CN105427986A - High-performance SmCo permanent magnet - Google Patents
High-performance SmCo permanent magnet Download PDFInfo
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- CN105427986A CN105427986A CN201510835209.4A CN201510835209A CN105427986A CN 105427986 A CN105427986 A CN 105427986A CN 201510835209 A CN201510835209 A CN 201510835209A CN 105427986 A CN105427986 A CN 105427986A
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Abstract
Disclosed by the present invention is a high-performance SmCo permanent magnet. The SmCo magnet has an Sm(CobalFe0.3Cu0.043Zr0.03)z solid-solution state magnet, wherein a value of z is any one of the following figures: 7.60, 7.84, 8.06; and the solid-solution state magnet has Sm2O3, and the processing procoss comprises: alloy ingot forging, hydrogen decrepitation, jet mill, press molding, sintering and solid dissolving and aging treatment, wherein the process of sintering and solution curing is to sinter a blank obtained by press molding for 0.3-1 h under 1170-1220 DEG C, then dissolve a solid for 2-6 h under 1155-1185 DEG C, and cooling the solid solution by air to the room temperature rapidly to obtain a sintered billet. The high-performance SmCo permanent magnet disclosed by the present invention is better in mass-production and easy to be promoted and applied in large scale, and has a high energy product, a high remanence, a low inherent coercive force and a high heat-resistant temperature, and can effectively meet technical requirements of a drive motor of an electric vehicle.
Description
Technical field
The invention discloses a kind of samarium cobalt permanent magnet body, particularly a kind of high-performance SmCo permanent magnet, especially high Fe content high-performance 2:17 type SmCo magnet.
Background technology
In recent years, the development of functional material effectively facilitates the social progress of human society, and permanent magnetic material is the one in functional material, because it has Conversion of Energy function and various magnetic physical effect, has been widely used in current information-intensive society at present.Rare earth permanent-magnetic material is a kind of permanent magnetic material that now known combination property is the highest, and it is higher than the magnetic property of magnet steel more than 100 times, than ferrite, aluminium nickel cobalt superior performance many.Due to the use of rare earth permanent-magnetic material, not only facilitate permanent magnet devices to miniaturization, improve the performance of product, and impel the generation of some particular device, so rare earth permanent-magnetic material one occurs, cause the very big attention of various countries immediately, develop very rapid.Rare earth permanent-magnetic material can mainly be divided into by composition: 1. rare earth cobalt permanent magnets, comprises the large class of Rare-Earth Cobalt (1-5 type) permanent magnetic material SmCo5 and Rare-Earth Cobalt (2-17 type) permanent magnetic material Sm2Co17 two; 2. rare earth neodymium permanent magnetic material, NdFeB permanent magnetic material; 3. rare earth Fe-N (RE-Fe-N system) or Rare-earth Iron carbon (RE-Fe-C system) permanent magnetic material.
Samarium cobalt permanent magnet body comes across the sixties in 20th century, difference according to composition is divided into SmCo5 and Sm2Co17, be respectively a mat woven of fine bamboo strips generation and the mat woven of fine bamboo strips two generation rare earth permanent-magnetic material, it has higher magnetic energy product and reliable coercive force, although due to samarium and strategy metal cobalt that its raw material is reserves rareness, raw material is rare, expensive and make it develop to be restricted, along with the development of NdFeB material, its application reduces gradually, but in rare earth permanent magnet series, shows good temperature characterisitic due to samarium cobalt permanent magnet body.Compared with neodymium iron boron, SmCo is more suitable for being operated in hot environment, is therefore still widely used in the high temperature harsh environment such as military industrial technology.
The magnetic property of samarium cobalt magnet and the tissue of magnetic and granularity closely related.For anisotropic permanent magnet, the magnetocrystalline in magnet all arranges according to the direction of easy magnetizing axis, and the anisotropy of magnet is strong, and magnetic property is good; Permanent-magnet alloy has higher coercive force due to the dimensional effect of crystal grain in addition, the permanent-magnet alloy that preparation crystallite dimension is less, thus raising coercive force is also one of developing direction of samarium-cobalt permanent-magnetic material, for hard magnetic material, the essential condition obtaining high remanent magnetization is that the anisotropy of magnetocrystalline is strong.
