CN101320608B - Preparation method of complex orientation magnet - Google Patents
Preparation method of complex orientation magnet Download PDFInfo
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- CN101320608B CN101320608B CN2008100605102A CN200810060510A CN101320608B CN 101320608 B CN101320608 B CN 101320608B CN 2008100605102 A CN2008100605102 A CN 2008100605102A CN 200810060510 A CN200810060510 A CN 200810060510A CN 101320608 B CN101320608 B CN 101320608B
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Abstract
The invention discloses a preparation method of a complicated orientation magnet and belongs to the technology field of the rare-earth permanent magnetic material and the fabrication technology thereof, the nanometer material and the fabrication technology thereof and the motor application. Aims at the defects of the production yield of the complicated orientation magnet prepared by the prior art, the invention discloses a preparation method of the complicated orientation magnet. The method can remarkably increase the production yield of a complicated orientation powder sintering cobalt permanent magnetic material, an Nd-Fe-B permanent magnetic material, a hot-pressed and hot-deformed Nd-Fe-B magnet and permanent magnetic ferrite. By controlling the heating speed and the cooling speed in different periods, in particular to the temperature changing speed near to the critical temperature at the cooling speed of the hard magnetic phase, the invention can decrease the stress difference between the easy magnetization axis direction and the direction vertical to the easy magnetization axis of the magnet, thereby remarkably increasing the production yield of the complicated orientation magnet. The invention has the wide prospect on the production and the application of the permanent magnetic material.
Description
Technical field
The preparation method of complex orientation magnet belongs to fields such as rare earth permanent-magnetic material and manufacturing technology, nano material and manufacturing technology, motor application.
Background technology
In the technology of preparing of existing complex orientation magnet, powder sintered rare-earth cobalt permanent magnet material, powder sintered Nd-Fe-Bo permanent magnet material, the complex orientation magnet ring of powder sintered ferrite permanent-magnet materials, the rate of finished products of magnetic shoe and solid magnet is all lower, especially in industrial production the rate of finished products of powder sintered Nd-Fe-Bo permanent magnet material less than 10%, and market presses for the magnet of high performance complex orientation, as radially oriented magnet along the moulding magnet ring, the radial multi-pole orientation magnet, radially a pair of utmost point orientation magnet, the axial orientation magnet, the compound orientation magnet of radial-axial, as along moulding magnetic shoe one-way orientation magnet radially, the radial radiation orientation magnet is as being subjected to the magnet of force direction orientation along the main moulding of solid magnet; Adopt the magnet rate of finished products of complex orientation of powder hot-pressing thermal deformation preparation of rich rare-earth iron-boron permanent-magnet alloy fast quenching thin strap also lower.Prior art can't satisfy the production requirement of industrial complex orientation magnet to rare-earth cobalt permanent magnet material and Nd-Fe-Bo permanent magnet material, simultaneously, and the rate of finished products of the powder sintered ferrite permanent magnet of the high magnetic characteristics complex orientation space that also is greatly improved.
In the prior art, be mostly to prepare the moulds of industrial equipment design radially oriented, that radial multi-pole is orientated, the technology of Magnetic Field Design about powder sintered rare-earth cobalt permanent magnet material, powder sintered Nd-Fe-Bo permanent magnet material.As " radially oriented Nd-Fe-B permanent magnetic ring and manufacture method thereof ", Granted publication CN1175435, November 10 2004 Granted publication day.
But permanent magnetism itself is hard crisp phase mutually in the permanent magnetic material; Radially orientedly make hard crisp principal phase be orientated by radiation direction, in preparation technology's heating, cooling procedure, permanent magnetism hand down easy magnetizing axis and perpendicular to the expansion of easy magnetizing axis, shrink and present marked difference, and cause complex orientation magnet to ftracture.In the intensification of sintering, timeliness, especially in temperature-fall period, the overwhelming majority is broken as powder sintered neodymium iron boron radially oriented magnetic ring; Even seem intact magnet ring on the surface that remains after sintering, the Ageing Treatment, but in the process that leaves standstill, also can oneself break.Powder sintered rare-earth cobalt permanent magnet material also is like this.Even take some measures, also be difficult to make in batches the rare earth permanent magnet radially oriented magnetic ring of high magnetic characteristics.Four more than ten years went over, and for the radially oriented magnetic ring of high magnetic characteristics, still were difficult to prepared in batches.In the ferritic preparation of complex orientation, rate of finished products also remains further to be improved.
Therefore, the method that existing technology is taked to bond prepares radially oriented magnetic ring, but the bonding magnet ring generally contains binding agent, so bonding magnet ring magnetic property is lower, is difficult to satisfy the requirement of high magnetic characteristics radially oriented magnetic ring, also can't satisfy the requirement of elevated operating temperature.
To sum up, be badly in need of a kind of method that has than the complex orientation permanent magnet of the preparation high magnetic characteristics of high finished product rate.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of preparation method who prepares the complex orientation permanent magnet of high magnetic characteristics is provided, rate of finished products is higher, to satisfy the needs that engineering is used, has big using value.
The present invention notices in existing Rare-Earth Cobalt, neodymium iron boron, ferritic production technology, in sintering and heat treatment process subsequently, programming rate do not control substantially, take after sintered heat insulating finishes especially that gas is quenched, shrend, takes high as far as possible cooling rate to quench; Heat treatment then again is rapidly heated; After finishing, the heat treatment insulation also takes quick cooling basically.
