CN103996524A - Method for manufacturing La-and-Ce-contained neodymium iron boron rare earth permanent magnet - Google Patents
Method for manufacturing La-and-Ce-contained neodymium iron boron rare earth permanent magnet Download PDFInfo
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Abstract
The invention discloses a method for manufacturing a La-and-Ce-contained neodymium iron boron rare earth permanent magnet. Raw materials are formed by LR-Fe-B-Ma alloy, HR-Fe-B-Mb alloy and metallic oxide micro powder, wherein the LR represents four rare earth elements which include La, Ce, Nd and Pr, the HR represents one or more rare earth elements which include Dy or Tb, the Ma represents one or more of Al, Co, Nb, Ga, Zr and Cu, and the Mb represents one or more of Al, Co, Nb, Ga, Zr, Cu and Mo. The manufacturing method includes the following working procedures: LR-Fe-B-Ma alloy smelting, HR-Fe-B-Mb alloy smelting, alloy hydrogen decrepitation, metallic oxide micro powder surface adsorbing and making, magnetic field forming, sintering and aging, and the neodymium iron boron rare earth permanent magnet is manufactured.
Description
Technical field
The invention belongs to rare earth permanent magnet field, particularly relate to a kind of manufacture method of the Fe-B rare-earth permanent magnet containing La and Ce.
Background technology
Fe-B rare-earth permanent magnet, 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, Fe-B rare-earth permanent magnet 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 the Fe-B rare-earth permanent magnet of SUMITOMO CHEMICAL metal invention, announced characteristic, composition and the manufacture method of Fe-B rare-earth permanent magnet, confirmed that principal phase is Nd
2fe
14b phase, Grain-Boundary Phase is mainly comprised of rich Nd phase, rich B phase and rare earth oxide impurity etc.; Fe-B rare-earth permanent magnet is used widely with its excellent magnetic property, and is called as permanent magnetism king; The US Patent No. 5.645,651 of authorizing for 1997 is further clear and definite, and interpolation Co element and principal phase have tetragonal phase structure.
Along with the extensive use of Nd-Fe-B rare-earth permanent magnet, rare earth shortage, the especially heavy rare earth element shortage of resources that obviously becomes that becomes more and more, rare earth price one rises and rises again; For this reason, people have carried out many explorations, occur pairing technology for gold, implantation technique, improvement or restructuring Grain-Boundary Phase technology etc.; The disclosed heavy rare earth hydride nano-particle doped technology of preparing neodymium iron boron of patent CN101521069B, first adopt strip casting alloying sheet, then carry out hydrogen fragmentation and airflow milling powder, then the heavy rare earth hydride nano-particle that adopts physics vapor phase deposition technology to produce is mixed with aforesaid powder, by common process such as pressing under magnetic field, sintering, manufacture neodymium iron boron magnetic body again, although this patent has been found the coercitive method of raising magnet, batch production existing problems.
Patent CN1688000 discloses the method at increasing sintering Nd-Fe-B coercive force by adding nano-oxide in crystal boundary phase, the method is the improvement of pairing gold method, first main-phase alloy and Grain-Boundary Phase adopt respectively casting technique to make Nd Fe B alloys ingot or make rapid hardening alloy sheet by rapid hardening thin slice technique, adopt the quick-fried method of hydrogen or disintegrating machine to carry out respectively fragmentation, broken laggard row airflow milling abrasive dust, makes respectively the powder of 2-10 μ m; Then in Grain-Boundary Phase powder, add the nano-oxide of process dispersion treatment and the antioxidant of 1-10% of weight 2-20%, in batch mixer, evenly mix; Then the crystal-boundary phase alloy powder through nano-oxide doping is mixed with main-phase alloy powder, crystal-boundary phase alloy powder accounts for the 1-20% of total weight, adds the gasoline of 0.5-5% simultaneously, in batch mixer, mixes, and makes mixed-powder; Mixed-powder is compressing in the magnetic field of 1.2-2.0T makes neodymium iron boron magnetic body by oversintering; The core technology of the present patent application is to be dispersed in Grain-Boundary Phase by nano-oxide, coercive force to modified grain boundary phase with raising neodymium iron boron magnetic body, this technology principal phase and Grain-Boundary Phase be melting and powder process and repeatedly mixing respectively, because neodymium iron boron fine powder is very easy to oxidation, complex process is wayward; During main-phase alloy melting, because content of rare earth is low, approach Nd in addition
2fe
14b phase constituent, easily produces α-Fe, reduces remanent magnetism; During melting Grain-Boundary Phase, easily produce principal phase, affect coercive force; Also have because nano-oxide surface area is large, have the danger of blast when transportation, use, nano-oxide is made difficulty, and cost is high, affects the application of neodymium iron boron.