Sm2Co17 magnet has the maximum magnetic energy product of 30MGOe (240kJ/m3), and its machine work difficulty is very large, and it is lower than SmCo5 containing cobalt ratio, and the cost of raw material is lower; Sm2Co17 magnet has excellent corrosion resistance and magnetic property high-temperature stability, and other rare earth permanent magnet compares, and its Br reversible temperature coefficient is minimum, and representative value is-0.03%/DEG C.Be mainly used in servo motor, water pump coupling and transducer; Particularly be used in magnet working temperature high, hot and humid or other height corrosion environment in.
Summary of the invention
For solving the problem, high-performance SmCo permanent magnet disclosed by the invention, main purpose is on the basis of existing technology, the preparation technology of the advanced persons such as introducing rapid hardening, hydrogen are broken, airflow milling, realize the regulation and control that become more meticulous of samarium cobalt magnet composition and heterogeneous microstructure, promote the magnetic property of samarium cobalt magnet; Solve new technology and the industrial compatibility issue of existing samarium cobalt magnet, based on rising to of samarium cobalt magnet preparation of industrialization technology, complete batch, the quality stability of high energy product, high remanent magnetism, high temperature tolerance SmCo magnet steel, realize effective application of driving motor for electric automobile.
High-performance SmCo permanent magnet disclosed by the invention, has Sm (Co in SmCo magnet
balfe
0.3cu
0.043zr
0.03)
zsolid solution state magnet, wherein, z span is that (preferred z value is following arbitrary to 7.60-8.06: 7.60,7.84,8.06);
In solid solution state magnet, there is Sm
2o3 (this is that the introducing of oxygen in magnet preparation process causes);
The processing technology of high-performance SmCo permanent magnet comprises alloy cast ingot, hydrogen fragmentation, airflow milling, compressing, sintering solid solution, Ageing Treatment, wherein: sintering solid solution is that the compressing blank obtained is sintered 0.3-1 hour at 1170 DEG C-1220 DEG C, subsequently in 1155 DEG C-1185 DEG C solid solution 2-6 hour, and fast wind is as cold as room temperature, obtain sintered blank.
The dephasign that the present invention program produces after suppressing the solid solution of high Fe content magnet by regulation and control Sm content, finally obtains the cell structure of comparatively uniformity, improves the magnetic property of magnet.
The one of high-performance SmCo permanent magnet disclosed by the invention is improved, include crystalline A and crystallization B in (when z value is 7.60) solid solution state magnet, wherein crystallization B is discrete is distributed in (crystallization B accounts for the 5-12% of solid solution state magnet cumulative volume) in crystalline A.EDS characterization result shows, the Sm content in crystalline A region is higher than crystallization B region, and in crystalline A region, Fe content is more lower slightly than crystallization B region.
The one of high-performance SmCo permanent magnet disclosed by the invention is improved, and the element composition of crystalline A comprises (wt%): Sm26.5%; Co46.3%; Fe21.0%; Cu3.4%; Zr2.8%.
The one of high-performance SmCo permanent magnet disclosed by the invention is improved, and the element composition of crystallization B comprises (wt%): Sm23.4%; Co47.4%; Fe22.8%; Cu3.5%; Zr2.9%.
The one of high-performance SmCo permanent magnet disclosed by the invention is improved, and crystalline A is TbCu
7the 1:7H phase of type structure, its crystal zone axis is [1-1-1] direction.
The one of high-performance SmCo permanent magnet disclosed by the invention is improved, and crystallization B is Th
2zn
17the 2:17R phase of type structure and Th
2ni
17the 2:17H phase of type structure.
TEM characterizes display simultaneously, and crystalline A region does not have obvious sheet phase, and its blackstreak is thickness of sample information, and electron diffraction spot shows it for TbCu
7the 1:7H phase of type structure, its crystal zone axis is [1-1-1] direction.There is obvious sheet phase in crystallization B region, electron diffraction spot shows it for Th
2zn
17the 2:17R phase of type structure and Th
2ni
17type structure 2:17H phase, because the diffraction spot of 2:17H phase is very weak, its content is less, and its sheet may be 2:17H phase mutually.In addition, (-101) of 2:17R phase, (-102), (-201), (-202) and (-204) spot is all obviously elongated, and this illustrates that these crystal faces exist lot of face defects, namely unordered 2:17R phase.In addition because Co-Co dumbbell shape structure is to replacing CaCu at random
5type SmCo
5the Sm atom of middle part then defines TbCu
7type structure, if this is substituted by complete ordering replacement, forms Th
2zn
17type structure or Th
2ni
17type structure, then may form 2:17R containing many planar defects as this is substituted by partial order.Visible, B region is the mixture of partial order 2:17R phase and a small amount of 2:17H phase.
