CN109192426A - R-Fe-B based sintered magnet containing Tb and Hf and preparation method thereof - Google Patents
R-Fe-B based sintered magnet containing Tb and Hf and preparation method thereof Download PDFInfo
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- CN109192426A CN109192426A CN201811029506.XA CN201811029506A CN109192426A CN 109192426 A CN109192426 A CN 109192426A CN 201811029506 A CN201811029506 A CN 201811029506A CN 109192426 A CN109192426 A CN 109192426A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
Abstract
The R comprising core and shell is distributed in the invention discloses a kind of R-Fe-B based sintered magnet and preparation method thereof containing Tb and Hf, the surface region and interior zone of the sintered magnet2Fe14Type B main phase grain, the Tb content of the shell is higher than the Tb content in the core, having Hf content in the crystal grain boundary of the sintered magnet is the richness region Hf below 0.1wt% or more, 3.0wt%, the richness region Hf is in the distribution of uniform dispersion in the crystal grain boundary, and accounts for the 5.0vol%-11.0vol% of the sintered magnet.The sintered magnet has a magnetic property of preferable high temperature stability performance and room temperature, and preparation process facilitates controllable, and equipment is simple, easy to industrialized production.
Description
Technical field
The present invention relates to rare-earth permanent-magnet material technical field, more particularly to a kind of sintered magnet containing Tb and Hf and its
Preparation method.
Background technique
Nd-Fe-B sintered magnet is since the 1980s is found by the U.S. and Japanese Scientists, since it has height
The advantages such as magnetic energy product and high remanent magnetism, at present in motor, electro-acoustic element, computer hard disc driver (HDD), military industry equipment, people
Body NMR imaging instrument (MRI), short-wave communication tedhnology, controller, instrument etc. receive extensive use.
High-coercive force, high remanent magnetism permanent magnet are always the emphasis of the market demand, in Nd-Fe-B permanent-magnet material industrial production mistake
Cheng Zhong, different application field also can differences to the performance requirement of its material, it will usually be properly added it in blending process
His rare earth element replaces Nd atom to achieve the purpose that performance of control.Known heavy rare earth element tb or Dy can have it is bigger it is each to
Anisotropic field replaces the Nd of main phase in magnet that the coercivity of sintered magnet can be improved, is most by addition heavy rare earth element Tb or Dy
Coercivity may be improved, while not reducing remanent magnetism, it usually needs passes through the techniques such as grain boundary decision/osmosis after sintering process
So that Tb is enriched near crystal boundary, improvement heavy rare earth element is coupled with the anti-ferromagnetism between Fe atom for control.And it utilizes existing
When dual alloy method adds the heavy rare earth elements such as Dy, Tb into conventional magnet crystal boundary, the weight for being easy to cause magnet crystal boundary to add is dilute
Earth elements are to main phase grain excess diffusion, so that Dy, Tb etc. are in the main phase that homogenization is dispersed in sintered magnet, magnet remanence is big
It is big to reduce.
Therefore it is higher that stoicheiometry economical rationality, comprehensive performance are developed, and the rare earth permanent magnet that high-temperature behavior is relatively stable
Material is necessary.
Summary of the invention
In view of the foregoing, the present invention provides a kind of sintered magnet containing Tb and Hf, which has preferable
High temperature stability performance and excellent room temperature magnetic property, preparation process facilitate controllable, and equipment is simple, easy to industrialized production.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of R-Fe-B based sintered magnet containing Tb and Hf, the R is rare earth element, and includes at least Nd, feature
Be: the R comprising core and shell is distributed in the surface region and interior zone of the sintered magnet2Fe14Type B main phase is brilliant
Grain, the Tb content of the shell are higher than the Tb content in the core, contain in the crystal grain boundary of the sintered magnet with Hf
Amount is the richness region Hf below 0.1wt% or more, 3.0wt%, and the richness region Hf is in uniform dispersion in the crystal grain boundary
Distribution, and account for the 5.0vol%-11.0vol% of the sintered magnet.