Simultaneously, the inventor notices Luo Yang, Zhang Ning, and the thermal expansion of Nd-Fe-B magnet and hardness is with variation of temperature, Acta Metallurgica Sinica, Vol23, No1, A95～98,1987 year February.At Nd
2Fe
14More than the Curie temperature of B, with the reduction of temperature, more than 500 ℃, sintered magnet is along a little higher than change in size curve that is parallel to the magnetic field orientating direction of the change in size curve of perpendicular magnetic field orientation direction; But at 500 ℃ to overlapping substantially between the Curie temperature; Yet below Curie temperature, there is marked difference in magnet along perpendicular magnetic field orientation direction and the change in size curve that is parallel to the magnetic field orientating direction.
Test by analysis and in a large number, we propose the notion of Hard Magnetic phase velocity critical temperature, the speed critical temperature is that Hard Magnetic phase Curie temperature adds 10～40 ℃, control different cooling rates and firing rate up and down in the speed critical temperature, to slow down stress in the magnet, improve the rate of finished products of complex orientation permanent magnet moulding; Process is to the powder sintered process of permanent magnetic material, the analysis and the experiment of hot pressing thermal deformation process, proposition is controlled the invention thought of programming rate and cooling rate respectively stage by stage in heating, cooling procedure, thereby has increased substantially the rate of finished products of complex orientation permanent magnetic material.
Concrete invention is as follows:
In the preparation method of complex orientation magnet, the Hard Magnetic compound is R
2T
17, R
2T
14One of M, wherein R is at least a element or the element combinations of rare earth element and yttrium or the mixing of rare earth and yttrium in rare earth element and the yttrium, T is the combination between at least a transiting group metal elements or the transiting group metal elements, and M is at least a element that selects to periodic table IIIA, IVA and the VA family element; With the powder of Hard Magnetic compound respectively along radially oriented, the radial multi-pole orientation of moulding magnet ring, radially a pair of utmost point orientation, axial orientation, the compound orientation of radial-axial, respectively along moulding magnetic shoe radially one-way orientation, radial radiation orientation, be orientated by force direction along the main moulding of solid magnet in the powder of Hard Magnetic compound in the powder of Hard Magnetic compound; Blank is piled up at interval, be convenient to evenly heating and evenly cooling; Blank is rationally piled up, and certain space is left on the blank top of piling up, and is convenient to gas and orderly, the unobstructed discharge of volatile materials in the blank in heating process; Vacuumize earlier, the effumability material is removed in insulation while vacuumizing again, and control rate is heated to sintering temperature then; Take after the presintering sintering process or direct sintering technology again; In presintering or/and in the sintering process, continue earlier to vacuumize and fill inert protective gas again, and the control speed of filling the inertia protective gas; After sintered heat insulating finishes, take one of following mode temperature control: mode one control cooling rate is quenched into heat treatment temperature, direct heat is handled then, and mode two control cooling rates are quenched into the speed critical temperature, control cooling rate near the slow cool to room temperature of speed critical temperature or room temperature, control firing rate afterwards and slowly be warming up to the speed critical temperature, follow appropriate raising speed and be heated to the highest platform temperature of heat treatment and heat treatment again; Preferred temperature control method one; The speed critical temperature is that the Curie temperature of corresponding Hard Magnetic compound adds 10～40 ℃; Reach 90% when above of solid density in magnet density, in heating process or cooling procedure, all strict control alternating temperature speed; Especially in the speed critical temperature between the room temperature, alternating temperature speed all should be with rapid change temperature the most slowly; To the cooling procedure of next heating-up temperature platform and after the heat treatment insulation finishes, being cooled in the process of room temperature from a heat treatment heating-up temperature platform, when temperature is higher than the speed critical temperature, the cooling of control speed; When temperature was lower than the speed critical temperature, control rate slowly cooled to room temperature, came out of the stove then; Adopt this preparation method, the rate of finished products of complex orientation magnet increases substantially.
In the preparation method of above-mentioned complex orientation magnet, when Hard Magnetic is R mutually
2T
17The time, first powder magnetic field complex orientation, again blank at interval, rationally pile up, right fed to boiler vacuumizes 10～60min in room temperature, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
17The phase velocity critical temperature, the programming rate with 4～20 ℃/min is heated to calcined temperature again, in temperature-rise period, respectively at 140～220 ℃ of insulation 10～150min, at 450～520 ℃ of insulation 10～150min, is better than 1X10 in vacuum degree
-1After the Pa, at 1185～1240 ℃ of sintering 10～120min of calcined temperature, filling with inert gas and at 1130～1185 ℃ of sintering 30～240min is quenched to 900 ℃ with 10～180 ℃/min control speed more then; Then, arrive R at 900 ℃ at 900～370 ℃ of interrupted agings
2T
17In the cooling procedure of next temperature platform, control rate cools off with 0.8～5 ℃/min in the cooling procedure between the phase velocity critical temperature, at a temperature platform; Control fast cool to room temperature from 370 ℃ with 0.2～3 ℃/min, come out of the stove at last.