Summary of the invention
The present invention passes through research and probe, find a kind of Fe-B rare-earth permanent magnet and manufacture method containing La and Ce, overcome the shortcoming of prior art, obviously improve magnetic energy product, coercive force, corrosion resistance and the processing characteristics of Nd-Fe-B rare-earth permanent magnet, be suitable for batch production, reduced the consumption of the heavy rare earth element of expensive and scarcity of resources, to expanding the application market of Fe-B rare-earth permanent magnet, the especially energy-conservation application important in inhibiting with controlling motor, auto parts and components, new-energy automobile, field of wind power generation.The present invention also finds to improve the inhibiting grain growth of magnetic energy product, coercive force, corrosion resistance and the processing characteristics of Nd-Fe-B rare-earth permanent magnet, especially La and Ce's adds, in crystal boundary, form the oxide fine particle of La and Ce, the oxide fine particle of La and Ce effectively suppresses the abnormal grain growth of sintering process, has produced with principal phase PR
2(Fe
1-x-yco
xal
y)
14b is core mutually, principal phase ZR
2(Fe
1-w-nco
wal
n)
14b is enclosed in principal phase PR mutually
2(Fe
1-x-yco
xal
y)
14the periphery of B phase, ZR
2(Fe
1-w-nco
wal
n)
14b phase and PR
2(Fe
1-x-yco
xal
y)
14b mutually between without the compound principal phase structure of Grain-Boundary Phase.
A high-performance Ne-Fe-B rare-earth permanent magnet containing La and Ce, is comprised of following percentage by weight component: 19≤Ra≤32; 0.8≤B≤1.2; 0≤M≤4.0; 0.5≤Rb≤10; 30≤Ra+Rb≤33; All the other are Fe and impurity;
Wherein: Ra represents La, Ce, Pr and tetra-kinds of rare earth elements of Nd;
Rb represents one or more in Dy, Tb, Ho, Gd;
M represents more than one in Al, Co, Nb, Ga, Zr, Cu, Mo element;
Two kinds of rare earth elements of described Pr and Nd exist: Pr/Nd=0.25-0.45;
The content of described Al: 0.1≤Al≤0.9; Preferred 0.2≤Al≤0.5;
The content of described Co: 0≤Co≤5; Preferred 0.8≤Co≤2.4;
The content of described Cu: 0≤Cu≤0.5; Preferred 0.1≤Cu≤0.2;
The content of described Ga: 0≤Ga≤0.3; Preferred 0.1≤Ga≤0.2;
The content of described Nb: 0≤Nb≤0.9; Preferred 0.1≤Nb≤0.6;
The content of described Zr: 0≤Zr≤0.5; Preferred 0.05≤Zr≤0.2;
The described Fe-B rare-earth permanent magnet containing La and Ce is comprised of compound principal phase and Grain-Boundary Phase, and compound principal phase is with principal phase PR
2(Fe
1-x-yco
xal
y)
14b is core mutually, principal phase ZR
2(Fe
1-w-nco
wal
n)
14b is enclosed in principal phase PR mutually
2(Fe
1-x-yco
xal
y)
14the periphery of B phase, ZR
2(Fe
1-w-nco
wal
n)
14b phase and PR
2(Fe
1-x-yco
xal
y)
14b mutually between without Grain-Boundary Phase, wherein ZR represents that the content of the heavy rare earth in the rare earth element of principal phase is higher than the rare earth element sum of average heavy rare earth content, PR represents that the content of the heavy rare earth in the rare earth element of principal phase is lower than the rare earth element sum of average heavy rare earth content, 0≤x≤0.3,0≤y≤0.2,0≤w≤0.3,0≤n≤0.2, in Grain-Boundary Phase, have Ra oxide fine particle and oxidation Nd particulate, the oxygen content in Grain-Boundary Phase is higher than the oxygen content in principal phase;
Test finds that described w, n are less, and magnetic property is higher, reaches maximum when w=0, n=0, i.e. the core principal phase PR of compound principal phase
2(Fe
1-x-yco
xal
y)
14b is PR mutually
2fe
14during B, performance is best.
The described Fe-B rare-earth permanent magnet containing La and Ce is comprised of compound principal phase and Grain-Boundary Phase, and average grain size is within the scope of 3-15 μ m; Preferred average grain size is within the scope of 5-7 μ m.
In the Grain-Boundary Phase of the described Fe-B rare-earth permanent magnet containing La and Ce, there is oxidation Ce and oxidation Nd particulate.
In the Grain-Boundary Phase of the described Fe-B rare-earth permanent magnet containing La and Ce, there is Ce
2o
3and Nd
2o
3particulate.
Two above ZR of the described Fe-B rare-earth permanent magnet containing La and Ce
2(Fe
1-w-nco
wal
n)
14in the Grain-Boundary Phase of the intersection of B phase crystal grain, there is oxidation La and oxidation Nd particulate.
The present invention realizes by following manufacture method:
Raw material consists of LR-Fe-B-Ma alloy, HR-Fe-B-Mb alloy and metal oxide micro mist, four kinds of rare earth elements that wherein LR representative comprises La, Ce, Nd and Pr; One or more in Ma representative element Al, Co, Nb, Ga, Zr, Cu element; Mb represents one or more in containing element Al, Co, Nb, Ga, Zr, Cu, Mo element; More than one rare earth elements that HR representative comprises Dy or Tb; Preferred metal oxide micro mist is not for comprising one or more of the rare-earth oxide of lanthana, cerium oxide and Al, Co, Nb, Ga, Zr, Cu, V, Mo, Fe, Zn metal oxide; Further preferred metal oxide is for comprising Dy
2o
3, Tb
2o
3, Al
2o
3in one or more.