By adding Tb and Hf, sintered magnet phase composition and structure change, so that the sintered magnet made has
Preferable high temperature stability performance and excellent room temperature magnetic property.
It is a discovery of the invention that when the uniform dispersed distribution of Hf is in grain boundaries, is formed Hf content for 0.1wt% or more, 3.0wt% with
Under the rich region Hf, under Hf pinning effect, Tb enters main phase grain and is obstructed, and is easier to be enriched near the crystal boundary, rich dilute
Native mutually formed between main phase contains high concentration Tb transition zone, and the Tb content of crystal grain shell is higher than the Tb in crystal grain core
Content, to promote the magnetic property of magnet.
In the present invention, the surface region of sintered magnet refers to that the working face of magnet to 500 μm of regions below of working face, is burnt
The interior zone of knot magnet refers to that the working face apart from magnet is more than 500 μm of region.Here shell refers to the addition
The main phase grain region that heavy rare earth element in powder is diffused into, core here refer to that the weight in the addition powder is dilute
The main phase grain region that earth elements do not diffuse into.The shell does not refer to merely continuous shell, is also possible to interrupted
Shell, equally, also the uniform shell of not simple dinger thickness degree, is also possible to the inhomogenous shell of thickness distribution.
The present invention also provides following parallel technical solutions:
A kind of R-Fe-B based sintered magnet containing Tb and Hf, the sintered magnet are mixed by master alloying and auxiliary alloy
Sintering is prepared, and the mass ratio of the master alloying and the auxiliary alloy is (85-90): (10-15), the master alloying have by
Composition formula RaFecHfbBdXeThe composition of expression, the auxiliary alloy have by composition formula TbfFegMhThe composition of expression:
R is selected from at least one kind of of rare earth element, and the R includes Nd；
X be selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb,
It is at least one kind of in Ta, W, O, C, N, S or P；
M is selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Ta
Or it is at least one kind of in W；
A, b, c, d, e, f, g, h by weight percentage, a 26-33, b 0.03-1.8, d 1-1.15, e 0-3, c
For 100-a-b-d-e, f 8-30, h 0-3, g 100-f-h.
Present invention discover that Hf is originated from master alloying using dual alloy method, Tb is originated from auxiliary alloy, is easier to during the sintering process in Hf
Act on the distribution of down regulation Tb.Hf is distributed mainly on master alloying crystal boundary, and under Hf pinning effect, Tb enters main phase grain and is obstructed,
It is easier to be enriched near crystal boundary, is formed between crystal boundary and main phase and contain high concentration Tb transition zone, to contain in above-mentioned Tb and Hf
Measure the magnetic property that magnet is promoted in range；The presence of X and M improves the wellability of Nd-rich phase and main phase grain to a certain extent,
Micro-structure is refined, inhibits α-Fe to be mutually precipitated, drops low-alloyed flux irreversible loss, improve the stability of alloy.
It should be noted that in the present invention, the mass ratio of master alloying and auxiliary alloy in sintered magnet, the value 26-33, d of a
Value 1-1.15, e value 0-3, h value 0-3 be the industry conventional selection, therefore, in embodiment, not to it
Content range is tested and is verified.
Another object of the present invention is to provide a kind of preparation methods containing Tb and Hf sintered magnet.
A kind of preparation method of the R-Fe-B based sintered magnet containing Tb and Hf, the sintered magnet be by master alloying and
Auxiliary alloy mixed sintering is prepared, and the master alloying has by composition formula RaHfbFecBdXeThe composition of expression, the auxiliary alloy
With by composition formula TbfFegMhThe composition of expression:
R is selected from at least one kind of of rare earth element, and the R includes Nd；
X be selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb,
It is at least one kind of in Ta, W, O, C, N, S or P；
M be selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb,
It is at least one kind of in Ta or W；
A, b, c, d, e, f, g, h by weight percentage, a 26-33, b 0.03-1.8, d 1-1.15, e 0-3, c
For 100-a-b-d-e, f 8-30, h 0-3, g 100-f-h,
And include at least following process:
The process that the components fuse liquid of the master alloying and the auxiliary alloy is prepared into rapid hardening thin slice respectively；By the master
The process that fine powder is made in alloy rapid hardening thin slice and the auxiliary alloy rapid hardening thin slice mixing, suction hydrogen breaking and Crushing of Ultrafine；With described thin
Powder magnetic forming method or hot pressing thermal deformation obtain formed body, and with 1000 DEG C -1070 DEG C of temperature in vacuum or inert gas
Acquisition is sintered to the formed body.
