HOT DEFORMED MAGNET, AND A METHOD FOR PREPARING SAID HOT DEFORMED MAGNET
Technical Field
The present invention relates to a hot deformed magnet, as well as a method for preparing said hot deformed magnet.
Background Art
Generally, rare earth/iron/boron-based permanent magnet exhibits high remanence and coercivty, provides a high magnetic flux within a specific temperature range (for example -40 ~ 180 ℃ for EV/HEV traction motor) , and makes the electric motor have superior performances, for example high power density, high torque density and high efficiency.
The coercivity is the magnitude of magnetic field at which the magnetization of a permanent magnet is reduced to zero. It stands for the ability of the permanent magnet to generate a magnetic flux against the demagnetization field and also the ability of the permanent magnet to generate a magnetic flux agaist the high working temperature.
The remanence represents the magnitude of the maximum magnetic flux which can be generated by the permanent magnet. It represents the ability of the permanent magnet to provide a magnetic moment. Normally a high remanence is favorable to render a permanent magnet thinner and lighter in case of a fixed magnetic moment, and consequently reduce the size and volume of an electric motor, which is desirable for many applications.
Coarsen grain regions are mainly generated at the original place of the magnetic powder particulate surfaces during the hot deformation. In the coarsen grain regions, the RE2F14B grains are almost equiaxed instead of platelet, and often have a dimension of greater than 400 nm. These equiaxed large RE2F14B grains exhibit a low magnetic orientation, a low ability against the demagnetization field, and consequently deteriorated magnetic properties. Due to the presence of coarsen grain regions, a remanence as high as 1.45 T or above normally can not be achieved for the conventional hot deformed magnets.
Although great efforts on the design of the alloy composition and the preparation method for the rare earth/iron/boron-based magnetic powders and hot deformed magnets have been made in the prior art, the issue of coarse equiaxed grains or coarsen grain regions is still not overcome for the known magnetic powders and hot deformed magnets.
Summary of Invention
The object of the present invention is to provide a hot deformed magnet which has enhanced magnetic properties, especially enhanced remanence and coercivity, and almost has no coarse equiaxed grains with a diameter greater than 400 nm and consequently no coarse equiaxed grain regions in the microstructure.
Said object, according to one aspect, can be achieved by a hot deformed magnet having an alloy composition of the formula (1)
RExFe (100-x-y1-y2-z1-z2) Ty1My2Cuz1Bz2 (1) ,
wherein
RE is one or more rare earth elements, such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu, preferably Pr, Nd, Tb, and Dy;
T is one or more elements selected from the group consisting of Co, Al, Ga, Zr, Ti and Mo;
M is Nb and/or Ta;
Cu is copper;
B is boron;
the balance is Fe and inevitable impurities;
x is 13.0 ~ 15.0 at. %;
y1 is 1.2 ~ 10.0 at. %;
y2 is 0.1 ~ 0.8 at. %;
z1 is 0 ~ 0.5 at. %; and
z2 is 4.5 ~ 6.5 at. %.
Said object, according to another aspect, can be achieved by a method for preparing the hot deformed magnet according to the present invention, said method including the following steps:
1) preparing magnetic powders by melt quenching from an ingot having an alloy composition of the formula (1)
RExFe (100-x-y1-y2-z1-z2) Ty1My2Cuz1Bz2 (1) ,
wherein
RE is one or more rare earth elements, such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu, preferably Pr, Nd, Tb, and Dy;
T is one or more elements selected from the group consisting of Co, Al, Ga, Zr, Ti and Mo;
M is Nb and/or Ta;
Cu is copper;
B is boron;
the balance is Fe and inevitable impurities;
x is 13.0 ~ 15.0 at. %;
y1 is 1.2 ~ 10.0 at. %;
y2 is 0.1 ~ 0.8 at. %;
z1 is 0 ~ 0.5 at. %; and
z2 is 4.5 ~ 6.5 at. %;
2) pressing the magnetic powders prepared from step 1) to obtain a green body; and
3) hot deforming the green body prepared from step 2) to obtain the hot deformed magnet.