XRD collection of illustrative plates also shows, z=7.60 magnet XRD figure demonstrates obvious two phase characters, 2:17R phase and 1:7H phase are all derivative on the basis of 1:5 phase, both many interplanar distances are all very close, so a lot of crystallographic plane diffraction peak overlaps, but still the interplanar distance of some crystal face exists larger difference, there is obvious swarming phenomenon in some the diffraction maximum position therefore on XRD collection of illustrative plates.Due to representative (204)
2:17Rthere is elongation in (-204) diffraction spot of crystal face, i.e. (204)
2:17Rthere is many planar defects in crystal face, this will cause (204) in XRD
2:17Rthe reduction of crystallographic plane diffraction peak, so on its XRD collection of illustrative plates (204)
2:17Rcrystallographic plane diffraction peak is very weak.(204)
2:17Rthe height of crystallographic plane diffraction peak has reacted Th to a certain extent
2zn
17the ordering degree of type structure 2:17R phase, when (204)
2:17Rwhen crystallographic plane diffraction peak disappears completely, thing is the 2:17 phase of complete unordered replacement mutually, is 1:7H phase.When z is increased to 7.84, magnets exhibit goes out the feature of 1:7H phase, visible, and namely raising z value reduces Sm content and can effectively suppress to be separated, thus obtains single 1:7H phase solid solution.But when the nearly step of z value is elevated to 8.06, the stoichiometric proportion of alloying component deflection 2:17, now solid solution state magnet due to Sm content too low and be difficult to be formed uniform 1:7H phase; In addition, because speed is cold, the 2:17R phase that solid solution state magnet forming part is orderly, XRD collection of illustrative plates shows (204)
2:17Rthe reduction of crystallographic plane diffraction peak, but now the degree of order of 2:17R phase is obviously greater than the 2:17R phase in z=7.60 solid solution state magnet.The too low formation being also unfavorable for even 1:7H phase solid solution of visible Sm content.
The one of high-performance SmCo permanent magnet disclosed by the invention improves, and in crystallization B, 2:17R phase is the mode stacking along ABCABC.
The one of high-performance SmCo permanent magnet disclosed by the invention improves, and in crystallization B, 2:17H phase is the mode stacking along ABAB.
In this programme, adopt the sintering temperature of 1190 DEG C-1220 DEG C, mainly based on following consideration, high temperature sintering (>1210 DEG C) is although slightly improve remanent magnetism and the coercive force of magnet, but have clearly deteriorated the direction degree of magnet, as seen from the figure, squareness obviously worsens when sintering temperature is more than 1200 DEG C, and the deterioration of direction degree may be that Sm volatilizees the result causing microstructure uneven.In conjunction with the situation of remanent magnetism, coercive force and squareness, suitable sintering temperature should be 1200 DEG C.
High-performance SmCo permanent magnet disclosed by the invention, its performance is all not less than following detected value:
1)BH(max)≥30MGOe；
2)Br≥11KGs；
3)Hcj≥16KOe；
4) under 200 DEG C of working temperatures, residual magnetism temperature coefficient >=-4.5%%/DEG C.
In the present invention program, the remanent magnetism of magnet increases with the rising of z value, and rear reduction is first increased in the increase of coercivity z value, and maximum magnetic energy product affects by both and shows one and first increase the trend of falling afterwards.The monotone increasing of remanent magnetism may be the result that samarium content reduces and the degree of orientation improves, and samarium content reduces the ratio of 2:17R phase after increase timeliness, and it is owing to defining uniform single thing phase, causing remanent magnetism to improve that the degree of orientation improves.Owing to all defining the 2:17R phase of partial order under too high and too low samarium content, destroy the uniformity consistency of cellular structure, thus be degrading magnet coercive force.