In the preparation method of above-mentioned complex orientation magnet, when Hard Magnetic is R mutually
2T
17The time, first powder magnetic field complex orientation, again blank at interval, rationally pile up, right fed to boiler, room temperature vacuumizes 10～60min, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
17The phase velocity critical temperature, the programming rate with 4～20 ℃/min is heated to calcined temperature again, in temperature-rise period, respectively at 140～220 ℃ of insulation 10～150min, at 450～520 ℃ of insulation 10～150min, is better than 1X10 in vacuum degree
-1After the Pa, at 1185～1240 ℃ of sintering 10～120min of calcined temperature, filling with inert gas and at 1130～1185 ℃ of sintering 30～240min then; Work as R
2T
17When the phase velocity critical temperature is higher than 850 ℃, be quenched to R with 10～180 ℃/min control speed
2T
17The phase velocity critical temperature is taked to control fast mode again and slowly is cooled to 850 ℃ with 0.8～5 ℃/min; Work as R
2T
17When the phase velocity critical temperature is lower than 850 ℃, be quenched into 850 ℃ with 30～180 ℃/min control speed; And then at 850～370 ℃ of interrupted agings, in next temperature platform cooling procedure, control rate cools off with 0.8～5 ℃/min at a temperature platform; Control fast cool to room temperature since 370 ℃ with 0.2～3 ℃/min, come out of the stove at last.
In the preparation method of above-mentioned complex orientation magnet, when Hard Magnetic is R mutually
2T
17The time, first powder magnetic field complex orientation, again blank at interval, rationally pile up, right fed to boiler, room temperature vacuumizes 10～60min, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
17The phase velocity critical temperature, the programming rate with 4～20 ℃/min is heated to calcined temperature again, in temperature-rise period, respectively at 140～220 ℃ of insulation 10～150min, at 450～520 ℃ of insulation 10～150min, is better than 1X10 in vacuum degree
-1After the Pa, at 1185～1240 ℃ of sintering 10～120min of calcined temperature, filling with inert gas and at 1130～1185 ℃ of sintering 30～240min is quenched to 870～900 ℃ with 10～180 ℃/min control speed then then; At 830～900 ℃ of insulation 20～1200min, slowly be cooled to 370～400 ℃ with 0.2～2.5 ℃/min control speed afterwards then, again at 370～400 ℃ of insulation 480～800min; When being higher than heat treated high temperature platform temperature for 870 ℃, be 0.8～5 ℃/min to heat treated high temperature platform temperature cooling rate from 870 ℃; Slowly be cooled to 370～400 ℃ with 0.2～2.5 ℃/min control speed afterwards, again at 370～400 ℃ of insulation 480～800min; Afterwards, control fast cool to room temperature, come out of the stove at last since 370～400 ℃ with 0.2～3 ℃/min.
In the preparation method of above-mentioned complex orientation magnet, when Hard Magnetic is R mutually
2T
14During M, first powder magnetic field complex orientation, blank at interval, rationally pile up, right fed to boiler then vacuumizes 10～60min in room temperature, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
14The critical temperature of M phase velocity, the programming rate with 4～20 ℃/min is heated to calcined temperature then; In this heating process, respectively at 140～220 ℃ of insulation 10～150min, at 450～500 ℃ of insulation 10～150min, take rapid-hardening flake, hydrogen embrittlement and airflow milling powder process operation, then in sintering process, increase by 990～1010 ℃ of insulation 10～120min dehydrogenation operations as neodymium iron boron, be better than 1X10 in vacuum degree
-1After the Pa, at calcined temperature sintering 10～120min, then filling with inert gas and at 1030～1090 ℃ of sintering 30～240min is controlled fast quench cooled to 880～920 ℃ with 10～180 ℃/min again; And then at 880～920 ℃ of heat treatment 30～180min, be cooled to 470～650 ℃ with 1～50 ℃/min again; From 470～650 ℃ of heat treatment 30～240min, be cooled to R with 0.8～10 ℃/min control speed then
2T
14The critical temperature of M phase velocity; From R
2T
14The critical temperature of M phase velocity begins, and, comes out of the stove at last until room temperature with 0.2～3 ℃/min of speed cooling.
In the preparation method of complex orientation magnet, when Hard Magnetic is R mutually
2T
14During the made powder of M fast quenching thin strap, be better than 1X10 in vacuum degree
-1After the Pa, take to prepare 600～950 ℃ of temperature argon filling hot pressing thermal deformations the magnet of complex orientation, the moulding magnet ring is radially oriented, axial orientation respectively, and moulding magnetic shoe difference is one-way orientation, radial radiation orientation radially, deflection 50～90%, and rate of deformation is 5X10
-4～10
1/ s; From the heat distortion temperature to R
2T
14Between the critical temperature of M phase velocity, be cooled to R with 0.8～10 ℃/min control speed
2T
14The critical temperature of M phase velocity; From R
2T
14The critical temperature of M phase velocity, is come out of the stove until room temperature at last with the cooling of 0.2～3 ℃/min speed.
In the preparation method of complex orientation magnet, when Hard Magnetic with R
2T
14M is main nanocrystalline built-up magnet, and the magnet phase composition is respectively R
2T
14M+R
2T
17, R
2T
14M/ α-Fe, R
2T
14M/Fe
3B, by the hot pressing thermal deformation, magnet ring is radially oriented, axial orientation respectively, and radially one-way orientation, radial radiation are orientated the moulding magnetic shoe respectively; Be better than 1X10 in vacuum degree
-1After the Pa, take 600～950 ℃ of temperature argon filling hot pressing thermal deformations, deflection is 50～90%, and rate of deformation is 5X10
-4～10
1/ s; From the hot pressing heat distortion temperature to R
2T
14Between the critical temperature of M phase velocity, be cooled to R with 0.8～10 ℃/min control speed
2T
14The critical temperature of M phase velocity; From R
2T
14The critical temperature of M phase velocity is controlled fast cool to room temperature with 0.2～3 ℃/min.