Preferred Ma representative element Al, Co, Cu; Further preferred Ma representative element Al; Further, preferably not containing Ma, LR-Fe-B-Ma alloy is LR-Fe-B alloy; When in LR-Fe-B-Ma alloy, Ma reduces, remanent magnetism and the magnetic energy product of neodymium iron boron magnetic body increase, technology stability variation, and during not containing Ma there is maximum in remanent magnetism and magnetic energy product.
Preferred Mb representative element Al, Co, Nb, Ga, Zr, Cu, Mo; Further preferred Mb represents one or more in containing element Al, Co, Nb, Ga, Cu element; Further preferred Mb representative element Al, Co, Ga, Zr, Cu; Further preferred Mb representative element Al, Co, Ga, Cu again; In HR-Fe-B-Mb alloy when Mb representative element Al, Co, Ga, Cu, the refinement of HR-Fe-B-Mb alloy grain, has obtained magnetic property and the decay resistance of good magnet; When Mb representative element Al, Co, Ga, Zr, Cu, the further refinement of HR-Fe-B-Mb alloy grain, crystal boundary are evenly distributed; When Mb representative element Al, Co, Nb, Ga, Zr, Cu, HR-Fe-B-Mb alloy grain further improves, crystal boundary distribution optimization.
Metal oxide micro mist is preferably Tb
2o
3time magnetic property the highest, be preferably Dy
2o
3time magnetic property take second place, add Al
2o
3time magnetic property lower than Dy
2o
3, but corrosion resistance is best; Combine and add Tb
2o
3, Dy
2o
3, Al
2o
3, not only improve magnetic property but also reduce costs, can also improve the corrosion resistance of magnet; The preferred size of micro mist is less than 2 μ m; Further preferred granularity 20-100nm; Preferred granularity 0.5-1 μ m further; Add metal oxide micro mist, during airflow milling powder, the surface of Grain-Boundary Phase and principal phase is further pulverized and be adsorbed on to metal oxide micro mist; During sintering because the adhesion of La and oxygen is the strongest, under uniform temperature and vacuum degree, La is preferentially combined with oxygen, forms oxidation La particulate, the metallic element displacing in metal oxide micro mist enters principal phase or is enclosed in the periphery of principal phase, obviously improves coercive force and the corrosion resistance of magnet; In magnet, during without La, the priority of being combined with oxygen is: Ce, Pr, Nd.
Manufacture method comprises following operation:
(1) LR-Fe-B-Ma alloy melting
LR-Fe-B-Ma raw material induction heating under vacuum or argon shield 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, and the average grain size of alloy sheet is at 1.5-3.5 μ m.
(2) HR-Fe-B-Mb alloy melting
HR-Fe-B-Mb raw material induction heating under vacuum or argon shield 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 average grain size of described alloy sheet is at 0.1-2.9 μ m.
(3) hydrogen of alloy is broken
Pack LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy into vacuum hydrogen crushing furnace, after vacuumizing, be filled with hydrogen and inhale hydrogen, inhale hydrogen temperature 100-300 ℃, inhale hydrogen and finish to heat and vacuumize dehydrogenation, desorption temperature 350-900 ℃, dehydrogenation time 3-15 hour, afterwards that alloy is cooling.
Described vacuumize dehydrogenation after, or be filled with quantitative hydrogen in 100-600 ℃ of temperature range, afterwards alloy is continued cooling.
(4) metal oxide micro mist adsorption and powder process
The LR-Fe-B-Ma alloy that hydrogen is processed and HR-Fe-B-Mb alloy and metal oxide micro mist join batch mixer and carry out batch mixing; during batch mixing or add lubricant and antioxidant; batch mixing carries out under nitrogen protection; mixing time is greater than 30 minutes; the laggard row airflow milling powder of batch mixing, powder mean particle sizes scope 1-3.3 μ m.
The described LR-Fe-B-Ma alloy that hydrogen is processed and HR-Fe-B-Mb alloy and metal oxide micro mist join batch mixer and carry out batch mixing, during batch mixing or also add quantitative hydrogen.
Described airflow milling powder; or under nitrogen atmosphere; the hopper that powder after batch mixing is packed into feeder top; by feeder, powder is joined to mill chamber; utilize the high velocity air of nozzle ejection to carry out grinding; powder after grinding rises with air-flow; by entering cyclone collector after separation wheel, collect; part is coated with the fine powder of metal oxide micro mist and discharges with air-flow from the blast pipe of cyclone collector; be collected in cyclone collector gatherer afterwards; under nitrogen protection, carry out afterwards batch mixing, obtain alloy powder.
(5) pressing under magnetic field, sintering and timeliness
The alloy powder of preorder carried out under nitrogen protection to pressing under magnetic field, under vacuum or argon shield, carry out sintering and timeliness afterwards, make Fe-B rare-earth permanent magnet.