Accompanying drawing explanation
SEM figure (z=7.60,7.84,8.06) of the solid solution state magnet of Fig. 1, high-performance SmCo permanent magnet disclosed by the invention;
The solid solution state magnet crystalline A of Fig. 2, high-performance SmCo permanent magnet disclosed by the invention and the TEM in crystallization B region scheme and electron diffraction pattern (z=7.60);
The XRD collection of illustrative plates of the solid solution state magnet ingot casting of high-performance SmCo permanent magnet when Fig. 3, different z value disclosed by the invention;
The magnet of Fig. 4, high-performance SmCo permanent magnet disclosed by the invention is perpendicular to TEM figure (z=7.60 (a figure) and z=7.84 (b figure)) in c-axis plane;
The timeliness magnet of Fig. 5, high-performance SmCo permanent magnet disclosed by the invention is perpendicular to TEM figure (z=7.60 and z=7.84) in c-axis plane;
The magnetic property (impact that Z value is different) of Fig. 6, high-performance SmCo permanent magnet disclosed by the invention;
Magnetic property (z=7.84) when the solid solubility temperature of Fig. 7, high-performance SmCo permanent magnet disclosed by the invention is 1175 DEG C under different sintering temperature;
Magnetic property (z=7.84) when the sintering temperature of Fig. 8, high-performance SmCo permanent magnet disclosed by the invention is 1200 DEG C under different solid solubility temperature;
The solid solubility temperature of Fig. 9, high-performance SmCo permanent magnet disclosed by the invention is 1155 DEG C, 1175 DEG C and 1185 DEG C time SEM figure (z=7.84).
Embodiment
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
Magnet embodiment 1
High-performance SmCo permanent magnet in the present embodiment, has Sm (Co in SmCo magnet
balfe
0.3cu
0.043zr
0.03)
zsolid solution state magnet, wherein, z span is 7.60; In solid solution state magnet, there is Sm
2o
3.
Magnet embodiment 2
High-performance SmCo permanent magnet in the present embodiment, has Sm (Co in SmCo magnet
balfe
0.3cu
0.043zr
0.03)
zsolid solution state magnet, wherein, z span is 7.84; In solid solution state magnet, there is Sm
2o
3.
Magnet embodiment 3
High-performance SmCo permanent magnet in the present embodiment, has Sm (Co in SmCo magnet
balfe
0.3cu
0.043zr
0.03)
zsolid solution state magnet, wherein, z span is 8.06; In solid solution state magnet, there is Sm
2o
3.
Magnet embodiment 4
High-performance SmCo permanent magnet in magnet the present embodiment, has Sm (Co in SmCo magnet
balfe
0.3cu
0.043zr
0.03)
zsolid solution state magnet, wherein, z span is 7.73; In solid solution state magnet, there is Sm
2o
3.
Magnet embodiment 5
High-performance SmCo permanent magnet in the present embodiment, has Sm (Co in SmCo magnet
balfe
0.3cu
0.043zr
0.03)
zsolid solution state magnet, wherein, z span is 7.91; In solid solution state magnet, there is Sm
2o
3.
Distinguish with above-described embodiment: include crystalline A and crystallization B in solid solution state magnet, wherein crystallization B is discrete is distributed in crystalline A.
Distinguish with above-described embodiment: the element of crystalline A forms and comprises (wt%): Sm26.5%; Co46.3%; Fe21.0%; Cu3.4%; Zr2.8%; The element composition of crystallization B comprises (wt%): Sm23.4%; Co47.4%; Fe22.8%; Cu3.5%; Zr2.9%.
Distinguish with above-described embodiment: crystalline A is TbCu
7the 1:7H phase of type structure, its crystal zone axis is [1-1-1] direction; Crystallization B is Th
2zn
17the 2:17R phase of type structure and Th
2ni
17the 2:17H phase of type structure.
To distinguish with above-described embodiment: in crystallization B, 2:17R phase is the mode stacking along ABCABC (namely forming three layers to be cycled to repeat); In crystallization B, 2:17H phase is the mode stacking along ABAB (namely formed bilayer be cycled to repeat).