The wt% referred in the present invention is weight percentage.
The vol% referred in the present invention is percent by volume.
The digital scope that the present invention announces includes all point values of this range.
Detailed description of the invention
Fig. 1 is the distribution situation of Tb, Nd, Hf, B in magnet in embodiment 1.1.
Fig. 2 is the distribution situation of Tb, Nd, B in magnet in comparative example 1.1.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, With reference to embodiment
The present invention will be further described in detail, but protection scope of the present invention is not limited to following embodiments, in the following example
Test method without specific conditions, usually according to normal condition.
The magnetic property evaluation procedure that refers in each embodiment, composition measurement, coercive force temperature coefficient are defined as follows:
Magnetic property evaluation procedure: sintered magnet carries out magnetic property inspection using the NIM-200C measuring system of metering institute of China
It surveys.
Composition measurement: each ingredient is surveyed using high-frequency inductive coupling plasma body ICP Atomic Emission Spectrophotometer method (ICP-OES)
It is fixed；Oxygen content is used and is measured based on gas dissolution-infrared absorption gas analyzing apparatus.
Coercive force temperature coefficient (20 DEG C -60 DEG C): the β=Δ H/ Δ unit of T × 100%: %/DEG C.
Rich Hf phase volume ratio passes through Dutch Panaco X-ray diffractometer, is measured point in conjunction with Fullprof structure refinement
Analysis.
Hf content carries out composition detection by BSE-EDS in the Tb and crystal boundary of main phase grain.
The detection of FE-EPMA (field emission electron probe microanalysis) detection referred in each embodiment is limited to the left side 100ppm
The right side, FE-EPMA equipment highest resolution reach 3nm.
In the embodiment of recommendation, the sintered magnet is mixed with by master alloying and auxiliary alloy, described
The mass ratio of master alloying and the auxiliary alloy is (85-90): (10-15), and the Hf is originated from the master alloying, the master alloying packet
The Hf of 0.03wt%-1.80wt% is included, the Tb is originated from the auxiliary alloy, and the auxiliary alloy includes the Tb of 8wt%-30wt%.
Hf and Tb are within the above range, it is easier to improve the phase composition of magnet during the sintering process, form core-shell structure.
In the embodiment of recommendation, the oxygen content of sintered magnet 1000ppm or less by weight.Low oxygen content
Magnet has higher magnetic property, more sensitive for the microstructure change response of sintered magnet, and Hf is uniform in crystal boundary
The influence to magnetic property such as dispersion and the formation of core-shell structure is more significant.
It should be noted that since the hypoxemia manufacturing process of sintered magnet has been the prior art, and all realities of the invention
It applies example and all uses hypoxemia manufacture, be no longer described in detail herein.
In the embodiment of recommendation, the b is preferably 0.08-1.0.Within this range by the content control of Hf, on a small quantity
The presence of Hf can efficiently play pinning effect during the sintering process, obtain comprehensive performance more preferably magnet.
In the embodiment of recommendation, the f is preferably 12-25.Within this range by the content control of Tb, it can have
Effect forms main phase grain surface and forms core-shell structure, while preventing excess diffusion caused by excessive Tb, reduces the influence to remanent magnetism.
In the embodiment of recommendation, the heating process of the sintering includes the following steps, from 350 DEG C -400 DEG C with 6 DEG C/
Min-9 DEG C/min is warming up to 600 DEG C -650 DEG C processes being pre-sintered, and the process being sintered at 1000 DEG C -1070 DEG C.