In the preparation method of complex orientation magnet, with the powder of permanent-magnet ferrite respectively along radially oriented, the radial multi-pole orientation of moulding magnet ring, radially a pair of utmost point orientation, axial orientation, the compound orientation of radial-axial, respectively along moulding magnetic shoe radially one-way orientation, radial radiation orientation, be orientated by force direction along the main moulding of solid magnet respectively in the powder of Hard Magnetic compound in the powder of Hard Magnetic compound; When adopting the wet type pressing under magnetic field, the air dry of blank elder generation, water content is lower than 2wt% shove charge again, and blank is at interval, rationally pile up, elder generation's control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, and the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process, at 80～99 ℃ of insulation 10～150min, at 450～510 ℃ of insulation 10～100min, then at 1160～1280 ℃ of sintering 30～180min, be quenched into and ferritic speed critical temperature with 5～30 ℃/min control speed afterwards, then cool off until room temperature, come out of the stove at last with 0.2～5 ℃/min control speed; When adopting the dry type pressing under magnetic field, blank at interval, rationally pile up, first control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process,, at 450～510 ℃ of insulation 10～100min, at 1160～1280 ℃ of sintering 30～180min, be quenched into and ferritic speed critical temperature with 5～30 ℃/min control speed then, cool off until room temperature with 0.2～5 ℃/min control speed afterwards, come out of the stove at last.
In the preparation method of complex orientation magnet, with the powder of permanent-magnet ferrite respectively along radially oriented, the radial multi-pole orientation of moulding magnet ring, radially a pair of utmost point orientation, axial orientation, the compound orientation of radial-axial, respectively along moulding magnetic shoe radially one-way orientation, radial radiation orientation, be orientated by force direction along the main moulding of solid magnet respectively in the powder of Hard Magnetic compound in the powder of Hard Magnetic compound; When adopting the wet type pressing under magnetic field, the air dry of blank elder generation, water content is lower than 2wt% shove charge again, and blank is at interval, rationally pile up, elder generation's control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, and the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process, at 80～99 ℃ of insulation 10～150min, at 450～510 ℃ of insulation 10～100min, at 1160～1280 ℃ of sintering 30～180min, be quenched into 930～960 ℃ with 5～30 ℃/min control speed then, and, be cooled to ferritic speed critical temperature with 2～20 ℃/min control speed afterwards at 930～960 ℃ of insulation 60～260min, then cool off until room temperature, come out of the stove at last with 0.2～5 ℃/min control speed; When adopting the dry type pressing under magnetic field, blank at interval, rationally pile up, first control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process, at 450～510 ℃ of insulation 10～100min, at 1160～1280 ℃ of sintering 30～180min, be quenched into 930～960 ℃ with 5～30 ℃/min control speed then, and, be cooled to ferritic speed critical temperature with 2～20 ℃/min control speed afterwards at 930～960 ℃ of insulation 60～260min, then cool off until room temperature, come out of the stove at last with 0.2～5 ℃/min control speed.
Compared with prior art, the present invention has following advantage:
1. the present invention's rate of finished products of preparing the powder sintered Rare-Earth Cobalt magnet of complex orientation, the powder sintered neodymium iron boron of complex orientation, complex orientation hot pressing heat distortion magnet increases substantially, and rate of finished products improves 40～80 percentage points;
2. the rate of finished products of the powder sintered ferrimagnet of complex orientation of the present invention's preparation improves 5～10 percentage points.
Embodiment
Embodiment 1
The rare earth cobalt alloy composition is Sm25.5wt%, Fe13.5wt%, Cu3.9wt%, Zr2.5wt%, the surplus Co of being, Hard Magnetic is R mutually
2T
17Adopt the Medium frequency induction melting, coarse crushing, middle fragmentation, stream of nitrogen gas is ground then, and the powder magnetic field radiation is orientated again, magnet ring size external diameter 30mm, internal diameter 20mm, high 10mm; With blank at interval, rationally pile up, right fed to boiler, room temperature vacuumizes 50min, takes to control fast mode and is warming up to R with 2.5 ℃/min
2T
17870 ℃ of speed critical temperatures; In temperature-rise period, at 200 ℃ of insulation 30min, at 500 ℃ of insulation 50min; Programming rate with 5 ℃/min is heated to calcined temperature again, is better than 1X10 in vacuum degree
-1After the Pa, at 1210 ℃ of sintering 20min of calcined temperature, filling with inert gas and at 1170 ℃ of sintering 120min is quenched to 900 ℃ with 30 ℃/min control speed more then, at 900 ℃ of insulation 120min; From 900 ℃ to R
2T
17870 ℃ of speed critical temperatures between, with 1.5 ℃/min cooling, then at 800 ℃ of isothermal 120min, 700 ℃ of isothermal 60min, 600 ℃ of isothermal 120min, 500 ℃ of isothermal 120min; Under 850 ℃, from a temperature platform to the cooling procedure of next temperature platform, control rate cools off with 1.5 ℃/min; Control fast cool to room temperature from 500 ℃ with 1.0 ℃/min, come out of the stove at last.
Prior art adopts the magnet ring rate of finished products of the present invention's preparation to improve 65 percentage points relatively.