Described pressing under magnetic field; or under nitrogen protection, the alloy powder of preorder is sent into nitrogen protection lutation magnetic field presser; after weighing, put into the mould cavity assembling; carry out afterwards pressing under magnetic field; after moulding, mould is withdrawn into dress powder position; opening mould takes out magnetic patch; under nitrogen protection, with plastics or gum cover, magnetic patch is packed; then magnetic patch is sent into isostatic pressing machine waits static pressure; Deng after static pressure, with packing, magnetic patch is sent into the nitrogen protection material feeding box of vacuum sintering furnace; in nitrogen protection material feeding box, by gloves, magnetic patch is removed to packing, pack sintering magazine into.
Described sintering and timeliness, or the magazine in the nitrogen protection material feeding box of vacuum sintering furnace is sent into the heating chamber of sintering furnace under nitrogen protection, vacuumize rear heating, first at 200-400 ℃ of heating 2-10 hour, again at 400-600 ℃ of heating 5-12 hour, 600-1050 ℃ of heating, within 5-20 hour, carry out presintering afterwards, after presintering, 950-1070 ℃ of heating, within 1-6 hour, carry out sintering, after sintering, carry out timeliness of 800-950 ℃ and the secondary ageing of 450-650 ℃, rapid cooling after secondary ageing, make sintered Nd-Fe-B permanent magnet, sintered magnet is made various rare earth permanent magnet devices through machining and surface treatment again.
After described presintering, the density of magnet is at 7-7.4g/cm
3, the magnet density after sintering is at 7.5-7.7g/cm
3.
The manufacture method of the described high-performance Ne-Fe-B rare-earth permanent magnet with compound principal phase, is characterized in that: described metal oxide micro mist is the Dy after 600-1200 ℃ of heat treatment
2o
3micro mist.
Described metal oxide micro mist is Al
2o
3micro mist.
Described alloy melting; raw material induction heating under vacuum or argon shield is fused into alloy; 1400-1470 ℃ of refining; after refining by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller; transfer roller rotating speed 1-10m/s; molten alloy forms alloy sheet after rotating roller is cooling, and alloy sheet leaves falls that on rotating disk, to carry out secondary cooling after rotation copper roller immediately, after alloy sheet is cooling, comes out of the stove.
The described alloy melting of further improvement technology; raw material induction heating under vacuum or argon shield is fused into alloy; 1400-1470 ℃ of refining; after refining by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, transfer roller rotating speed 1-10m/s, molten alloy forms alloy sheet after rotating roller is cooling; alloy sheet falls after leaving rotation copper roller immediately; lower backward alloy sheet carries out fragmentation, enters rewinding case after fragmentation, with inert gas, alloy sheet is cooling afterwards.
Further improve the described alloy melting of technology, raw material induction heating under vacuum or argon shield is fused into alloy, 1400-1470 ℃ of refining, after refining 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 temperature of alloy sheet is greater than 400 ℃ and is less than 700 ℃, alloy sheet leaves falls that on coldplate, to carry out secondary cooling after rotation copper roller immediately, the cooling rear alloy sheet temperature of secondary is less than 400 ℃, then carry out fragmentation, after fragmentation, be incubated, holding temperature 200-600 ℃, with inert gas, alloy sheet is cooling after insulation.
Described HR-Fe-B-Mb alloy melting operation, or first just HR-Fe-B-Mb raw material induction heating under vacuum or argon shield is fused into alloy, after refining, the aluminium alloy of melting is cast in junker mold, form alloy pig or by trough casting to being with in water-cooled rotating roller, molten alloy forms alloy sheet after rotating roller is cooling, then alloy pig or alloy sheet are broken into the fritter that the length of side is less than 10mm, then alloy block is joined in the water jacketed copper crucible of arc heating formula vacuum furnace under argon gas atmosphere, with the heating of electric arc alloy piece, make alloy block be fused into molten alloy liquid, outer rim with water-cooled High Rotation Speed molybdenum wheel contacts with the aluminium alloy of melting, molten alloy liquid is thrown out of, form fibrous HR-Fe-B-Mb alloy, the average grain size of alloy is at 0.6-0.9 μ m.
Described is fused into alloy by HR-Fe-B-Mb raw material induction heating under vacuum or argon shield, after refining by the aluminium alloy of melting by trough casting to being with in water-cooled rotating roller, molten alloy forms after alloy sheet after rotating roller is cooling, again alloy sheet is broken into the alloy block that the length of side is less than 10mm, then alloy block is joined in the water jacketed copper crucible of arc heating formula vacuum quick quenching furnace under argon gas atmosphere, with the heating of electric arc alloy piece, make alloy block be fused into molten alloy liquid, outer rim with water-cooled High Rotation Speed molybdenum wheel contacts with the aluminium alloy of melting, molten alloy liquid is thrown out of, form fibrous HR-Fe-B-Mb alloy, the average grain size of alloy is at 0.6-1.9 μ m.
The described preferred average grain size 2-3 of LR-Fe-B-Ma alloy μ m; The preferred average grain size 0.6-1.9 of HR-Fe-B-Mb alloy μ m.