Include, without being limited to the enforcement that alloy material in above embodiment involved by magnet and magnet preparation thereof are all applicable to include, without being limited to the technical scheme shown in following preparation embodiment, and do not exceed scope of the presently claimed invention
Preparation embodiment 1
In the present embodiment, the processing technology of high-performance SmCo permanent magnet, comprise alloy cast ingot, hydrogen fragmentation, airflow milling, compressing, sintering solid solution, Ageing Treatment, wherein: sintering solid solution is that the compressing blank obtained is sintered 0.5 hour at 1175 DEG C, subsequently in 1155 DEG C of solid solutions 3 hours, and fast wind is as cold as room temperature, obtain sintered blank.
Preparation embodiment 2
In the present embodiment, the processing technology of high-performance SmCo permanent magnet, comprise alloy cast ingot, hydrogen fragmentation, airflow milling, compressing, sintering solid solution, Ageing Treatment, wherein: sintering solid solution is that the compressing blank obtained is sintered 0.3 hour at 1200 DEG C, subsequently in 1185 DEG C of solid solutions 4 hours, and fast wind is as cold as room temperature, obtain sintered blank.
Preparation embodiment 3
In the present embodiment, the processing technology of high-performance SmCo permanent magnet, comprise alloy cast ingot, hydrogen fragmentation, airflow milling, compressing, sintering solid solution, Ageing Treatment, wherein: sintering solid solution is that the compressing blank obtained is sintered 1 hour at 1220 DEG C, subsequently in 1165 DEG C of solid solutions 2 hours, and fast wind is as cold as room temperature, obtain sintered blank.
Preparation embodiment 4
In the present embodiment, the processing technology of high-performance SmCo permanent magnet, comprise alloy cast ingot, hydrogen fragmentation, airflow milling, compressing, sintering solid solution, Ageing Treatment, wherein: sintering solid solution is that the compressing blank obtained is sintered 0.7 hour at 1170 DEG C, subsequently in 1175 DEG C of solid solutions 6 hours, and fast wind is as cold as room temperature, obtain sintered blank.
Preparation embodiment 5
In the present embodiment, the processing technology of high-performance SmCo permanent magnet, comprise alloy cast ingot, hydrogen fragmentation, airflow milling, compressing, sintering solid solution, Ageing Treatment, wherein: sintering solid solution is that the compressing blank obtained is sintered 0.45 hour at 1180 DEG C, subsequently in 1173 DEG C of solid solutions 5 hours, and fast wind is as cold as room temperature, obtain sintered blank.
Illustrate that technical solution of the present invention is in the excellent part in claimed range below in conjunction with accompanying drawing:
Fig. 1 is Sm (Co
balfe
0.3cu
0.043zr
0.03)
zthe SEM figure of (z=7.60,7.84,8.06) solid solution state magnet.All containing oxide white Sm in solid solution state magnet
2o
3, this is that the introducing of oxygen in magnet preparation process causes.There is A and the B region of two different contrasts in the magnet of z=7.60, demonstrate the feature of two-phase, and z=7.84 and 8.06 demonstrates single-phase feature.Show the EDS characterization result in z=7.60 magnet A and B region, the Sm content of a-quadrant is higher than B region, and its Fe content is more lower slightly than B region.
Fig. 2 (a) and Fig. 2 (c) is respectively Sm (Co
balfe
0.3cu
0.043zr
0.03)
7.60solid solution state magnet in FIG a-quadrant and B region TEM figure.Fig. 2 (b) and Fig. 2 (d) is respectively the electron diffraction pattern figure of the encircled of its correspondence.A-quadrant does not have obvious sheet phase, and its blackstreak is thickness of sample information, and electron diffraction spot shows it for TbCu
7the 1:7H phase of type structure, its crystal zone axis is [1-1-1] direction.There is obvious sheet phase in B region, electron diffraction spot shows it for Th
2zn
17the 2:17R phase of type structure and Th
2ni
17type structure 2:17H phase, because the diffraction spot of 2:17H phase is very weak, its content should be less, and composition graphs 2 (c) is known, and its sheet may be 2:17H phase mutually.In addition, (-101) of 2:17R phase, (-102), (-201), (-202) and (-204) spot is all obviously elongated, and this illustrates that these crystal faces exist lot of face defects, namely unordered 2:17R phase.Co-Co dumbbell is to replacing CaCu at random
5type SmCo
5the Sm atom of middle part then defines TbCu
7type structure, if this is substituted by complete ordering replacement, forms Th
2zn
17type structure or Th
2ni
17type structure, then may form 2:17R containing many planar defects as this is substituted by partial order.Visible, B region is the mixture of partial order 2:17R phase and a small amount of 2:17H phase.
