progress of the present invention by contrast.
The content of table 2 oxide micropowder and magnet performance
By relatively further illustrating of embodiment and comparative example, adopt technology of the present invention obviously to improve the performance of magnet, be the technology and equipment technology that has very much development.
Claims (13)
1. the manufacture method of a permanent-magnet rare-earth NdFeB alloy, it is characterized in that: first R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating and R-Fe-B-M raw material melted and be refined into molten alloy, in this process, add T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet;
Wherein R represents more than one in the rare earth element that comprises Nd;
One or more in M representative element Al, Co, Nb, Ga, Zr, Cu, V, Ti, Cr, Ni, Hf element;
T
2o
3represent oxide Dy
2o
3, Tb
2o
3, Ho
2o
3, Y
2o
3, Al
2o
3, Ti
2o
3in one or more;
Described T
2o
3the addition of oxide micropowder: 0≤T
2o
3≤ 2%.
2. the manufacture method of a kind of permanent-magnet rare-earth NdFeB alloy according to claim 1, is characterized in that: first by R-Fe-B-M raw material and T
2o
3oxide micropowder is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating R-Fe-B-M raw material is fused into alloy, after refining by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, molten alloy forms alloy sheet after rotating roller is cooling.
3. the manufacture method of a kind of permanent-magnet rare-earth NdFeB alloy according to claim 1, it is characterized in that: first R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, being filled with afterwards argon gas continuation heating is fused into R-Fe-B-M raw material alloy and carries out refining, refining temperature, at 1400-1470 DEG C, adds T
2o
3after oxide micropowder by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, transfer roller rotating speed 1-4m/s, molten alloy forms alloy sheet after rotating roller is cooling.
4. the manufacture method of a kind of permanent-magnet rare-earth NdFeB alloy according to claim 1, it is characterized in that: first R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating and R-Fe-B-M heating raw materials melted and be refined into molten alloy, in this process, add T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet, alloy sheet leaves falls that on rotating disk, to carry out secondary cooling after rotation copper roller immediately.
5. the manufacture method of a kind of permanent-magnet rare-earth NdFeB alloy according to claim 1, it is characterized in that: first R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating and R-Fe-B-M heating raw materials melted and be refined into molten alloy, in this process, add T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet, alloy sheet falls after leaving rotation copper roller immediately, lower backward alloy sheet carries out fragmentation, enters rewinding tank after fragmentation.
6. the manufacture method of a kind of permanent-magnet rare-earth NdFeB alloy according to claim 1, it is characterized in that: first R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, be filled with afterwards argon gas continuation heating and R-Fe-B-M heating raw materials melted and be refined into molten alloy, in this process, add T
2o
3oxide micropowder, afterwards by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, form alloy sheet, alloy sheet leaves falls that on coldplate, to carry out secondary cooling after rotation copper roller immediately, the cooling rear alloy sheet of secondary carries out fragmentation, after fragmentation, be incubated, with inert gas, alloy sheet is cooling after insulation.
7. a manufacture method for Fe-B rare-earth permanent magnet, is characterized in that: manufacture method is as follows:
First R-Fe-B-M raw material is heated to more than 500 DEG C under vacuum condition, is filled with afterwards argon gas continuation heating and R-Fe-B-M raw material is melted and be refined into molten alloy, in this process, add T
2o
3oxide micropowder, afterwards the aluminium alloy of melting is formed to alloy sheet by trough casting to being with in water-cooled rotating roller, afterwards alloy sheet is carried out to hydrogen fragmentation, the broken laggard row airflow milling powder of hydrogen, pressing under magnetic field, sintering and timeliness operation are made Fe-B rare-earth permanent magnet, then make various rare earth permanent magnet devices through machining and surface treatment; Wherein:
R represents more than one in rare earth element;
One or more in M representative element Al, Co, Nb, Ga, Zr, Cu, V, Ti, Cr, Ni, Hf element;
T
2o
3represent oxide Dy
2o
3, Tb
2o
3, Ho
2o
3, Y
2o
3, Al
2o
3, Ti
2o
3in more than one;
HR represent Dy, Tb, Ho, Y rare earth element more than one.