Brief Description of Drawings
Each aspect of the present invention will be illustrated in more detail in conjunction with the accompanying drawings, wherein :
Figure 1 shows the magnetization curves of the hot deformed magnets without Nb (a) (Example 1) and with about 0.2%of Nb (b) (Example 2) ;
Figure 2 shows the back-scattered SEM images of the hot deformed magnets without Nb (a) and (c) (Example 1) and with about 0.2%of Nb (b) and (d) (Example 2) ;
Figure 3 shows the BSE-SEM images of the hot deformed magnets without Nb (a) (Example 1) and with about 0.2%of Nb (b) (Example 2) ;
Figure 4 shows the STEM-EDS mapping of Nd and Nb of the hot deformed magnets with about 0.2%of Nb (a) (Example 2) and with about 0.6%of Nb (b) (Example 4) .
Detailed Description of Preferred Embodiments
All publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
The present invention, according to one aspect, relates to a hot deformed magnet having an alloy composition of the formula (1)
RExFe (100-x-y1-y2-z1-z2) Ty1My2Cuz1Bz2 (1) ,
wherein
RE is one or more rare earth elements, such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu, preferably Pr, Nd, Tb, and Dy;
T is one or more elements selected from the group consisting of Co, Al, Ga, Zr, Ti and Mo;
M is Nb and/or Ta;
Cu is copper;
B is boron;
the balance is Fe and inevitable impurities;
x is 13.0 ~ 15.0 at. %;
y1 is 1.2 ~ 10.0 at. %;
y2 is 0.1 ~ 0.8 at. %;
z1 is 0 ~ 0.5 at. %; and
z2 is 4.5 ~ 6.5 at. %.
In accordance with an embodiment of the hot deformed magnet according to the present invention, the hot deformed magnet can contain a predominant magnetic phase and one or more grain boundary phases.
In particular, the predominant magnetic phase is the RE2Fe14B phase having a tetragonal crystal structure. In the context of the present invention, the formula RE2Fe14B as used herein includes all the compositions having the RE2Fe14B tetragonal crystal structure, which may or may not include any other elements as stated above, as long as these other elements do not destroy the RE2Fe14B tetragonal crystal structure.
On the other hand, the specific compositions and crystal structures of said one or more grain boundary phases are quite complicated. At least one of the grain boundary phases are believed to have a lower melting temperature and a greater proportion of rare earth element (s) than those of the predominant magnetic phase, and therefore, can also be called as RE-rich phase. Another grain boundary phase is believed to be present in form of nano-sized Nb-rich and/or Ta-rich precipatets.
In accordance with another embodiment of the hot deformed magnet according to the present invention, the hot deformed magnet can exhibit anisotropy with a RE2Fe14B grain morphology in form of platelet. In particular, the hot deformed magnet can exhibit anisotropy with the crystallographic c-axes of the RE2Fe14B grains aligned or orientated substantially parallel to one another. The crystallographic c-axes of the RE2Fe14B grains in form of platelet are perpendicular to the major surfaces of the platelets and parallel to their smallest dimension. The preferred magnetic alignment direction of the RE2Fe14B grains is along their crystallographic c-axes.
In accordance with another embodiment of the hot deformed magnet according to the present invention, the thickness of the platelet can be up to 200 nm, preferably 25 ~ 120 nm, more preferably 25 ~ 100 nm. In the context of the present invention, the thickness of the platelet shall be understood as its smallest dimension.
In accordance with another embodiment of the hot deformed magnet according to the present invention, the length of the platelet can be up to 1 μm, preferably 100 ~ 600 nm, more preferably 100 ~ 300 nm. In the context of the present invention, the length of the platelet shall be understood as its largest dimension.
In accordance with another embodiment of the hot deformed magnet according to the present invention, the hot deformed magnet almost has no coarse equiaxed grains with a diameter greater than 400 nm and consequently no coarse equiaxed grain regions in the microstructure.