Sintered magnet includes above step, can avoid main phase particle abnormal growth, while the effective Nd-rich phase that reduces is in crystal boundary triangle
The enrichment in area, makes it be evenly distributed on grain boundaries；It is rapidly heated to after 600 DEG C -650 DEG C, in powder processed and forming process, absorption
Antioxidant, lubricant and partial oxidation etc. be discharged inside formed body along crack, slit, magnet is shunk, and density starts to increase
Add, while the promotion of temperature, inside starts liquid phase occur, and particle is subjected to displacement by the promotion of liquid phase surface tension, and Hf is excellent
High-temperature stability and pinning effect, so that the Tb in the region crystal boundary richness Hf is adjusted arrangement, Tb is easier to be enriched near the crystal boundary.
In the heating process of the vacuum-sintering, the soaking time in each stage is the conventional selection of the industry, therefore,
In embodiment, above range is not tested and verified.
The settable multistage pre-sintering of sintering process, the present invention are no for other stages of the multistage pre-sintering particularly
Limitation, can suitably select according to the purpose of those skilled in the art.For example, it is pre- to may also include 350 DEG C -400 DEG C of low temperature
It burns, 800 DEG C -850 DEG C of medium temperature pre-burning.
The present invention is not particularly limited the sintered heat treatment, can be according to the mesh of those skilled in the art
And suitably select.For example, second level can be selected to anneal, the first order is annealed 840 DEG C -900 DEG C, keeps the temperature 3h-4h, second level annealing
440 DEG C -500 DEG C, heat preservation 4h-5h etc..
Embodiment one
Raw material preparation: the master alloying being made of Nd, Fe, Pr, Hf, B, Al and Cu, the auxiliary conjunction being made of Tb, Fe, Co and Zr
Gold.
Smelting and pouring: being respectively prepared the rapid hardening thin slice with a thickness of 0.5mm for the components fuse liquid of master alloying and auxiliary alloy, right
Its ingredient is analyzed, as shown in table 1.
Hydrogen crushing: master alloying rapid hardening thin slice and auxiliary alloy rapid hardening thin slice are mixed with the mass ratio of 90:10, broken using hydrogen
Broken technique is made hydrogen and breaks powder.
Air-flow crushing: hydrogen is broken into powder again and is milled into fine powder through air-flow.
Forming sintering: fine powder magnetic forming method is obtained into formed body, and is 5*10 in vacuum degree-2In the sintering furnace of Pa into
Row vacuum-sintering is specially warming up to 350 DEG C and heat preservation 1h, then is warming up to 620 DEG C and heat preservation 2h with 8 DEG C/min, then heats up
To 820 DEG C and 2h is kept the temperature, 1060 DEG C is warming up to later and is sintered, then carry out second level annealing, obtain sintered magnet.
It observes and measures through Electronic Speculum, surface region and the interior zone distribution for the sintered magnet that embodiment 1.1-1.5 is obtained
There is the R comprising core and shell2Fe14Type B main phase grain, the Tb content of shell are higher than the Tb content in core, are being sintered
Having Hf content in the crystal grain boundary of magnet is the richness region Hf below 0.1wt% or more, 3.0wt%.
Through XRD determining, the rich region Hf for the sintered magnet that embodiment 1.1-1.5 is obtained accounts for the sintered magnet
5.0vol%-11.0vol%.
The oxygen content for measuring the sintered magnet that embodiment 1.1-1.5 is obtained is 1000ppm or less.
Performance evaluation is carried out to the sintered magnet that each embodiment and each comparative example obtain, Evaluation results are as shown in table 2.