Fig. 3 is Sm (Co
balfe
0.3cu
0.043zr
0.03)
zthe XRD figure of (z=7.60,7.84,8.06) solid solution state magnet.Z=7.60 magnet XRD figure demonstrates obvious two phase characters, 2:17R phase and 1:7H phase are all derivative on the basis of 1:5 phase, both many interplanar distances are all very close, so a lot of crystallographic plane diffraction peak overlaps, but still the interplanar distance of some crystal face exists larger difference, there is obvious swarming phenomenon in some the diffraction maximum position therefore on XRD collection of illustrative plates.Due to representative (204)
2:17Rthere is elongation in (-204) diffraction spot of crystal face, i.e. (204)
2:17Rthere is many planar defects in crystal face, this will cause (204) in XRD
2:17Rthe reduction of crystallographic plane diffraction peak, so on its XRD collection of illustrative plates (204)
2:17Rcrystallographic plane diffraction peak is very weak.(204)
2:17Rthe height of crystallographic plane diffraction peak has reacted Th to a certain extent
2zn
17the ordering degree of type structure 2:17R phase, when (204)
2:17Rwhen crystallographic plane diffraction peak disappears completely, thing is the 2:17 phase of complete unordered replacement mutually, is 1:7H phase.When z is increased to 7.84, magnets exhibit goes out the feature of 1:7H phase, visible, and namely raising z value reduces Sm content and can effectively suppress to be separated, thus obtains single 1:7H phase solid solution.But when the nearly step of z value is elevated to 8.06, the stoichiometric proportion of alloying component deflection 2:17, now solid solution state magnet due to Sm content too low and be difficult to be formed uniform 1:7H phase; In addition, because speed is cold, the 2:17R phase that solid solution state magnet forming part is orderly, XRD collection of illustrative plates shows (204)
2:17Rthe reduction of crystallographic plane diffraction peak, but now the degree of order of 2:17R phase is obviously greater than the 2:17R phase in z=7.60 solid solution state magnet.The too low formation being also unfavorable for even 1:7H phase solid solution of visible Sm content.
Fig. 4 is Sm (Co
balfe
0.3cu
0.043zr
0.03)
z(z=7.60 and 7.84) magnet perpendicular in c-axis plane TEM figure.Wherein, Fig. 4 (a) and Fig. 4 (b) is respectively the cell structure of the magnet of z=7.60 and 7.84, the cell structure of z=7.60 magnet shows obvious difference on crystal boundary both sides, a-quadrant is decomposed to form by the 1:7 phase timeliness that samarium content is relatively high, its born of the same parents' shape size is comparatively tiny, be only about 55nm, and B region is relatively low by samarium content, the 2:17R phase timeliness of partial order is decomposed to form, its born of the same parents' shape size is comparatively thick, is about 75nm.The cell structure of the magnet of z=7.84 is decomposed by single 1:7 phase solid solution timeliness, and the magnet that its cell structure compares z=7.60 wants uniformity.Visible, more easily obtain the cell structure of uniformity after single 1:7 phase solid solution timeliness.