The present invention, by improving magnet composition and production technology, obviously improves magnetic property, and especially coercive force and magnetic energy product are significantly improved and enhanced; Under identical coercitive condition, obviously reduce the consumption of heavy rare earth, saved rare rare earth resources; Because Nd-Fe-B rare-earth permanent magnet is easily oxidized, have a strong impact in industries such as automobile, wind power generations and use, adopt the technology of the present invention, obviously reduce weightlessness, improved the oxidation resistance of magnet, expanded the range of application of Nd-Fe-B rare-earth permanent magnet;
Due to La
2fe
14b, Ce
2fe
14remanent magnetism and the coercive force of B are starkly lower than Nd
2fe
14b, Pr
2fe
14b, Dy
2fe
14b, Tb
2fe
14b, especially coercive force is much lower, generally believes, adds La and Ce can reduce magnetic property in magnet, the present invention passes through further investigation, and discovery is by the method for remanent magnetism, coercive force, magnetic energy product and the corrosion resistance of interpolation La and Ce raising magnet and new production technology.
Embodiment
Contrast below by embodiment further illustrates remarkable result of the present invention.
Embodiment 1
By table one embodiment 1 composition, choose respectively LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy 600Kg melting, under molten condition by alloy casting to being with cooling formation alloy sheet on water-cooled rotation copper roller, in fusion process, by adjustment, rotate the cooling rate of adjustment of rotational speed LR-Fe-B-Ma alloy and the HR-Fe-B-Mb alloy of copper roller, the average grain size that obtains LR-Fe-B-Ma alloy is 2.8 μ m; The average grain size of HR-Fe-B-Mb alloy is 1.8 μ m; By the listed ratio of table one, choose LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy sheet carries out hydrogen fragmentation, alloy sheet after the hydrogen fragmentation metal oxide listed with table one put into batch mixer together with the ratio of table one, batch mixing under nitrogen protection, mixing time 60 minutes, the laggard row airflow milling powder of batch mixing, together with the superfine powder that the powder that cyclone collector is collected is collected with filter, put into rear batch mixer and carry out rear batch mixing, rear batch mixing also carries out under nitrogen protection, mixing time 90 minutes, the oxygen content of protective atmosphere is less than 100ppm; Deliver to afterwards nitrogen protection magnetic field orientating press-molding; alignment magnetic field 1.8T; 3 ℃ of mould cavity temperatures; magnetic patch size 40 * 30 * 20mm, direction of orientation is 20 dimensional directions, after shaping, in guard box, encapsulates; then take out and wait static pressure; send into afterwards sintering furnace and carry out presintering, 940 ℃ of insulations of pre-sintering temperature 15 hours, presintering density 7.3g/cm
3,, carry out afterwards sintering and twice timeliness, 1070 ℃ of insulations of sintering temperature 1 hour, magnetic patch grinds processing after taking out, and then measures magnetic property and weightlessness, and result is listed table one in, and the magnet weight percentage composition after sintering is after testing: La
0.1ce
0.4(Nd
0.7pr
0.3)
29dy
1.0b
0.9al
0.1co
1.2cu
0.15fe
surplus, magnetic energy product, coercive force and weightless measurement result are also listed table one in.
Comparative example 1
The magnet composition of choosing by table two comparative example 1 is (Nd
0.7pr
0.3)
29.5dy
1.0b
0.9al
0.1co
1.2cu
0.15fe
surplusfirst carry out alloy melting, under molten condition by alloy casting to being with cooling formation alloy sheet on water-cooled rotation copper roller, follow involutory gold plaque carry out hydrogen fragmentation, airflow milling powder, magnetic field orientating press-molding, etc. static pressure, sintering and twice timeliness, grind afterwards processing, then measure magnetic property and weightlessness, result is listed table one in.
Although embodiment 1 is identical with the magnet composition of comparative example 1, adopt the performances such as magnetic energy product, coercive force and weightlessness of the embodiment 1 of the technology of the present invention apparently higher than comparative example 1.
Other components unchanged that keep embodiment 1, only change the changes of contents of Co, and when 0≤Co≤5, metal oxide is within the scope of 0.01-0.05%, and magnetic property is along with Co content increases and changes, and amplitude of variation is less than 4%, and performance is apparently higher than comparative example 1; Scope 0≤Co≤3 of preferred Co, variation diminishes; Scope 1.0≤Co≤2.4 of further preferred Co, performance change is less, lower than 2%; Keep Co content constant, adjust the content of Cu, when 0≤Cu≤0.3, metal oxide is within the scope of 0.01-0.05%, and performance is along with Cu changes of contents amplitude is less than 3%, and performance is apparently higher than comparative example 1; Scope 0.1≤Cu≤0.3 of preferred Cu, performance is along with Cu changes of contents amplitude is less than 2%; The scope of further preferred Cu is 0.1≤Cu≤0.2 preferably, and performance is along with Cu changes of contents amplitude is less than 1%; Test explanation: combine and add Co, Cu and 0.8≤Co≤2.4,0.1≤Cu≤0.2 o'clock, magnetic property and decay resistance are optimum, preferably combine and add Co, Cu and 0.8≤Co≤2.4,0.1≤Cu≤0.2.