1 constituent analysis of table (wt%)
2 performance evaluation situation of table
As conclusion we it follows that
When Hf content is less than 0.03wt% in master alloying, since Hf content is very few, it is difficult to play and Tb is hindered to enter main phase
Internal effect, can not form stable core-shell structure；Hf content is higher than 1.8wt%, and the addition of refractory metal Hf will lead to
Sintering temperature increases, and then influences magnet coercivity；Hf content mentions sintered magnet magnetic property in 0.08wt%-1.0wt%
It rises, especially high temperature stability performance is more beneficial.
The ingredients such as Nd, Pr, Tb, Hf and Co of sintered magnet are made to embodiment 1.1 and carry out FE-EPMA detection, as a result such as
Shown in Fig. 1, it is observed that heavy rare earth element Tb and Hf are distributed mainly on grain boundaries, and Hf is in the distribution of uniform dispersion,
Simultaneously because the addition of Hf, sintered magnet are formed by core-shell structure and are more clear；Comparative example 1.1 be made sintered magnet Nd,
The ingredients such as Pr, Tb and Co carry out FE-EPMA detection, as a result as shown in Figure 2, it can be observed that heavy rare earth element Tb excess diffusion
To inside main phase grain, core-shell structure is unobvious.
Similarly, other each embodiments are detected, it is observed that Tb is mainly distributed on grain boundaries, after Hf is added
The Tb of crystal boundary trigonum is significantly reduced, and the Tb for being distributed in grain boundaries is more obvious.
Comparative example 1.2, Hf content are higher than 1.8wt%, and magnet coercivity significantly reduces.
Embodiment two
Raw material preparation: the master alloying being made of Nd, Fe, Pr, Hf, B, Zn and Cu, the auxiliary conjunction being made of Tb, Fe, Co and Cr
Gold.
Smelting and pouring: being respectively prepared the rapid hardening thin slice with a thickness of 0.3mm for the components fuse liquid of master alloying and auxiliary alloy, right
Its ingredient is analyzed, as shown in table 3.
Hydrogen crushing: master alloying rapid hardening thin slice and auxiliary alloy rapid hardening thin slice are mixed with the mass ratio of 85:15, broken using hydrogen
Broken technique is made hydrogen and breaks powder.
Air-flow crushing: hydrogen is broken into powder again and is milled into fine powder through air-flow.
Forming sintering: fine powder magnetic forming method is obtained into formed body, and is 3*10 in vacuum degree-2In the sintering furnace of Pa into
Row vacuum-sintering is specially warming up to 400 DEG C and heat preservation 0.5h, then is warming up to 650 DEG C and heat preservation 1.5h with 8 DEG C/min, then
850 DEG C and heat preservation 1.5h are warming up to, 1070 DEG C is warming up to later and is sintered, then carry out second level annealing, obtain sintered magnet.
It observes and measures through Electronic Speculum, surface region and the interior zone distribution for the sintered magnet that embodiment 2.1-2.5 is obtained
There is the R comprising core and shell2Fe14Type B main phase grain, the Tb content of shell are higher than the Tb content in core, are being sintered
Having Hf content in the crystal grain boundary of magnet is the richness region Hf below 0.1wt% or more, 3.0wt%.
Through XRD determining, the rich region Hf for the sintered magnet that embodiment 2.1-2.5 is obtained accounts for the sintered magnet
5.0vol%-11.0vol%.
The oxygen content for measuring the sintered magnet that embodiment 2.1-2.5 is obtained is 1000ppm or less.
Performance evaluation is carried out to the sintered magnet that each embodiment and each comparative example obtain, Evaluation results are as shown in table 4.
3 constituent analysis of table (wt%)
4 performance evaluation situation of table
As conclusion we it follows that
When Tb content is less than 8wt% in auxiliary alloy, since Hf is in the distribution of crystal boundary, it is difficult to form nucleocapsid in sintering stage
Structure, it is unobvious to the promotion of magnet performance；Relatively, when Tb content is more than 30wt%, although coercivity improves, with
Heavy rare earth Tb is entered inside main phase, and remanent magnetism has great deterioration；Tb content is in 12wt%-25wt%, to sintered magnet magnetism
The promotion of energy is more beneficial.