The present invention, according to another aspect, relates to a method for preparing the hot deformed magnet according to the present invention, including the following steps:
1) preparing magnetic powders by melt quenching from an ingot having an alloy composition of the formula (1)
RExFe (100-x-y1-y2-z1-z2) Ty1My2Cuz1Bz2 (1) ,
wherein
RE is one or more rare earth elements, such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu, preferably Pr, Nd, Tb, and Dy;
T is one or more elements selected from the group consisting of Co, Al, Ga, Zr, Ti and Mo;
M is Nb and/or Ta;
Cu is copper;
B is boron;
the balance is Fe and inevitable impurities;
x is 13.0 ~ 15.0 at. %;
y1 is 1.2 ~ 10.0 at. %;
y2 is 0.1 ~ 0.8 at. %;
z1 is 0 ~ 0.5 at. %; and
z2 is 4.5 ~ 6.5 at. %;
2) pressing the magnetic powders prepared from step 1) to obtain a green body; and
3) hot deforming the green body prepared from step 2) to obtain the hot deformed magnet.
1) Preparation of magnetic powders
In step 1) , magnetic powders can be prepared by melt quenching from an ingot having the alloy composition of the formula (1) .
In accordance with an embodiment of the method according to the present invention, the ingot can be melted at a temperature of above 1000 ℃, preferably 1000 ~ 1100 ℃, preferably under a protect atmosphere, such as Argon, and then cast or injected onto a rotating wheel, such as a copper wheel, with a circumferential velocity of 10 ~ 40 m/s, so as to obtain melt-spun ribbons or magnetic powders. The cooling rate can be set according to the circumferential velocity of the rotating wheel and the amount of the molten metal cast or injected.
In accordance with another embodiment of the method according to the present invention, melt-spun ribbons can be directly obtained by melt quenching from the ingot, and preferably have a thickness of less than 50 μm. Then the melt-spun ribbons can be optionally crushed into magnetic powders preferably having a length of less than 200 μm.
In accordance with another embodiment of the method according to the present invention, the magnetic powders or the melt-spun ribbons can be crystalline or even amorphous, or have crystallitic grains with a grain size of less than 50 nm, in each case according to the cooling rate.
2) Pressing
In step 2) , the magnetic powders prepared from step 1) can be pressed to obtain a green body.
In accordance with another embodiment of the method according to the present invention, the magnetic powders prepared from step 1) can be cold pressed at room temperature, wherein the pressure and the duration of the cold pressing are not particularly limited and can be selected in such a way to reach up to 70%or even more of the saturated density, for example 50 ~ 400 MPa and 1 ~ 5 seconds; and then hot pressed to obtain the green body, wherein the temperature of the hot pressing is not particularly limited, for example 550 ~ 850 ℃, preferably 600 ~ 700 ℃, and can be selected in such a way not to liquefy the predominant magnetic phase, but liquefy the grain boundary phase sufficiently, otherwise the densification might be insufficient and even cracks might be initiated and propagated in the green body; the pressure of the hot pressing is not particularly limited, for example 20 ~ 200 MPa, preferably 20 ~ 100 MPa, and can be selected in such a way to reach the full densification; the duration of the hot pressing is not particularly limited, for example 10 ~ 240 seconds, and can be selected in such a way to reach the full densification, but shall not be too long to cause abnormal growth of the RE4Fe14B grains and consequently deteriorate the microstructure of the green body; and the atmosphere of the hot pressing is not particularly limited, for example an inert gas protected atmosphere, an oxidation atmosphere, a reduction atmosphere, and vacuum, preferably vacuum.
3) Hot deformation
In step 3) , the green body prepared from step 2) can be hot deformed to obtain the hot deformed magnet.