Keep embodiment 1 material composition and test method constant, only change kind and the content of metal oxide, evidence, when metal oxide micro mist is Al
2o
3, content range is at 0.01-0.05%, and magnetic property increases with content, and content range is at 0.01-0.08%, and it is 0.01 performance that magnetic property keeps being greater than content; As metal oxide micro mist Dy
2o
3, Tb
2o
3while substituting, there is same rule, Dy
2o
3performance is higher than Al
2o
3, Tb
2o
3performance is higher than Dy
2o
3; The scope of preferable alloy oxide micropowder is at 0.01-0.05%; Further the scope of preferable alloy oxide micropowder is at 0.02-0.03%; Preferred metal oxide is Al
2o
3; Further preferred metal oxide is Dy
2o
3; Further preferred metal oxide is Tb
2o
3; Combine interpolation oxide micropowder magnet performance is further improved, preferably Dy
2o
3and Al
2o
3; Further preferred and Al
2o
3and Tb
2o
3or Tb
2o
3and Dy
2o
3; Preferred Dy further
2o
3, Tb
2o
3and Al
2o
3.
Embodiment 2
By the composition in table one embodiment 2, choose respectively LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy 600Kg melting, under molten condition by alloy casting to being with cooling formation alloy sheet on water-cooled rotation copper roller, in fusion process, by adjustment, rotate the cooling rate of adjustment of rotational speed LR-Fe-B-Ma alloy and the HR-Fe-B-Mb alloy of copper roller, the average grain size that obtains LR-Fe-B-Ma alloy is 2.3 μ m; The average grain size of HR-Fe-B-Mb alloy is 1.3 μ m; By the listed ratio of table one, choose LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy sheet carries out hydrogen fragmentation, alloy sheet after the hydrogen fragmentation metal oxide listed with table one put into batch mixer together with the ratio of table one, batch mixing under nitrogen protection, mixing time 40 minutes, the laggard row airflow milling powder of batch mixing, together with the superfine powder that the powder that cyclone collector is collected is collected with filter, put into rear batch mixer and carry out rear batch mixing, rear batch mixing also carries out under nitrogen protection, mixing time 70 minutes, the oxygen content of protective atmosphere is less than 50ppm; Deliver to afterwards nitrogen protection magnetic field orientating press-molding; alignment magnetic field 1.8T; 4 ℃ of mould cavity temperatures; magnetic patch size 40 * 30 * 20mm, direction of orientation is 20 dimensional directions, after shaping, in guard box, encapsulates; then take out and wait static pressure; send into afterwards sintering furnace and carry out presintering, 910 ℃ of insulations of pre-sintering temperature 10 hours, presintering density 7.2g/cm
3,, carry out afterwards sintering and twice timeliness, 1060 ℃ of insulations of sintering temperature 1 hour, magnetic patch grinds processing after taking out, and then measures magnetic property and weightlessness, and result is listed table one in; Magnet composition after sintering is after testing: La
0.2ce
0.8(Nd
0.75pr
0.25)
24dy
4tb
2co
1cu
0.1b
0.95al
0.2ga
0.1fe
surplus, test result is also listed table one in.
Comparative example 2
According to table two, be selected to and be divided into (Nd
0.75pr
0.25)
25dy
4tb
2co
1cu
0.1b
0.95al
0.2ga
0.1fe
surpluscompare experiment, experimental technique is with comparative example 1, and test result is listed table one equally in.
Generally, while replacing Pr or Nd with Ce, magnetic property obviously declines.By table one, can find out, 1% Ce replaces 1% (Nd
0.75pr
0.25) time, adopt technology magnetic property of the present invention to significantly improve; Keep other constituent contents constant, only change the content of Ce, experiment finds that magnetic property and decay resistance remain unchanged when 0≤Ce≤2.4; When 2.5≤Ce≤3, magnetic property and decay resistance slightly decline; When 3.1≤Ce≤4.5, magnetic property and decay resistance decline and are less than 3%; When 5≤Ce≤9, magnetic property and decay resistance decline and are less than 5%; Therefore preferred 5≤Ce≤9; Further preferred 3.1≤Ce≤4.5; Further preferred 2.5≤Ce≤3 again; Preferred 2.5≤Ce≤3 further.
With La, replace Ce and do experiment, be selected to and be divided into La
1(Nd
0.75pr
0.25)
24dy
4tb
2co
1cu
0.1b
0.95al
0.2ga
0.1fe
surplusdo experiment and obtain above-mentioned identical rule; I.e. preferred 5≤La≤9; Further preferred 3.1≤La≤4.5; Further preferred 2.5≤La≤3 again; Preferred 2.5≤La≤3 further.