8. according to claim
7the manufacture method of described a kind of Fe-B rare-earth permanent magnet, it is characterized in that: the broken broken equipment of continuous hydrogen that adopts of described hydrogen, the material frame of alloy sheet is housed, under the driving of transmission device, order is by suction hydrogen chamber, Heating Dehydrogenation chamber, the cooling chamber of the broken equipment of continuous hydrogen, enter discharge chamber by outlet valve, alloy sheet after hydrogen is broken is derived from material frame, fall into the storage tank of discharge chamber bottom, under nitrogen protection, storage tank is encapsulated, material frame shifts out from the discharge door of discharge chamber, again circular flow after charging; The suction hydrogen temperature 50-350 DEG C of described suction hydrogen chamber, described Heating Dehydrogenation chamber is more than one, desorption temperature 600-900 DEG C, described cooling hydrogen chamber is more than one.
9. according to claim
7the manufacture method of described a kind of Fe-B rare-earth permanent magnet; it is characterized in that: first described airflow milling powder joins batch mixer by the alloy sheet after hydrogen fragmentation and carry out front batch mixing; front batch mixing carries out or adds lubricant and antioxidant under nitrogen protection; after batch mixing, adopt nitrogen protection airflow milling powder; the powder of after airflow milling powder, whirlwind collector being collected is put into batch mixer and carries out rear batch mixing together with the fine powder of collecting afterwards; rear batch mixing carries out under nitrogen protection, and mixing time is more than 10 minutes.
10. according to claim
7the manufacture method of described a kind of Fe-B rare-earth permanent magnet; it is characterized in that: described pressing under magnetic field; first the powder after rear batch mixing is sent under nitrogen protection to nitrogen protection Magnetic field press and carried out magnetic field orientating moulding; after moulding, under nitrogen protection, with plastics or gum cover, magnetic patch is packed; make after magnetic patch and isolated from atmosphere; magnetic patch is taken out in batches; send into isostatic pressing machine and wait static pressure; Deng the nitrogen protection material feeding box of with packaging, magnetic patch being sent into vacuum sintering furnace after static pressure; in nitrogen protection material feeding box, by gloves, magnetic patch is removed to packaging, pack sintering magazine into.
The manufacture method of 11. a kind of Fe-B rare-earth permanent magnets according to claim 7, is characterized in that: described Nd-Fe-B permanent magnet is made up of principal phase and Grain-Boundary Phase, and principal phase has R
2(Fe, Co)
14b structure, wherein principal phase from the heavy rare earth HR content in inside 1/3 scope of outer rim the heavy rare earth HR content higher than principal phase center, in Grain-Boundary Phase, there is small Nd
2o
3particulate, R represent comprise Nd rare earth element more than one, HR represents more than one in Dy, Tb, Ho, Y rare earth element.
The manufacture method of 12. a kind of Fe-B rare-earth permanent magnets according to claim 7, is characterized in that: the structure of described Nd-Fe-B permanent magnet has at R
2(Fe
1-xco
x)
14the surrounding of B crystal grain surrounds heavy rare earth content higher than R
2(Fe
1-xco
x)
14the ZR of B phase
2(Fe
1-xco
x)
14the structure of B phase, ZR
2(Fe
1-xco
x)
14b phase and R
2(Fe
1-xco
x)
14between B without Grain-Boundary Phase, ZR
2(Fe
1-xco
x)
14between B phase, connect by Grain-Boundary Phase; In literary composition, ZR is illustrated in the rare earth higher than the phase of the content of the heavy rare earth in average content of rare earth of heavy rare earth content in crystalline phase; 0≤x≤0.5.
The manufacture method of 13. a kind of Fe-B rare-earth permanent magnets according to claim 7, is characterized in that: more than two ZR in the structure of described Nd-Fe-B permanent magnet
2(Fe
1-xco
x)
14in the Grain-Boundary Phase of the intersection of B phase crystal grain, there is small Nd
2o
3particulate.
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| CN108962581A (en) * | 2018-07-02 | 2018-12-07 | 江苏博瑞通磁业有限公司 | A kind of high voltage vacuum permanent magnet switch preparation method of integral radiation ring |
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| CN112582164A (en) * | 2019-09-29 | 2021-03-30 | 京磁材料科技股份有限公司 | Sintered Nd-Fe-B rapid hardening alloy Nd-rich phase grain boundary doping method |
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