Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept.

8-10, 2008, Crete, Greece __________________________________________________________________________________________________

Development of Composite/Nanocomposite Magnets George C. Hadjipanayis1, Alexander Gabay1, Melania Marinescu2 and Jinfang Liu2 1 Department of Physics and Astronomy, University of Delaware, Newark, DE, USA 2 Electron Energy Corporation, Landisville, PA, U.S.A. The paper reviews the recent efforts to fabricate composite magnets with hard and soft magnetic components or with two hard magnetic components. Within the more traditional "top-down" approach, the composite magnets were produced from isotropic nanocrystalline precursors. Texture was developed through a hot plastic deformation. The explored systems included the Nd(Pr)-Fe-B, Sm-Co and Sm-Fe-N hard magnetic components. The other, "bottom-up" approach consists of the assembly, alignment and consolidation of separate hard and soft particles. Anisotropic Sm-Co nanoparticles can be produced via surfactant-assisted high-energy milling. A uniform distribution of soft phase can be achieved via coating of the hard magnetic particles with chemically synthesized Fe nanoparticles. Keywords: nanoparticles, nanocomposites, coating, surfactant-assisted milling, hot deformation. Contact author: George C. Hadjipanayis, University of Delaware, 217 Sharp Lab, Newark, DE 19716, U.S.A., Fax: 1-302-831-1637, Phone: 1-302-831-6289, E-mail: hadji@udel.edu.

Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece __________________________________________________________________________________________________

1. Introduction Traditional magnets with a single magnetic phase have nearly reached the limits of their maximum energy product, (BH)max. Furthermore, the demand for a higher temperature stability leads to a sacrifice of a considerable fraction of the room-temperature properties. In principle, these two issues can be addressed by combining two different materials with high magnetization and high coercivity or two materials with a good room-temperature performance and high thermal stability. The concept of nanocomposite magnets with exchange-coupled high-coercivity (hard) and high-magnetization (soft) phases [1,2] promised at least doubled values of (BH)max. The practical realizations of this concept so far fell short of the expectations, and the highest roomtemperature (BH)max remains that of the traditionally sintered Nd-Fe-B. The reasons for this underachievement are fairly well understood. Firstly, it is difficult to obtain a uniform nanostructure with the size of the soft elements not exceeding the exchange length. Secondly, it is even more difficult to have such nanostructure with a crystallographically oriented hard phase. Finally, when dealing with the not-as-high-as-predicted coercivity of the nanocomposite magnet, one has to bear in mind the Browns paradox, which refers to the discrepancy which exists between the theoretical nucleation field and coercivity of the real hard magnetic materials. In this paper, we review our recent efforts to fabricate composite magnets with superior room-temperature (BH)max and with enhanced temperature stability. Two approaches have been used. In the more traditional "top-down" approach, the hard-soft composite magnets were produced from isotropic nanocrystalline precursors susceptible to the development of texture via hot plastic deformation. In the other approach (we may call it the "bottom-up"), single-crystalline hard and soft particles have to be arranged, crystallographically oriented and then consolidated. Even though we did not yet obtain breakthrough magnetic properties, it may be worth it to discuss the strong and weak sides

of either approach and to point out the specific difficulties associated with them. 2. Hot-deformed composite magnets 2.1. Hard-soft magnets based on R2Fe14B The R-Fe-B systems with R = Pr and Nd offer (in addition the R2Fe14B compounds with their excellent hard magnetic properties) the possibility to align the easy magnetization directions of the 2:14:1 nanocrystallites through a thermomechanical process (hot plastic deformation) [3]. The alignment, however, normally occurs only in the alloys enriched with R, because of the presence of the liquid R-rich grain-boundary phase [4]. In 2006, we reported [5] that the moderately R-lean R-Fe-B nanocrystalline alloys with approximately 15% soft magnetic phase became susceptible for the thermomechanical treatment if a small amount of copper was added, as it is shown in Fig. 1(a). More recently, we found that small additions of indium generated a low-melting-temperature phase in the Sm-Co alloys [6]. According to the differential thermal analysis (DTA), a similar effect takes place in the Pr-lean Pr-Fe-In-B alloy: the Pr11Fe82In1B6 ingot exhibits what seems to be a melting temperature of a minor phase at 930 oC (see Fig. 2). This solidus temperature, however, is significantly higher than the one associated with the "usual" Pr-rich

Fig. 1. Demagnetization curves of (a) Pr11.25Fe77.75Co5B6 (1), Pr11.25Fe76.75Co5Cu1B6 (2) and (b) Pr11Fe82In1B6 hot-deformed magnets made from melt-spun alloys. Curves were measured parallel and perpendicularly to the pressure direction.

Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece __________________________________________________________________________________________________

Fig. 2. DTA (heating) curves of Pr15Fe78In1B6 (1) and Pr11Fe82In1B6 (2) ingots. The Curie temperature TC and solidus temperatures Tm are shown. phase (for Pr15Fe78In1B6 also shown in Fig. 2 that temperature was 660 oC). After the meltspun and consolidated Pr11Fe82In1B6 alloy was deformed at 950 oC, it showed only a moderate degree of texture and an intrinsic coercivity Hc of less than 2 kOe, Fig. 1(b). According to recent studies [7,8], die-upset magnets made from blends of nanocrystalline Rrich R-Fe-B alloys and coarse Fe(Co) powders exhibit a uniform demagnetization behavior and increased values of remanence Mr and (BH)max parallel to the pressure direction. Backscatteredelectron (BSE) scanning electron microscopy (SEM) image shown in Fig. 3 presents a vivid example of such composite made from ground Nd10.5Dy3.5Fe79.5Ga0.5B6 melt-spun ribbons and the Fe-Co melt-spun ribbons cut into pieces as large as 1 mm 2 mm in size. Deformation at 900 oC arranges the Fe-Co inclusions into fairly uniform layers perpendicular to the pressure direction. Fig. 4(a) presents the separate demagnetization curves of the different components: those of the hot-deformed Nd10.5Dy3.5Fe79.5Ga0.5B6 magnet and Fe-Co ribbons. The weighted averaged of these separate curves (the weight ratio 90/10) plotted in Fig. 4(b) has, of course, a distinct kink at zero field. The M(H) curve of the composite magnet, however, reveals a perfect magnetic coupling between the hard and soft components. Without doubt, in such coarse mixtures the coupling can only be of magnetostatic origin.

Fig. 3. BSE SEM micrograph of a hotdeformed magnet made from (Nd,Dy)14Fe79.5Ga0.5B6 melt-spun alloy blended with 10% Fe49Co49V2 melt-spun alloy. Arrows indicate the pressure direction. Inset shows a hot-pressed precursor.

Fig. 4. Demagnetization curves of (a) hotdeformed (Nd,Dy)14Fe79.5Ga0.5B6 magnet and Fe49Co49V2 ribbons and (b) hot-deformed magnet made from (Nd,Dy)14Fe79.5Ga0.5B6 blended with 10% Fe49Co49V2. Broken lines show weighted average calculated for the curves (a). The small increase in 4Mr and (BH)max due to the Fe-Co addition to the above (Nd,Dy)-FeGa-B magnets (from 10.7 kG and 27.3 MGOe to 11.5 kG and 28 MGOe, respectively) may seem disappointing. In fact, no increase at all should be expected in composites coupled only magnetostatically [9]. The magnetostatic coupling in layered composites like the one shown in Fig. 3 should rather be seen as

Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece __________________________________________________________________________________________________