Comparative example 1: to the rare earth cobalt alloy composition is Sm25.5wt%, Fe13.5wt%, Cu3.9wt%, Zr2.5wt%, the surplus Co of being, Hard Magnetic is R mutually
2T
17Powder process similarly to Example 1, magnet ring size, the limit vacuumizes, and the limit is raised to calcined temperature from room temperature about 40min, at 1210 ℃ of sintering 20min, filling with inert gas and at 1170 ℃ of sintering 120min then, argon gas is quenched near the room temperature again; Be warmed up to 850 ℃ with 15～30 ℃/min again from room temperature, then at 850 ℃ of isothermal 120min, 700 ℃ of isothermal 60min, 600 ℃ of isothermal 120min, 500 ℃ of isothermal 240min, 400 ℃ of 600min finish the back and come out of the stove 400 ℃ of quenchings afterwards; Is about 10min at a temperature platform to next temperature platform temperature fall time; The radially oriented magnetic ring rate of finished products is about 5%.
Embodiment 2
The rare earth cobalt alloy composition is Sm25.5wt%, Fe13.5wt%, Cu3.9wt%, Zr2.5wt%, the surplus Co of being, Hard Magnetic is R mutually
2T
17Adopt the Medium frequency induction melting, coarse crushing, middle fragmentation, stream of nitrogen gas is ground then, and the powder magnetic field radiation is orientated again, magnet ring size external diameter 30mm, internal diameter 20mm, high 10mm; With blank at interval, rationally pile up, right fed to boiler, room temperature vacuumizes 40min, takes to control fast mode and is warming up to R with 2.5 ℃/min
2T
17870 ℃ of speed critical temperatures; In temperature-rise period, at 210 ℃ of insulation 30min, at 510 ℃ of insulation 50min; Programming rate with 8 ℃/min is heated to calcined temperature again, is better than 1X10 in vacuum degree
-1After the Pa, at 1200 ℃ of sintering 30min of calcined temperature, filling with inert gas and at 1160 ℃ of sintering 120min is quenched to R with 30 ℃/min control speed more then
2T
17870 ℃ of speed critical temperatures; From 870 to 850 ℃ with 1.5 ℃/min cooling, then at 850 ℃ of isothermal 120min, and 700 ℃ of isothermal 60min, 600 ℃ of isothermal 120min, 500 ℃ of isothermal 240min, last 400 ℃ of 600min; Under 850 ℃, from a temperature platform to the cooling procedure of next temperature platform, control rate cools off with 1.5 ℃/min; Control fast cool to room temperature from 400 ℃ with 1.0 ℃/min, come out of the stove at last; Prior art adopts the magnet ring rate of finished products of the present invention's preparation to improve 65 percentage points relatively.
Embodiment 3
The rare earth cobalt alloy composition is Sm25.5wt%, Fe15.0wt%, Cu8.0wt%, Zr3.0wt%, the surplus Co of being, Hard Magnetic is R mutually
2T
17Adopt the Medium frequency induction melting, coarse crushing, middle fragmentation, stream of nitrogen gas is ground then, and the powder magnetic field radiation is orientated again, magnet ring size external diameter 40mm, internal diameter 30mm, high 15mm; With blank at interval, rationally pile up, right fed to boiler, room temperature vacuumizes 40min, takes to control fast mode and is warming up to R with 2.0 ℃/min
2T
17870 ℃ of speed critical temperatures; In temperature-rise period, at 210 ℃ of insulation 30min, at 510 ℃ of insulation 50min; Programming rate with 9 ℃/min is heated to calcined temperature again, is better than 1X10 in vacuum degree
-1After the Pa, at 1200 ℃ of sintering 30min of calcined temperature, filling with inert gas and at 1160 ℃ of sintering 120min is quenched to R with 30 ℃/min control speed more then
2T
17870～900 ℃ of speed critical temperatures; From 870 to 830 ℃ with 1.5 ℃/min cooling, then at 830 ℃ of isothermal 900min, from 830 ℃ to 400 ℃, control rate cools off with 0.7 ℃/min; Again at 400 ℃ of insulation 600min; Control fast cool to room temperature from 400 ℃ with 1.0 ℃/min, come out of the stove at last; Prior art adopts the magnet ring rate of finished products of the present invention's preparation to improve 65 percentage points relatively.
Embodiment 4
The rare-earth iron-boron composition is Nd31.0wt%, Dy0.5wt%, Nb0.1, B1.0, surplus Fe, first vacuum induction melting, rapid-hardening flake casting again, roller speed 1.0m/s, hydrogen embrittlement, airflow milling powder process then; Magnet ring external diameter 80, internal diameter 30, high by 40, external diameter be 6 pairs of utmost point orientations radially; Blank at interval, rationally pile up, right fed to boiler then vacuumizes 60min in room temperature, takes to control fast mode and is warming up to R with 2 ℃/min
2T
14350 ℃ of M phase velocity critical temperatures, the programming rate with 12 ℃/min is heated to calcined temperature then; In temperature-rise period, at 210 ℃ of insulation 70min, at 460 ℃ of insulation 80min, again in 1000 ℃ of insulation 100min dehydrogenation; Be better than 1X10 in vacuum degree
-1Pa at 1050 ℃ of argon filling sintering 120min, is controlled fast quench cooled to 900 ℃ with 90 ℃/min again; And then at 900 ℃ of heat treatment 110min, be cooled to 590 ℃ of heat treatment 120min with 2 ℃/min again; Be cooled to R with 2 ℃/min control speed then
2T
14350 ℃ of M phase velocity critical temperatures; From R
2T
14The critical temperature of M phase velocity begins, and, comes out of the stove at last until room temperature with 0.8 ℃/min of speed cooling.Prior art adopts the magnet ring rate of finished products of the present invention's preparation to improve 60 percentage points relatively.
