3.2. Coercivity of (Fe0.7Co0.3)2B Bonded Magnet from Nanowires
The coercivity contributed by MSA, decreases with increasing packing fraction of magnetic particles (or a decrease in the inter-particle distance) due to inter-particle magnetostatic interactions [
34,
35]. When the distance between neighboring nanowires is zero, the coercivity from MSA disappears. We can prepare bonded magnets using the (Fe
0.7Co
0.3)
2B nanowires as the starting materials to take advantage of the coercivity contributed by magnetic shape anisotropy. The magnetic powder is mixed with binder such as epoxy resin, nylon, etc., and formed into bulk magnets with specific shapes and sizes using methods like compression and injection molding [
36]. The non-magnetic binder separates the magnetic nanowires in the bonded magnet, which helps to retain the coercivity originating from MSA. In addition, the non-magnetic binder bonds the magnetic particles together, enabling the necessary mechanical properties for applications.
Although the bonded magnet can partially retain the coercivity from the contribution of magnetic shape anisotropy, the binder dilutes the magnetic powder content which, in turn, decreases magnetic remanence and maximum energy product. To evaluate the potential performance of (Fe
0.7Co
0.3)
2B bonded magnet, we calculate the magnetic properties as a function of the volume fraction of the particles. Four types of (Fe
0.7Co
0.3)
2B magnetic particles are selected as feedstock powder for the bonded magnet: 1) s-nanowire with a diameter of 16 nm and a length of 256 nm; 2) s-nanowire with a diameter of 16 nm and a length of 256 nm, including a surface defect layer of 2 nm with reduced MCA of
K1 shell =0.7*
K1 core ; 3) c-nanowire with a diameter of 16 nm and a length of 256 nm; 4) c-nanowire with a diameter of 16 nm and a length of 256 nm, including a surface defect layer of 2 nm with reduced MCA of
K1 shell =0.7*
K1 core. The morphologies of the s-nanowire (3) and c-nanowire (4) with defects were also shown in
Figure 3 and described in the previous section. The nanowires are assumed to be magnetically aligned along a single direction and uniformly distributed in the bonded magnets.
The strong magnetostatic interaction between nanowires will reduce the coercivity of the assembly of magnetic nanowires. Several groups have studied the correlation between coercivity and packing fraction for acicular-shaped magnetic particles[
37,
38,
39,
40,
41]. The coercivity with a contribution of MCA and MSA can be approximated phenomenologically by [
41]
P, A, and
B are volume packing fractions, MCA contributed coercivity, and isolated particle coercivity due to MSA, respectively. For isolated particles (
P=0), the coercivity is the sum of the parts originating from MCA and MSA. The predicted linear correlation between coercivity and packing fraction from Eq.1 has also been confirmed in cobalt nanowire assemblies from micromagnetic simulations [
42]. The coercivity value of several simulated nanowires with
K1=0 has been calculated to derive parameter
B. The shape, size, magnetization, and exchange parameters of the simulated nanowires are the same as those of nanowires 1, 2, 3, and 4, respectively. The calculated coercivity of the simulated nanowires is entirely contributed by magnetic shape anisotropy (i.e.,
B). Parameter A can be estimated from the coercivity difference between the actual and simulated nanowires. The calculated parameters
A and
B are listed in
Table 2. The
A values differ, but the
B values are the same for nanowire-1 and nanowire-2. The result is unsurprising, as nanowires 1 and 2 have the same geometry, size, and magnetic parameters except for MCA constant
K1. The parameter
A is mainly determined by MCA while
B arises from magnetic shape anisotropy. Similar observations are made for nanowire-3 and nanowire-4 (
Table 2).
Theoretically, the packing density for orderly packing of ellipsoids is 0.7707 for the particles with an aspect ratio larger than 1.732 [
43]. The packing density of circular cylinders with a high aspect ratio is slightly higher than π/
based on geometry analysis [
44]. So, we estimate the extrinsic magnetic properties of nanowire bonded magnets with a packing fraction up to 0.7.
Figure 5 shows the calculated extrinsic magnetic properties of (Fe
0.7Co
0.3)
2B bonded magnets with different types of particles. As expected, the coercivity decreases while the
Br values increase linearly with increasing volume packing fraction. Relative to equation 1 above, the coercivity originating from MCA remains unchanged (
A), while the coercivity arising from MSA linearly reduces with increasing magnetic particle volume fraction. The
Br values of bonded magnets are the same for different magnetic particles with the same volume fraction since we assume they have the same magnetization. As shown in
Figure 5, all
Hci values are higher than half of the
Br values in these bonded magnets. The magnetic particles are assumed to be aligned entirely along their magnetic easy-axis direction, i.e., a 100 % DOA (degree of alignment), resulting in a demagnetization curve with excellent squareness in the bonded magnet (
Figure 6). The
(BH)m = (
Br)
2/4, shows a similar trend, being determined by the volume fraction of the different magnetic nanowires. For 40–70 vol.% c-nanowires with 30% reduced MCA defect shell, the bonded magnets can achieve a
Hci value of
~7.3-8.2 kOe and a
(BH)m of 6.8-20.6 MGOe.