Fig. 5 is Sm (Co
balfe
0.3cu
0.043zr
0.03)
z(z=7.60 and 7.84) magnet along in c-axis plane TEM figure, its c-axis direction and sheet perpendicular.Fig. 5 (a) and Fig. 5 (b) is respectively Sm (Co
balfe
0.3cu
0.043zr
0.03)
zmagnet in FIG A and B two regions forms sheet phase structure after timeliness is decomposed.Two regions of z=7.60 magnet and z=7.84 magnet all define typical sheet phase structure.The sheet of a-quadrant is compared thin, and the sheet in B region is compared thick, and the strip of sheet in B regional vision is by the phase composition of many strip of sheet mutually in fact, and the formation of this slab-like phase may be relevant with there is 2:17H phase in presoma.2:17R phase is the mode stacking along ABCABC, and 2:17H phase is the mode stacking along ABAB, in the process of ordering of 2:17R phase, because atom stacking fault can form the 2:17H phase thin slice district be mingled with in the middle of 2:17R phase, 2:17R phase is poor Zr, in 2:17H phase, the solid solubility of Zr is then larger, so Zr migration in 2:17H phase defines the sheet phase of the 2:17H structure of rich Zr during timeliness, also causes sheet to be 1:3R structure by 2:17H Structure Transformation if Zr content continues to raise.In precursor B region, 2:17H is that in follow-up ag(e)ing process, rich Zr sheet is formed mutually and provides forming core point, therefore Fig. 5 (b) shows closeer rich Zr sheet phase.In addition, the c-axis direction in two regions is not completely the same, and this illustrates that the z=7.60 magnet degree of orientation is not high, and this may be separated and caused.
Fig. 6 shows Sm (Co
balfe
0.3cu
0.043zr
0.03)
z(z=7.60,7.84,8.06) magnet magnetic property is with the change of z value.Remanent magnetism increases with the rising of z value, and rear reduction is first increased in the increase of coercivity z value, and maximum magnetic energy product affects by both and shows one and first increase the trend of falling afterwards.The monotone increasing of remanent magnetism may be the result that samarium content reduces and the degree of orientation improves, and samarium content reduces the ratio of 2:17R phase after increase timeliness, and it is owing to defining uniform single thing phase, causing remanent magnetism to improve that the degree of orientation improves.Owing to all defining the 2:17R phase of partial order under too high and too low samarium content, destroy the uniformity consistency of cellular structure, thus be degrading magnet coercive force.
Fig. 7 is solid solubility temperature when being 1175 DEG C Sm (Co under different sintering temperature
balfe
0.3cu
0.043zr
0.03)
7.84magnetic property.As seen from the figure, remanent magnetism Br and coercivity H j increases with the rising of sintering temperature on the whole, but change is all not obvious.The faint increase of remanent magnetism may be because during high temperature sintering, the volatilization of Sm causes, when in magnet, the minimizing of Sm content makes timeliness, the ratio increase of 2:17R phase makes the ratio of 1:5 phase reduce simultaneously, 2:17R is the main source phase of magnet height remanent magnetism, and its ratio increase can improve remanent magnetism.In addition, 1:5 phase reduces, under identical Cu content, cell wall mutually in may have higher Cu content, the pinning effect of the relative domain wall of 1:5 of high Cu content is stronger, thus makes the coercive force of high temperature sintering magnet higher.High temperature sintering (>1210 DEG C) is although slightly improve remanent magnetism and the coercive force of magnet, but have clearly deteriorated the direction degree of magnet, as seen from the figure, squareness obviously worsens when sintering temperature is more than 1200 DEG C, and the deterioration of direction degree may be that Sm volatilizees the result causing microstructure uneven.In conjunction with the situation of remanent magnetism, coercive force and squareness, suitable sintering temperature should be 1200 DEG C.
Fig. 8 is sintering temperature when being 1200 DEG C Sm (Co under different solid solubility temperature
balfe
0.3cu
0.043zr
0.03)
7.84magnetic property.Remanent magnetism Br first increases rear reduction with the rising of solid solubility temperature, reaches peak in 1175 DEG C; Coercive force also first increases rear reduction with the rising of solid solubility temperature, but occurs when solid solubility temperature is 1185 DEG C obviously declining; Squareness is dull with the rising of solid solubility temperature to be raised, and magnetic energy product also shows the trend of falling after rising by the impact of three.In comprehensive institute, suitable solid solubility temperature should be selected at 1175 DEG C.