Embodiment 3
By the composition in table one embodiment 3, choose respectively LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy 600Kg melting, under molten condition by alloy casting to being with cooling formation alloy sheet on water-cooled rotation copper roller, in fusion process, by adjustment, rotate the cooling rate of adjustment of rotational speed LR-Fe-B-Ma alloy and the HR-Fe-B-Mb alloy of copper roller, the average grain size that obtains LR-Fe-B-Ma alloy is 2.8-3.2 μ m; The average grain size of HR-Fe-B-Mb alloy is 2.1-2.4 μ m; By the listed ratio of table one, choose LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy sheet carries out hydrogen fragmentation, alloy sheet after the hydrogen fragmentation metal oxide listed with table one put into batch mixer together with the ratio of table one, batch mixing under nitrogen protection, mixing time 90 minutes, the laggard row airflow milling powder of batch mixing, together with the superfine powder that the powder that cyclone collector is collected is collected with filter, put into rear batch mixer and carry out rear batch mixing, rear batch mixing also carries out under nitrogen protection, mixing time 60 minutes, the oxygen content of protective atmosphere is less than 150ppm; Deliver to afterwards nitrogen protection magnetic field orientating press-molding, alignment magnetic field 1.5T, magnetic patch size 40 * 30 * 20mm, direction of orientation is 20 dimensional directions, sends into afterwards sintering furnace and carries out presintering, 990 ℃ of insulations of pre-sintering temperature 8 hours, presintering density 7.4g/cm
3,, carry out afterwards sintering and twice timeliness, 1080 ℃ of insulations of sintering temperature 1 hour, magnetic patch grinds processing after taking out, and then measures magnetic property and weightlessness, and result is listed table one in; Magnet composition after sintering is La after testing
1.0ce
0.5(Nd
0.8pr
0.2)
20dy
6ho
2gd
2co
2.4cu
0.2b
1.0al
0.3ga
0.1zr
0.1nb
0.1fe
surplus, test result is also listed table one in.
Comparative example 3
The magnet composition of choosing by table two comparative example 3: (Nd
0.8pr
0.2)
21.5dy
6ho
2gd
2co
2.4cu
0.2b
1.0al
0.3ga
0.1zr
0.1nb
0.1fe
surplusfirst carry out alloy melting, under molten condition by alloy casting to being with cooling formation alloy sheet on water-cooled rotation copper roller, follow involutory gold plaque carry out hydrogen fragmentation, airflow milling powder, magnetic field orientating press-molding, etc. static pressure, sintering and twice timeliness, grind afterwards processing, then measure magnetic property and weightlessness, result is listed table one in
The test result of embodiment 3 and comparative example 3 are compared, and the magnetic property of embodiment 3 and decay resistance, apparently higher than comparative example 3, further illustrate technology of the present invention a little.
By embodiment 1-3 and comparative example 1-3, illustrate, technical method of the present invention has the technical advantage of bright phase; Add Al, Ga, Zr, Nb, to improving magnetic property and the decay resistance of magnet, have a clear superiority in; Preferred 0≤Al≤0.6; Preferred 0≤Ga≤0.2; Preferred 0≤Zr≤0.3; Preferred 0≤Nb≤0.3; Further preferred 0.1≤Al≤0.3; Further preferred 0.05≤Ga≤0.15; Further preferred 0.1≤Zr≤0.2; Further preferred 1≤Nb≤0.2.
The composition of table one, embodiment and comparative example and performance
The composition of the RE permanent magnetic alloy of table two, comparative example:
| Numbering | Composition |
| Comparative example 1 | (Ｎd 0.7Pr 0.3) 29.5Dy 1.0Ｂ 0.9Al 0.1Co 1.2Cu 0.15 Fe Surplus |
| Comparative example 2 | (Nd 0.75Pr 0.25) 25Dy 4Tb 2Co 1Cu 0.1B 0.95Al 0.2Ga 0.1Fe Surplus |
| Comparative example 3 | (Nd 0.8Pr 0.2) 21.5Dy 6Ho 2Gd 2Co 2.4Cu 0.2B 1.0Al 0.3Ga 0.1Zr 0.1Nb 0.1Fe Surplus |
By relatively further illustrating of embodiment and comparative example, adopt technology and equipment of the present invention obviously to improve magnetic energy product, coercive force and the decay resistance of magnet, the present invention adds metal oxide micro mist by the melting respectively of pairing gold, primary fragmentation with when the airflow milling, improved the structure of powder, form the surface of the metal oxide after grinding, reduced magnetic and be further oxidized; La-HR-Fe-B-Mb alloy powder is adsorbed on La-LR-Fe-B-Ma alloy powder around, during sintering, through alloying, forms special structure of the present invention; Compare with oozing Dy technology, the present invention is not limited by the shape and size of magnet, is the technology that has very much development.
Claims (13)
1. contain a manufacture method for the Fe-B rare-earth permanent magnet of La and Ce, it is characterized in that: raw material consists of LR-Fe-B-Ma alloy, HR-Fe-B-Mb alloy and metal oxide micro mist, wherein: four kinds of rare earth elements that LR representative comprises La, Ce, Nd and Pr; More than one rare earth elements that HR representative comprises Dy or Tb; One or more in Ma representative element Al, Co, Nb, Ga, Zr, Cu element; Mb represents one or more in containing element Al, Co, Nb, Ga, Zr, Cu, Mo element; Its manufacture method comprises following operation:
(1) LR-Fe-B-Ma alloy melting
LR-Fe-B-Ma raw material induction heating under vacuum or argon shield 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;
(2) HR-Fe-B-Mb alloy melting
HR-Fe-B-Mb raw material induction heating under vacuum or argon shield 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, then alloy sheet is joined in the water jacketed copper crucible of arc heating formula vacuum quick quenching furnace under argon gas atmosphere, with the heating of electric arc alloy, make alloy melting become molten alloy liquid, outer rim with water-cooled High Rotation Speed molybdenum wheel contacts with the aluminium alloy of melting, molten alloy liquid is thrown out of, and forms fibrous Ce-HR-Fe-B-Mb alloy;
(3) hydrogen of alloy is broken
Pack LR-Fe-B-Ma alloy and HR-Fe-B-Mb alloy into vacuum hydrogen crushing furnace, after vacuumizing, be filled with hydrogen and inhale hydrogen, inhale hydrogen temperature 100-300 ℃, inhale hydrogen and finish to heat and vacuumize dehydrogenation, desorption temperature 350-900 ℃, afterwards that alloy is cooling;
(4) metal oxide micro mist adsorption and powder process
The LR-Fe-B-Ma alloy that hydrogen is processed and HR-Fe-B-Mb alloy and metal oxide micro mist join batch mixer and carry out batch mixing, during batch mixing or add lubricant and antioxidant, batch mixing carries out under nitrogen protection, and the laggard row airflow milling powder of batch mixing obtains alloy powder;
(5) pressing under magnetic field, sintering and timeliness
The alloy powder of preorder carried out under nitrogen protection to pressing under magnetic field, under vacuum or argon shield, carry out sintering and timeliness afterwards, make Fe-B rare-earth permanent magnet.