It can be seen that the promotion with Tb content from embodiment 2.1- embodiment 2.5, sintered magnet coercivity can be changed
Kind, remanent magnetism is not substantially change, and conjecture is since under the collaboration of Hf addition, Tb only forms one layer thin in grain surface
Tb2Fe14B shell, and the Tb of high HA (anisotropy field)2Fe14B improves the anisotropy of interface magnetocrystalline in shell, improves brilliant
Boundary's structure, so that coercivity is improved, and since Tb is not spread substantially into crystal grain, thus remanent magnetism Br does not almost decline.
Comparative example 2.1 is free of Tb, and not formed core-shell structure, coercivity is significantly insufficient；It can see in comparative example 2.2, Tb
Also unsuitable excessively high, even if there are Hf in crystal boundary, also results in magnet Br and be decreased obviously.
Embodiment three
Raw material preparation: the master alloying being made of Nd, Fe, Hf, B and Al, the auxiliary alloy being made of Tb, Fe, Co and Si.
Smelting and pouring: being respectively prepared the rapid hardening thin slice with a thickness of 0.4mm for the components fuse liquid of master alloying and auxiliary alloy, right
Its ingredient is analyzed, as shown in table 5.
Hydrogen crushing: master alloying rapid hardening thin slice and auxiliary alloy rapid hardening thin slice are mixed with the mass ratio of 88:12, broken using hydrogen
Broken technique is made hydrogen and breaks powder.
Air-flow crushing: hydrogen is broken into powder again and is milled into fine powder through air-flow.
Forming sintering: fine powder magnetic forming method is obtained into formed body, and is 7*10 in vacuum degree-2In the sintering furnace of Pa into
Row vacuum-sintering is specially warming up to 380 DEG C and heat preservation 0.5h, then is warming up to the temperature of table 6 with the heating rate of table 6 with table 6
Soaking time be pre-sintered, be then warming up to 800 DEG C and heat preservation 2.5h, be warming up to 1000 DEG C later and be sintered, then
Second level annealing is carried out, sintered magnet is obtained.
It observes and measures through Electronic Speculum, surface region and the interior zone distribution for the sintered magnet that embodiment 3.1-3.5 is obtained
There is the R comprising core and shell2Fe14Type B main phase grain, the Tb content of shell are higher than the Tb content in core, are being sintered
Having Hf content in the crystal grain boundary of magnet is the richness region Hf below 0.1wt% or more, 3.0wt%.
Through XRD determining, the rich region Hf for the sintered magnet that embodiment 3.1-3.5 is obtained accounts for the sintered magnet
5.0vol%-11.0vol%.
The oxygen content for measuring the sintered magnet that embodiment 3.1-3.5 is obtained is 1000ppm or less.
Performance evaluation is carried out to the sintered magnet that each embodiment and each comparative example obtain, Evaluation results are as shown in table 7.
5 constituent analysis of table (wt%)
Table 6
Performance evaluation is carried out to the sintered magnet that each embodiment and each comparative example obtain, the results are shown in Table 7.
7 performance evaluation situation of table
As conclusion we it follows that
Increase by one section of pre-sintered operation in the heating process of vacuum-sintering, main phase grain surface can be relatively beneficial to and form core
Shell structure reduces the influence to remanent magnetism, obtains comprehensive performance more preferably magnet.This may be due to be rapidly heated to 600 DEG C-
After 650 DEG C, in powder processed and forming process, the edge inside formed body such as antioxidant, lubricant and partial oxidation of absorption is split
Gap, slit discharge, magnet are shunk, and density starts to increase, while the promotion of temperature, and inside starts liquid phase occur, and particle is by liquid phase
The promotion of surface tension is subjected to displacement, and Hf excellent high-temperature stability and pinning effect, adjusts the Tb in the region crystal boundary richness Hf
Arrangement, Tb are easier to be enriched near crystal boundary.