In order to explain Sm (Co
balfe
0.3cu
0.043zr
0.03)
7.84magnetic property with the change of solid solubility temperature, analyze the microstructure of different solid solubility temperature lower magnet here.Fig. 9 be solid solubility temperature be respectively (figure a) 1155 DEG C, (figure b) 1175 DEG C and (figure c) 1185 DEG C time magnet micro-structure diagram.As seen from the figure, in the micro-structure diagram of magnet, all there is obvious oxide white, but oxide more fine uniform when 1175 DEG C.In addition, except oxide, also have other grey dephasign can observe in the magnet at 1155 DEG C and 1185 DEG C, and dephasign at 1185 DEG C is more.The appearance of dephasign reduces the remanent magnetism of magnet on the one hand, thus makes the remanent magnetism of magnet show a trend of falling after rising with the increase of solid solubility temperature; Dephasign destroys the single 1:7 phase solid solution state of magnet on the other hand, and be unfavorable for the formation of cell structure during follow-up timeliness, dephasign is more, more serious to coercitive deterioration, so coercive force obviously declines at 1185 DEG C.When solid solubility temperature is lower than 1185 DEG C, squareness increases with the rising of solid solubility temperature, and this is because the optimization of microstructure causes; And when solid solubility temperature is elevated to 1185 DEG C, although there is dephasign, because coercitive reduction makes squareness raise on the contrary.
The technical scope midrange non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned technological means, also comprises the technical scheme be made up of above technical characteristic combination in any.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (8)
1. high-performance SmCo permanent magnet, is characterized in that: have Sm (Co in described SmCo magnet
balfe
0.3cu
0.043zr
0.03)
zsolid solution state magnet, wherein, z span is 7.60-8.06;
In described solid solution state magnet, there is Sm
2o
3;
The processing technology of described high-performance SmCo permanent magnet comprises alloy cast ingot, hydrogen fragmentation, airflow milling, compressing, sintering solid solution, Ageing Treatment, wherein: sintering solid solution is that the compressing blank obtained is sintered 0.3-1 hour at 1170 DEG C-1220 DEG C, subsequently in 1155 DEG C-1185 DEG C solid solution 2-6 hour, and fast wind is as cold as room temperature, obtain sintered blank.
2. high-performance SmCo permanent magnet according to claim 1, is characterized in that: include crystalline A and crystallization B in described solid solution state magnet, wherein crystallization B is discrete is distributed in crystalline A.
3. high-performance SmCo permanent magnet according to claim 2, is characterized in that: the element composition of described crystalline A comprises (wt%): Sm26.5%; Co46.3%; Fe21.0%; Cu3.4%; Zr2.8%.
4. high-performance SmCo permanent magnet according to claim 2, is characterized in that: the element composition of described crystallization B comprises (wt%): Sm23.4%; Co47.4%; Fe22.8%; Cu3.5%; Zr2.9%.
5. the high-performance SmCo permanent magnet according to Claims 2 or 3, is characterized in that: described crystalline A is TbCu
7the 1:7H phase of type structure, its crystal zone axis is [1-1-1] direction.
6. the high-performance SmCo permanent magnet according to claim 2 or 4, is characterized in that: described crystallization B is Th
2zn
17the 2:17R phase of type structure and Th
2ni
17the 2:17H phase of type structure.
7. high-performance SmCo permanent magnet according to claim 6, is characterized in that: in described crystallization B, 2:17R phase is the mode stacking along ABCABC.
8. high-performance SmCo permanent magnet according to claim 6, is characterized in that: in described crystallization B, 2:17H phase is the mode stacking along ABAB.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102047536A (en) * | 2008-05-30 | 2011-05-04 | 株式会社东芝 | Permanent magnet and manufacturing method therefor, permanent magnet for motor and permanent magnet motor |
| WO2015037041A1 (en) * | 2013-09-13 | 2015-03-19 | 株式会社 東芝 | Permanent magnet, motor, and power generator |
| CN104685581A (en) * | 2013-03-26 | 2015-06-03 | 株式会社东芝 | Permanent magnet, and motor and generator using the same |
-
2015
- 2015-11-26 CN CN201510835209.4A patent/CN105427986A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102047536A (en) * | 2008-05-30 | 2011-05-04 | 株式会社东芝 | Permanent magnet and manufacturing method therefor, permanent magnet for motor and permanent magnet motor |
| CN104685581A (en) * | 2013-03-26 | 2015-06-03 | 株式会社东芝 | Permanent magnet, and motor and generator using the same |
| WO2015037041A1 (en) * | 2013-09-13 | 2015-03-19 | 株式会社 東芝 | Permanent magnet, motor, and power generator |
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| L. SCHRAMM ET AL.: "Structural effects of Zr substitution in the 1:7- and 2:17-type structure", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
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