Embodiment 5
The rare-earth iron-boron composition is Nd31.0wt%, Dy0.5wt%, Nb0.1, B1.0, surplus Fe, first vacuum induction melting, and fast quenching again, the linear velocity on chill roll surface is 30m/s, after the powder process, is better than 1X10 in vacuum degree
-1After the Pa, take to prepare magnet ring external diameter 80, internal diameter 30, high by 40, radially oriented 680 ℃ of temperature argon filling hot pressing thermal deformations, deflection 68%, rate of deformation is 5X10
-2/ s; From 680 ℃ of heat distortion temperatures to R
2T
14Between 350 ℃ of the M phase velocity critical temperatures, with the cooling of 1.8 ℃/min control speed; From R
2T
14The critical temperature of M phase velocity, is come out of the stove until room temperature at last with the cooling of 0.7 ℃/min speed.Prior art adopts the magnet ring rate of finished products of the present invention's preparation to improve 58 percentage points relatively.
Embodiment 6
With magnetically hard alloy Nd
12.0Fe
82.4Ga
0.3B
5.3Elder generation's vacuum induction melting master alloy ingot, vacuum argon filling fast quenching again, fast quenching running roller linear velocity is 30m/s; Above vacuum all reaches 10
-2Pa.The amorphous thin slice that fast quenching is made is broken and sieve and obtain powder, with Hard Magnetic powder and the soft magnet powder mould of packing into, and 700 ℃ of hot pressing, and thermal deformation, deflection is 66%, rate of deformation is 5X10
-1S
-1, prepare radially oriented magnetic shoe; After distortion finishes, from the heat distortion temperature to R
2T
14Between 345 ℃ of the M phase velocity critical temperatures, be cooled to R with 5 ℃/min control speed
2T
14The critical temperature of M phase velocity; From R
2T
14The critical temperature of M phase velocity, is come out of the stove until room temperature at last with the cooling of 0.5 ℃/min speed.Now, adopt the magnet ring rate of finished products of the present invention's preparation to improve 50 percentage points to prior art.
Embodiment 7
With iron phosphorus 85.6wt%, strontium carbonate 13.9wt%, calcium carbonate 0.5wt% ball milling, doping, granulation, moulding, a pair of utmost point oriental magnetic ring size: external diameter 25mm, internal diameter 12mm, high 7mm; The air dry of blank elder generation, water content is lower than 2wt% shove charge again, blank at interval, rationally pile up, control rate heats up with 2 ℃/min, at 90 ℃ of insulation 30min, be heated to 500 ℃, at 500 ℃ of insulation 30min, the speed with 10 ℃/min is heated to 1270 ℃ of pre-burning 180min then, then at 1220 ℃ of sintering 120min, be quenched into 470 ℃ on ferrite with 20 ℃/min control speed then, cool off until room temperature with 0.4 ℃/min control speed afterwards, come out of the stove at last.
Claims (10)
1. the preparation method of complex orientation magnet is characterized in that:
A. the Hard Magnetic compound is R
2T
17, R
2T
14One of M, wherein R is at least a element in rare earth element and the yttrium, and T is at least a transiting group metal elements, and M is at least a element in periodic table IIIA, IVA and the VA family element;
B. with the powder of Hard Magnetic compound respectively along radially oriented, the radial multi-pole orientation of moulding magnet ring, radially a pair of utmost point orientation, axial orientation, the compound orientation of radial-axial, respectively along moulding magnetic shoe radially one-way orientation, radial radiation orientation, be orientated by force direction along the main moulding of solid magnet in the powder of Hard Magnetic compound in the powder of Hard Magnetic compound;
C. blank is piled up at interval, be convenient to evenly heating and evenly cooling; Blank is rationally piled up, and certain space is left on the blank top of piling up, and is convenient to gas and orderly, the unobstructed discharge of volatile materials in the blank in heating process;
D. vacuumize earlier, the effumability material is removed in insulation while vacuumizing again, and control rate is heated to sintering temperature then;
E. take after the presintering sintering process or direct sintering technology again; In presintering or/and in the sintering process, continue earlier to vacuumize and fill inert protective gas again, and the control speed of filling the inertia protective gas;
F. after sintered heat insulating finishes, take one of following mode temperature control: mode one control cooling rate is quenched into heat treatment temperature, direct heat is handled then, and mode two control cooling rates are quenched into the speed critical temperature, control cooling rate near the slow cool to room temperature of speed critical temperature or room temperature, control firing rate afterwards and slowly be warming up to the speed critical temperature, follow appropriate raising speed and be heated to the highest platform temperature of heat treatment and heat treatment again;
G. the speed critical temperature is that the Curie temperature of corresponding Hard Magnetic compound adds 10～40 ℃; Reach 90% when above of solid density in magnet density, in heating process or cooling procedure, all strict control alternating temperature speed; To between the room temperature, alternating temperature speed all should be with rapid change temperature the most slowly in the speed critical temperature;
H. being cooled in the process of room temperature to the cooling procedure of next heating-up temperature platform and after the heat treatment insulation finishes from a heat treatment heating-up temperature platform, when temperature was higher than the speed critical temperature, control speed was cooled off; When temperature was lower than the speed critical temperature, control rate slowly cooled to room temperature, came out of the stove then;