In accordance with another embodiment of the method according to the present invention, the green body prepared from step 2) can be hot deformed, for example by extrusion, or die up-setting, so as to reshape the green body into the predetermined shape and geometry, such as cylinder, rectangular block or segment, and simultaneously align the crystallographic c-axes of the RE2Fe14B grains to the predetermined direction, and finally obtain the hot deformed magnet, wherein the temperature of the hot deformation is not particularly limited, for example 750 ~ 850 ℃, preferably 780 ~ 820 ℃, and can be selected in such a way to subject the green body to a plastic deformation, but not initiate and propagate cracks in the green body; the pressure of the hot deformation is not particularly limited, for example 20 ~ 250 MPa, preferably 20 ~ 200 MPa; and the atmosphere of the hot deformation is not particularly limited, for example an inert gas protected atmosphere, a reduction atmosphere, vacuum or a low oxidation atmosphere.
The anisotropy of the RE2Fe14B grains can be achieved based on such a mechanism that the RE2Fe14B grains can rotate during the hot deformation under pressure with the help of the grain boundary phase liquefied at the hot deformation temperature, so that the crystallographic c-axes of the RE2Fe14B grains can be aligned or orientated substantially parallel to one another. The crystallographic c-axes of the RE2Fe14B grains in form of platelet are perpendicular to the major surfaces of the platelets and parallel to their smallest
dimension. The preferred magnetic alignment direction of the RE2Fe14B grains is along their crystallographic c-axes.
In accordance with another embodiment of the method according to the present invention, the hot deformed magnet can be further processed by thermal annealing, grain boundary diffusion or other post treatment under cold or warm conditions.
Examples
1) Preparation of magnetic powders
Raw materials according to the alloy compositions as listed in Table 1 were melted under Argon at a temperature of above 1000 ℃ until homogeneous, and cast into ingots. The ingots were melted again under Argon at a temperature of above 1000 ℃, and then injected onto a copper wheel with a circumferential velocity of 20 m/sto obtain melt-spun ribbons. Then the melt-spun ribbons were crushed into magnetic powders having a length of less than 200 μm.
Table 1 Alloy compositions according to Examples 1 ~ 19 (all in at. %)
| Example |
Nd |
Fe |
Co |
B |
Al |
Ga | Nb |
Cu | |
| 1 |
12.83 |
75.97 |
4.5 |
5.31 |
0.43 |
0.53 |
0 |
0 |
| 2 |
12.59 |
75.67 |
4.5 |
5.44 |
0.67 |
0.52 |
0.21 |
0 |
| 3 |
12.9 |
75.21 |
4.49 |
5.52 |
0.55 |
0.51 |
0.4 |
0 |
| 4 |
13.09 |
74.87 |
4.49 |
5.56 |
0.48 |
0.52 |
0.64 |
0 |
| 5 |
13.41 |
75.42 |
4.33 |
5.3 |
0.31 |
0.51 |
0.22 |
0.19 |
| 6 |
14.42 |
75.33 |
4.5 |
5.22 |
0 |
0.53 |
0 |
0 |
| 7 |
14.42 |
75.13 |
4.5 |
5.22 |
0 |
0.53 |
0.2 |
0 |
| 8 |
14.42 |
74.93 |
4.5 |
5.22 |
0 |
0.53 |
0.4 |
0 |
| 9 |
14.42 |
74.73 |
4.5 |
5.22 |
0 |
0.53 |
0.6 |
0 |
| 10 |
14.42 |
74.93 |
4.5 |
5.22 |
0 |
0.53 |
0.2 |
0.2 |
| 11 |
13.64 |
75.29 |
4.51 |
5.58 |
0.4 |
0.54 |
0 |
0 |
| 12 |
13.52 |
75.13 |
4.48 |
5.51 |
0.5 |
0.53 |
0.2 |
0 |
| 13 |
13.5 |
74.99 |
4.51 |
5.54 |
0.5 |
0.52 |
0.41 |
0 |
| 14 |
13.56 |
74.74 |
4.5 |
5.58 |
0.5 |
0.53 |
0.61 |
0 |
| 15 |
14.15 |
75.11 |
4.5 |
5.09 |
0.3 |
0.52 |
0.17 |
0.19 |
| 16 |
13 |
75.54 |
4.48 |
5.4 |
0.63 |
0.52 |
0.21 |
0 |
| 17 |
13.03 |
75.17 |
4.49 |
5.38 |
0.57 |
0.51 |
0.4 |
0 |
| 18 |
12.88 |
75.14 |
4.49 |
5.47 |
0.51 |
0.51 |
0.66 |
0 |
| 19 |
13 |
75.85 |
4.07 |
5.34 |
0.34 |
0.52 |
0.25 |
0.19 |
2) Pressing
The magnetic powders prepared from step 1) were cold pressed at room temperature for about 5 seconds to reach at least 70%of the saturated density, and then hot pressed under vacuum at about 700 ℃ and about 100 MPa for about 120 seconds to obtain green bodies.