Example IV
Raw material preparation: the master alloying being made of Nd, Fe, Pr, Hf, B, Zn and Cu, by Tb, Fe and Zr auxiliary alloy formed or
The auxiliary alloy being made of Dy, Fe and Zr.
Smelting and pouring: being respectively prepared the rapid hardening thin slice with a thickness of 0.5mm for the components fuse liquid of master alloying and auxiliary alloy, right
Its ingredient is analyzed, as shown in table 8.
Hydrogen crushing: master alloying rapid hardening thin slice and auxiliary alloy rapid hardening thin slice are mixed with the mass ratio of 90:10, broken using hydrogen
Broken technique is made hydrogen and breaks powder.
Air-flow crushing: hydrogen is broken into powder again and is milled into fine powder through air-flow.
Forming sintering: fine powder magnetic forming method is obtained into formed body, and is 5*10 in vacuum degree-2In the sintering furnace of Pa into
Row vacuum-sintering is specially warming up to 400 DEG C and heat preservation 0.5h, then is warming up to 600 DEG C and heat preservation 2h with 8 DEG C/min, then rises
Temperature is to 850 DEG C and keeps the temperature 1.5h, is warming up to 1070 DEG C later and is sintered, then carries out second level annealing, obtain sintered magnet.
It observes and measures through Electronic Speculum, surface region and the interior zone distribution for the sintered magnet that embodiment 4.1-4.3 is obtained
There is the R comprising core and shell2Fe14Type B main phase grain, the Tb content of shell are higher than the Tb content in core, are being sintered
Having Hf content in the crystal grain boundary of magnet is the richness region Hf below 0.1wt% or more, 3.0wt%.
Through XRD determining, the rich region Hf for the sintered magnet that embodiment 4.1-4.3 is obtained accounts for the sintered magnet
5.0vol%-11.0vol%.
The oxygen content for measuring the sintered magnet that embodiment 4.1-4.3 is obtained is 1000ppm or less.
Performance evaluation is carried out to the sintered magnet that each embodiment and each comparative example obtain, Evaluation results are as shown in table 9.
8 constituent analysis of table (wt%)
9 performance evaluation situation of table
As conclusion we it follows that
From comparative example 4.1- comparative example 4.3 as can be seen that only replacing Tb with Dy, sintered magnet does not show embodiment
4.1-
Magnetic property shown in embodiment 4.3 is promoted, and conjecture is failed to be formed and is conducive to since Dy and Hf collective effect is unobvious
The factor of shell structurre, while the part Dy enters main phase and remanent magnetism is caused slightly to decline.And to be conducive to main phase dilute with richness by Tb and Hf
The formation of native phase core-shell structure, Hf is in the pinning effect of grain boundaries, so that Tb is difficult to enter inside main phase grain, coercivity is obvious
It improves, while remanent magnetism being kept not have significant change.
Above-described embodiment is only used for explaining technical solution provided by the present invention, can not limit the present invention
System, any simple modification, equivalent change and modification to the above embodiments, fall according to the technical essence of the invention
Enter in the protection scope of technical solution of the present invention.
Claims (9)
1. a kind of R-Fe-B based sintered magnet containing Tb and Hf, the R is rare earth element, and includes at least Nd, and feature exists
In: the R comprising core and shell is distributed in the surface region and interior zone of the sintered magnet2Fe14Type B main phase grain,
The Tb content of the shell is higher than the Tb content in the core, and there is in the crystal grain boundary of the sintered magnet Hf content to be
The richness region Hf below 0.1wt% or more, 3.0wt%, the richness region Hf is in the crystal grain boundary in point of uniform dispersion
Cloth, and account for the 5.0vol%-11.0vol% of the sintered magnet.
2. a kind of R-Fe-B based sintered magnet containing Tb and Hf according to claim 1, it is characterised in that: the sintering
Magnet is mixed with by master alloying and auxiliary alloy, and the mass ratio of the master alloying and the auxiliary alloy is (85-90):
(10-15), the Hf are originated from the master alloying, and the master alloying includes the Hf of 0.03wt%-1.80wt%, and the Tb is originated from institute
Auxiliary alloy is stated, the auxiliary alloy includes the Tb of 8wt%-30wt%.