I. adopt this preparation method, the rate of finished products of complex orientation magnet increases substantially.
2. according to the described preparation method of claim 1, it is characterized in that:
A. working as Hard Magnetic is R mutually
2T
17The time, first powder magnetic field complex orientation, again blank at interval, rationally pile up, right fed to boiler vacuumizes 10～60min in room temperature, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
17The phase velocity critical temperature, the programming rate with 4～20 ℃/min is heated to calcined temperature again, in temperature-rise period, respectively at 140～220 ℃ of insulation 10～150min, at 450～520 ℃ of insulation 10～150min, is better than 1X10 in vacuum degree
-1After the Pa, at 1185～1240 ℃ of sintering 10～120min of calcined temperature, filling with inert gas and at 1130～1185 ℃ of sintering 30～240min is quenched to 900 ℃ with 10～180 ℃/min control speed more then;
B. then at 900～370 ℃ of interrupted agings, arrive R at 900 ℃
2T
17In the cooling procedure of next temperature platform, control rate cools off with 0.8～5 ℃/min in the cooling procedure between the phase velocity critical temperature, at a temperature platform;
C. control fast cool to room temperature from 370 ℃ with 0.2～3 ℃/min, come out of the stove at last.
3. according to the described preparation method of claim 1, it is characterized in that:
A. working as Hard Magnetic is R mutually
2T
17The time, first powder magnetic field complex orientation, again blank at interval, rationally pile up, right fed to boiler, room temperature vacuumizes 10～60min, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
17The phase velocity critical temperature, the programming rate with 4～20 ℃/min is heated to calcined temperature again, in temperature-rise period, respectively at 140～220 ℃ of insulation 10～150min, at 450～520 ℃ of insulation 10～150min, is better than 1X10 in vacuum degree
-1After the Pa, at 1185～1240 ℃ of sintering 10～120min of calcined temperature, filling with inert gas and at 1130～1185 ℃ of sintering 30～240min then; Work as R
2T
17When the phase velocity critical temperature is higher than 850 ℃, be quenched to R with 10～180 ℃/min control speed
2T
17The phase velocity critical temperature is taked to control fast mode again and slowly is cooled to 850 ℃ with 0.8～5 ℃/min; Work as R
2T
17When the phase velocity critical temperature is lower than 850 ℃, be quenched into 850 ℃ with 30～180 ℃/min control speed;
B. and then at 850～370 ℃ of interrupted agings, in next temperature platform cooling procedure, control rate cools off with 0.8～5 ℃/min at a temperature platform;
C. control fast cool to room temperature since 370 ℃ with 0.2～3 ℃/min, come out of the stove at last.
4. according to the described preparation method of claim 1, it is characterized in that:
A. working as Hard Magnetic is R mutually
2T
17The time, first powder magnetic field complex orientation, again blank at interval, rationally pile up, right fed to boiler, room temperature vacuumizes 10～60min, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
17The phase velocity critical temperature, the programming rate with 4～20 ℃/min is heated to calcined temperature again, in temperature-rise period, respectively at 140～220 ℃ of insulation 10～150min, at 450～520 ℃ of insulation 10～150min, is better than 1X10 in vacuum degree
-1After the Pa, at 1185～1240 ℃ of sintering 10～120min of calcined temperature, filling with inert gas and at 1130～1185 ℃ of sintering 30～240min is quenched to 870～900 ℃ with 10～180 ℃/min control speed then then; At 830～900 ℃ of insulation 20～1200min, slowly be cooled to 370～400 ℃ with 0.2～2.5 ℃/min control speed afterwards then, again at 370～400 ℃ of insulation 480～800min; When being higher than heat treated high temperature platform temperature for 870 ℃, be 0.8～5 ℃/min to heat treated high temperature platform temperature cooling rate from 870 ℃;
B. after, control fast cool to room temperature, come out of the stove at last since 370～400 ℃ with 0.2～3 ℃/min.
5. according to the described preparation method of claim 1, it is characterized in that:
A. working as Hard Magnetic is R mutually
2T
14During M, first powder magnetic field complex orientation, blank at interval, rationally pile up, right fed to boiler then vacuumizes 10～60min in room temperature, takes to control fast mode and is warming up to R with 0.5～8 ℃/min
2T
14The critical temperature of M phase velocity, the programming rate with 4～20 ℃/min is heated to calcined temperature then; In this heating process, respectively at 140～220 ℃ of insulation 10～150min, at 450～500 ℃ of insulation 10～150min; Be better than 1X10 in vacuum degree
-1After the Pa, at calcined temperature sintering 10～120min, then filling with inert gas and at 1030～1090 ℃ of sintering 30～240min is controlled fast quench cooled to 880～920 ℃ with 10～180 ℃/min again;
B. and then at 880～920 ℃ of heat treatment 30～180min, be cooled to 470～650 ℃ with 1～50 ℃/min again;
C. from 470～650 ℃ of heat treatment 30～240min, be cooled to R with 0.8～10 ℃/min control speed then
2T
14The critical temperature of M phase velocity;
D. from R
2T
14The critical temperature of M phase velocity begins, and, comes out of the stove at last until room temperature with 0.2～3 ℃/min of speed cooling.
6. according to the described preparation method of claim 5, it is characterized in that:
When neodymium iron boron is taked rapid-hardening flake, hydrogen embrittlement and airflow milling powder process operation, then in sintering process, increase by 990～1010 ℃ of insulation 10～120min dehydrogenation operations.