3) Hot deformation
The green bodies prepared from step 2) were hot deformed by extrusion under vacuum at about 800 ℃ and about 180 MPa to obtain hot deformed magnets.
Evaluation of magnetic properties
Figure 1 shows the magnetization curves of the hot deformed magnets without Nb (a) (Example 1) and with about 0.2%of Nb (b) (Example 2) . The magnetic properties of the hot deformed magnets prepared according to Examples 1 ~ 5 are listed in Table 2.
Table 2 Magnetic properties of the magnets according to Examples 1 ~ 5
The hot deformed magnets prepared according to Examples 1 ~ 5 exhibit very high remanences, for example 1.54 T as the highest and a corresponding anisotropy of 0.96, wherein the anisotropy is represented as the ratio of the remanence to the saturation magnetic flux density of 1.6 T.
It is also apparent from Table 2 that the remanence has been increased from 1.48 T (no Nb) to 1.54 T (about 0.2%of Nb) , and the coercivity also has been enhanced from 0.77 T (no Nb) to 1.08 T (about 0.2%of Nb) .
Evaluation of microstructure
Figure 2 shows the back-scattered SEM images of the hot deformed magnets without Nb (a) and (c) (Example 1) and with about 0.2%of Nb (b) and (d) (Example 2) .
It is apparent from Figure 2 that the formation of coarsen grains or coarsen grain regions in the microstructure of the hot deformed magnets has been suppressed by adding small amount of Nb. A microstructure almost having no coarse equiaxed grains with a diameter
greater than 400 nm and consequently no coarse equiaxed grain regions is favorable for the magnetic properties of the hot deformed magnets.
It is also apparent from Figure 2 that the platelet-shaped morphology of the RE2Fe14B grains has been optimized by adding Nb. In particular, both the grain size and the aspect ratio of the RE2Fe14B grains have been reduced, which is beneficial to enhance the coercivity and the thermal stability of the coericivty of the hot deformed magnets. In the context of the present invention, the aspect ratio of the platelet shall be understood as the ratio of the length to the thickness of the platelet.
Figure 3 shows the BSE-SEM images of the hot deformed magnets without Nb (a) (Example 1) and with about 0.2%of Nb (b) (Example 2) . It is apparent from Figure 3 that both the grain size and the aspect ratio of the RE2Fe14B grains have been reduced.
Figure 4 shows the STEM-EDS mapping of Nd and Nb of the hot deformed magnets with about 0.2%of Nb (a) (Example 2) and with about 0.6%of Nb (b) (Example 4) .
It is apparent from the Nb mapping in the microstructure of the hot deformed magnets that Nb mainly forms nano-sized Nb-rich precipitates at the grain boundary and slightly segregates inside the RE2Fe14B grains.
Potential applications of the hot deformed magnet according to the present invention include, but are not limited to, electric motor for automotives, power tools, home appliances, drive &control, and others.
While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. The attached claims and their equivalents are intended to cover all the modifications, substitutions and changes as would fall within the scope and spirit of the invention.