3. a kind of R-Fe-B based sintered magnet containing Tb and Hf according to any one of claim 1 or 2, feature exist
In: the oxygen content of the sintered magnet is 1000ppm or less.
4. a kind of R-Fe-B based sintered magnet containing Tb and Hf according to claim 2, which is characterized in that the main conjunction
Fitting has by composition formula RaFecHfbBdXeThe composition of expression, the auxiliary alloy have by composition formula TbfFegMhThe composition of expression:
R is selected from at least one kind of of rare earth element, and the R includes Nd；
X be selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Ta, W,
O, at least one kind of in C, N, S or P；
M is selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Ta or W
In it is at least one kind of；
A, by weight percentage, a 26-33, b 0.03-1.8, d 1-1.15, e 0-3, c are by b, c, d, e, f, g, h
100-a-b-d-e, f 8-30, h 0-3, g 100-f-h.
5. a kind of R-Fe-B based sintered magnet containing Tb and Hf according to claim 4, it is characterised in that: the b is
0.08-1.0。
6. a kind of R-Fe-B based sintered magnet containing Tb and Hf according to claim 4, it is characterised in that: the f is
12-25。
7. a kind of R-Fe-B based sintered magnet containing Tb and Hf, the sintered magnet is burnt by master alloying and the mixing of auxiliary alloy
Knot is prepared, which is characterized in that the mass ratio of the master alloying and the auxiliary alloy is (85-90): (10-15), the master
Alloy has by composition formula RaFecHfbBdXeThe composition of expression, the auxiliary alloy have by composition formula TbfFegMhThe composition of expression:
R is selected from at least one kind of of rare earth element, and the R includes Nd；
X be selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Ta, W,
O, at least one kind of in C, N, S or P；
M is selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Ta or W
In it is at least one kind of；
A, by weight percentage, a 26-33, b 0.03-1.8, d 1-1.15, e 0-3, c are by b, c, d, e, f, g, h
100-a-b-d-e, f 8-30, h 0-3, g 100-f-h.
8. a kind of preparation method of the R-Fe-B based sintered magnet containing Tb and Hf, which is characterized in that the sintered magnet is logical
It crosses master alloying and auxiliary alloy mixed sintering is prepared, the mass ratio of the master alloying and the auxiliary alloy is (85-90): (10-
15), the master alloying has by composition formula RaHfbFecBdXeThe composition of expression, the auxiliary alloy have by composition formula TbfFegMh
The composition of expression:
R is selected from at least one kind of of rare earth element, and the R includes Nd；
X be selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Ta, W,
O, at least one kind of in C, N, S or P；
M be selected from Co, Al, Cu, Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Ta or
It is at least one kind of in W；
A, by weight percentage, a 26-33, b 0.03-1.8, d 1-1.15, e 0-3, c are by b, c, d, e, f, g, h
100-a-b-d-e, f 8-30, h 0-3, g 100-f-h,
And include at least following process:
The process that the components fuse liquid of the master alloying and the auxiliary alloy is prepared into rapid hardening thin slice respectively；By the master alloying
The process that fine powder is made in rapid hardening thin slice and the auxiliary alloy rapid hardening thin slice mixing, suction hydrogen breaking and Crushing of Ultrafine；With the fine powder magnetic
Forming process or hot pressing thermal deformation obtain formed body, and in vacuum or inert gas with 1000 DEG C -1070 DEG C of temperature to institute
It states formed body and is sintered acquisition.
9. a kind of preparation method of R-Fe-B based sintered magnet containing Tb and Hf according to claim 8, feature exist
In, the heating process of the sintering includes the following steps, from 350 DEG C -400 DEG C with 6 DEG C/min-9 DEG C/min be warming up to 600 DEG C -
650 DEG C of processes being pre-sintered, and the process being sintered at 1000 DEG C -1070 DEG C.
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