7. the preparation method of complex orientation magnet is characterized in that:
A. working as Hard Magnetic is R mutually
2T
14During the made powder of M fast quenching thin strap, be better than 1X10 in vacuum degree
-1After the Pa, take to prepare 600～950 ℃ of temperature argon filling hot pressing thermal deformations the magnet of complex orientation, the moulding magnet ring is radially oriented, axial orientation respectively, and moulding magnetic shoe difference is one-way orientation, radial radiation orientation radially, deflection 50～90%, and rate of deformation is 5X10
-4～10
1/ s;
B. from the heat distortion temperature to R
2T
14Between the critical temperature of M phase velocity, be cooled to R with 0.8～10 ℃/min control speed
2T
14The critical temperature of M phase velocity;
C. from R
2T
14The critical temperature of M phase velocity, is come out of the stove until room temperature at last with the cooling of 0.2～3 ℃/min speed.
8. the preparation method of complex orientation magnet is characterized in that:
A. work as Hard Magnetic with R
2T
14M is main nanocrystalline built-up magnet, and the magnet phase composition is respectively R
2T
14M+R
2T
17, R
2T
14M/ α-Fe, R
2T
14M/Fe
3B, by the hot pressing thermal deformation, magnet ring is radially oriented, axial orientation respectively, and radially one-way orientation, radial radiation are orientated the moulding magnetic shoe respectively;
B. be better than 1X10 in vacuum degree
-1After the Pa, take 600～950 ℃ of temperature argon filling hot pressing thermal deformations, deflection is 50～90%, and rate of deformation is 5X10
-4～10
1/ s; From the hot pressing heat distortion temperature to R
2T
14Between the critical temperature of M phase velocity, be cooled to R with 0.8～10 ℃/min control speed
2T
14The critical temperature of M phase velocity;
C. from R
2T
14The critical temperature of M phase velocity is controlled fast cool to room temperature with 0.2～3 ℃/min.
9. the preparation method of complex orientation magnet is characterized in that:
A. with the powder of permanent-magnet ferrite respectively along radially oriented, the radial multi-pole orientation of moulding magnet ring, radially a pair of utmost point orientation, axial orientation, the compound orientation of radial-axial, respectively along moulding magnetic shoe radially one-way orientation, radial radiation orientation, be orientated by force direction along the main moulding of solid magnet respectively in the powder of Hard Magnetic compound in the powder of Hard Magnetic compound;
B. when adopting the wet type pressing under magnetic field, the air dry of blank elder generation, water content is lower than 2wt% shove charge again, and blank is at interval, rationally pile up, elder generation's control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, and the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process, at 80～99 ℃ of insulation 10～150min, at 450～510 ℃ of insulation 10～100min, then at 1160～1280 ℃ of sintering 30～180min, be quenched into and ferritic speed critical temperature with 5～30 ℃/min control speed afterwards, then cool off until room temperature, come out of the stove at last with 0.2～5 ℃/min control speed;
When adopting the dry type pressing under magnetic field, blank at interval, rationally pile up, first control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process, at 450～510 ℃ of insulation 10～100min,, be quenched into and ferritic speed critical temperature with 5～30 ℃/min control speed then at 1160～1280 ℃ of sintering 30～180min, cool off until room temperature with 0.2～5 ℃/min control speed afterwards, come out of the stove at last.
10. the preparation method of complex orientation magnet is characterized in that:
A. with the powder of permanent-magnet ferrite respectively along radially oriented, the radial multi-pole orientation of moulding magnet ring, radially a pair of utmost point orientation, axial orientation, the compound orientation of radial-axial, respectively along moulding magnetic shoe radially one-way orientation, radial radiation orientation, be orientated by force direction along the main moulding of solid magnet respectively in the powder of Hard Magnetic compound in the powder of Hard Magnetic compound;
B. when adopting the wet type pressing under magnetic field, the air dry of blank elder generation, water content is lower than 2wt% shove charge again, and blank is at interval, rationally pile up, elder generation's control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, and the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process, at 80～99 ℃ of insulation 10～150min, at 450～510 ℃ of insulation 10～100min, at 1160～1280 ℃ of sintering 30～180min, be quenched into 930～960 ℃ with 5～30 ℃/min control speed then, and, be cooled to ferritic speed critical temperature with 2～20 ℃/min control speed afterwards at 930～960 ℃ of insulation 60～260min, then cool off until room temperature, come out of the stove at last with 0.2～5 ℃/min control speed;
When adopting the dry type pressing under magnetic field, blank at interval, rationally pile up, first control rate is warming up to the critical temperature of ferrite cooling rate with 0.5～6 ℃/min, the speed with 3～20 ℃/min is heated to sintering temperature then; In heating process, at 450～510 ℃ of insulation 10～100min, at 1160～1280 ℃ of sintering 30～180min, be quenched into 930～960 ℃ with 5～30 ℃/min control speed then, and at 930～960 ℃ of insulation 60～260min, be cooled to ferritic speed critical temperature with 2～20 ℃/min control speed afterwards, then cool off until room temperature, come out of the stove at last with 0.2～5 ℃/min control speed.
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| CN103317135B (en) * | 2013-06-14 | 2015-07-08 | 宁波华辉磁业有限公司 | High-temperature sintering process for neodymium iron boron |
| CN107578871A (en) * | 2017-09-26 | 2018-01-12 | 浙江东阳东磁稀土有限公司 | A kind of preparation method of the radially oriented magnetic shoe of high-performance |
| CN110136916B (en) | 2019-06-11 | 2021-01-26 | 深圳市瑞达美磁业有限公司 | Radiation orientation solid cylindrical magnet and production method and equipment thereof |
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