For the 40–70 vol.% s-nanowire as feedstock, the bonded magnets would have
Hci of 9.1-10.5 kOe and a
(BH)m of 6.8-20.6 MGOe. In addition to the morphology, structural defect, and volume fraction of the nanowires, the bonded magnet's performance also depends on the nanowire size.
Table 3 lists the magnetic properties of several typical nanowire-based bonded magnets in which the
(BH)m ranged between 10 and 20 MGOe. It should be noted that we, here, considered only the perfect alignment situation (i.e., 100% DOA). However, misalignment of the nanowires will deteriorate the coercivity, remanence, and squareness of demagnetization curves. The (Fe
0.7Co
0.3)
2B bonded magnets have magnetic performance better than Sr- or Ba-ferrite and Alnico, comparable to Nd-Fe-B bonded magnets, but inferior to sintered Nd-Fe-B and Sm-Co magnets. They can be potential gap magnets with performance intermediated between the SrFe
12O
19 ferrite and the Nd-Fe-B magnets.
3.3. Challenge and Roadmap for Developing (Fe0.7Co0.3)2B Based Permanent Magnets
Due to the relatively low MCA of (Fe
0.7Co
0.3)
2B, one way to improve coercivity is to optimize microstructure. The size and morphology significantly affect coercivity for magnetic phases with moderate or low MCA at the particle or crystal grain level. Appropriately tailored (Fe
0.7Co
0.3)
2B nanowires can achieve coercivity higher than the theoretical value of the MCA field since combining the contribution from MCA and MSA. This will be potentially a practical approach to enable coercivity of hard magnetic phases with moderate MCA, such as Fe-based rare earth free magnets. One challenge is effectively preparing the (Fe
0.7Co
0.3)
2B nanowires at a large scale. Although there are reports on the synthesis of Fe-Co-B magnetic micro- or nanowires in recent years [
25,
26], the synthesis of single crystal and single domain (Fe
0.7Co
0.3)
2B nanowires is still the most challenging task for developing Fe-Co-B hard magnets that leverage the MCA and MSA contributions to coercivity. Developing novel synthesis technologies will be important in developing nanowire-based permanent magnets.
Another challenge is assembling the particles into bulk (full density or bonded) magnets.
Figure 6a shows the schematic microstructure of a bonded magnet in which the (Fe
0.7Co
0.3)
2B nanowires retain their size and shape and are separated by the binder matrix. Hence, the coercivity of particles arising from MSA can also be partially retained (
Figure 5) since the binder helps to keep the particles separated. On the other hand, full-density bulk magnets would have a polycrystalline microstructure containing polyhedron grains with no specific morphology (
Figure 6b). The coercivity originates from MCA. In addition to the proper selection of binder and fabrication methods, one challenge for nanowire bonded magnets is how to achieve high DOA, which has a direct impact on remanence, coercivity contributed from MSA part, the squareness of demagnetization curve, and maximum energy product.
Figure 6c shows the calculated demagnetization curves for the nanowire bonded magnet and the full-density polycrystal magnet. The bonded magnet has a 65 vol% of (Fe
0.7Co
0.3)
2B s-nanowires (Fig 6a). The s-nanowire has a size of Φ16×256 nm and a 2 nm thick surface shell with an MCA reduction of 30%. This results in a bonded magnet with
Br=8.4 kG,
Hci=9.9 kOe, and
(BH)m=17.8 MGOe (
Figure 6c), comparable with anisotropic Nd-Fe-B bonded magnet. The large coercivity enables a linear second quadrant induction demagnetization B-H curve with no knee point (
Figure 6c, black dash line). Such a B-H curve is ideal for dynamic applications, e.g., electric motors and generators.
The full-density polycrystalline bulk magnet has a mean grain size of 20 nm and a local MCA reduction of up to 30% (Figure6b) and shows typical extrinsic magnetic properties of
Br=12.3 kG,
Hci=2.7 kOe, and
(BH)m=25.6 MGOe from micromagnetic simulation (
Figure 6c). Although they can result in higher
Br and
(BH)m, the low intrinsic coercivity results in a nonlinear second quadrant induction demagnetization curve (B-H curve) with a knee point in the second quadrant of the hysteresis loop. This limits them to some static applications (i.e., the working point is fixed).