2. the manufacture method of a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 1, is characterized in that: described metal oxide micro mist is Dy
2o
3micro mist.
3. the manufacture method of a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 1, is characterized in that: described metal oxide micro mist is Al
2o
3micro mist.
4. the manufacture method of a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 1, is characterized in that: described metal oxide is for comprising Dy
2o
3, Tb
2o
3, Al
2o
3in one or more.
5. the manufacture method of a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 1, is characterized in that: described vacuumize dehydrogenation after, in 100-600 ℃ of temperature range, be filled with quantitative hydrogen, afterwards alloy is continued cooling; Or add quantitative hydrogen in follow-up batch mixing process.
6. the manufacture method of a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 1, is characterized in that: the average grain size of described LR-Fe-B-Ma alloy sheet is at 2.0-3.5 μ m; The average grain size of HR-Fe-B-Mb alloy fiber is at 0.6-1.9 μ m.
7. the manufacture method of a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 1; it is characterized in that: described airflow milling powder; the powder that airflow milling cyclone collector is collected and the fine powder of discharging with cyclone collector gas exhaust piping mix; be blended under nitrogen protection and carry out, mixed powder is for pressing under magnetic field operation.
8. containing a Fe-B rare-earth permanent magnet of La and Ce, by following percentage by weight component, formed: 19≤Ra≤32; 0.8≤B≤1.2; 0≤M≤4.0; 0.5≤Rb≤10; 30≤Ra+Rb≤33; All the other are Fe and impurity;
Wherein: Ra represents La, Ce, Pr and tetra-kinds of rare earth elements of Nd;
Rb represents one or more in Dy, Tb, Ho, Gd;
M represents more than one in Al, Co, Nb, Ga, Zr, Cu, Mo element;
The described Fe-B rare-earth permanent magnet with La and Ce is comprised of compound principal phase and Grain-Boundary Phase, and compound principal phase is with principal phase PR
2(Fe
1-x-yco
xal
y)
14b is core mutually, principal phase ZR
2(Fe
1-w-nco
wal
n)
14b is enclosed in principal phase PR mutually
2(Fe
1-x-yco
xal
y)
14the periphery of B phase, ZR
2(Fe
1-w-nco
wal
n)
14b phase and PR
2(Fe
1-x-yco
xal
y)
14b mutually between without Grain-Boundary Phase, wherein ZR represents that the content of the heavy rare earth in the rare earth element of principal phase is higher than the rare earth element sum of average heavy rare earth content, PR represents that the content of the heavy rare earth in the rare earth element of principal phase is lower than the rare earth element sum of average heavy rare earth content, 0≤x≤0.3,0≤y≤0.2,0≤w≤0.3,0≤n≤0.2, in Grain-Boundary Phase, have Ra oxide fine particle and oxidation Nd particulate, the oxygen content in Grain-Boundary Phase is higher than the oxygen content in principal phase.
9. a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 8, is characterized in that: the described Fe-B rare-earth permanent magnet containing La and Ce is comprised of compound principal phase and Grain-Boundary Phase, and average grain size is within the scope of 6-15 μ m.
10. a kind of Fe-B rare-earth permanent magnet containing La and Ce according to claim 8, is characterized in that: in the Grain-Boundary Phase of the described Fe-B rare-earth permanent magnet containing La and Ce, have oxidation La particulate and oxidation Ce particulate.
11. a kind of Fe-B rare-earth permanent magnets containing La and Ce according to claim 8, is characterized in that: in the Grain-Boundary Phase of the described Fe-B rare-earth permanent magnet containing La and Ce, have La
2o
3and Ce
2o
3particulate.
12. a kind of Fe-B rare-earth permanent magnets containing La and Ce according to claim 8, is characterized in that: two kinds of rare earth elements of described Pr and Nd, exist Pr/Nd=0.25-0.45 relation.
13. a kind of Fe-B rare-earth permanent magnets containing La and Ce according to claim 8, is characterized in that: described percentage by weight component forms: 0.6≤La+Ce≤2.4.
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