complementary to the exchange coupling, the way to relax the restrictions for the size of soft magnetic components. Unfortunately, the magnetostatic interaction places high requirements for the coercivity of the hard magnetic phase, which must be high enough to withstand the stray fields of the soft phase [9,10]. One underestimated problem with the dieupset composites made from R-rich R-Fe-B alloys and Fe(Co) is that during the hot deformation the liquid R-rich phase readily reacts with the Fe(Co) phase changing both the amount of the Fe(Co) phase and the average composition of the R-Fe-B matrix [10]. When the addition of 2 - 3 wt. % Fe (by deposition through sputtering onto the hard particles) reportedly increased 4Mr of the die-upset NdFe-B magnet from 13 to 15 kG [11], one should attribute this not to the higher magnetization of the Fe phase (3 wt.% Fe can add to the total magnetization only about 0.25 kG) but rather to changes in the Nd-Fe-B component. The high reactivity of the R-rich phase also makes it very susceptible to oxidation during milling and, therefore, complicates refinement of the R-Fe-B component in the R-Fe-B / Fe(Co) composites [10]. Though not critical for the effective exchange coupling, the size of hard magnetic elements ultimately determines the volume ratio of the soft component. It is quite obvious that the present "(BH)max challenge" cannot be answered by a composite magnet with only a few percent of a high-magnetization soft phase. 2.2. Hard-soft magnets based on R-Co Similarly to Nd-Fe-B, the RCo5 nanocrystalline alloys can develop texture through hot plastic deformation [13-15]. The RCo5/Co and RCo5/Fe anisotropic composite magnets (R = Pr, Sm) were fabricated via consolidation and deformation at 800 - 950 oC of milled RCo5 alloys (the milling included a highenergy step to assure a nanocrystalline structure and a low-energy step to refine the powder) blended with the Fe and Co powders. The RCo5/Fe hot-deformed magnets featured 0.3 - 2.0 m thick iron layers oriented perpendicularly to the pressure direction [see 4

Fig. 5(a)]. In a good agreement with the theory for magnetostatically coupled composites [9], the Fe addition markedly increased the saturation magnetization, but not the remanence. While the reaction between the RCo5 and Fe components must produce the Fe-rich (and magnetically soft) R2(Co,Fe)17 phase, the moderately hard Sm2Co17 phase forms at the boundaries of the Co inclusions in the SmCo5/Co composites, shown in Fig. 6. Such SmCo5/Sm2Co17/Co composite magnets exhibit an increased remanence [Fig. 5(b)], and they may offer us at least two interesting

Fig. 5. Demagnetization curves of hotdeformed magnets made from high-energy milled RCo5 powder blended with 10 wt. % of (a) 10 m Fe powder (deformation at 800 oC) and (b) 30 m Co powder (deformation at 950 o C). Inset is rendered from the BSE SEM micrograph.

Fig. 6. BSE SEM micrograph of hot-deformed magnet made from high-energy milled SmCo5 powder blended with 10% of 1.6 m Co powder. Arrows indicate the pressure direction.

Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece __________________________________________________________________________________________________

opportunities. The microstructure of these composites may be further optimized to take the full advantage of the recently reported [16] enhancement of the exchange coupling through a graded interface. Moreover, if the emerging 2:17 phase follows the (partial) texture of the parent 1:5 phase, the SmCo5/Co composites can be developed into anisotropic Sm2Co17/SmCo5 magnets (the 2:17 phase itself is not susceptible to the deformation-induced anisotropy [15]). 2.3. Hard-hard composite (hybrid) magnets It has been recently suggested [17] that hotdeformed composite magnets made from blended R-Fe-B and R'-Co nanocrystalline alloys may fill the gap in thermal stability between the permanent magnets based on the RFe-B and R'-Co systems. We would like to emphasize that the results of combining these dissimilar materials must be interpreted with caution. Fig. 7 presents demagnetization curves of the (Pr,Dy)-(Fe,Co)-B magnet and the (Pr,Dy)-(Fe,Co)-B/(Pr,Sm)Co5 composite, both deformed at 800 oC. One can see that the favorable effect of the (Pr,Sm)Co5 addition is more obvious at 25 oC than at 240 oC. This seemingly puzzling result has a simple explanation. According to the SEM observations [Figs. 8(a,b)], the (Pr,Sm)Co5 phase rapidly disappears during the hot pressing and hot deformation processing. Its transformation starts

Fig. 8. BSE SEM micrographs of (a) hotpressed and (b) hot-deformed blends of meltspun (Pr,Dy)14(Fe,Co)79.5Ga0.5B6 alloy with 10% high-energy milled Pr0.75Sm0.25Co5 alloy. (C) hot-deformed blend of the same melt-spun alloy with 10% high-energy milled Sm2Co17 alloy; also shown is Sm elemental map for marked area. Arrows indicate the pressure direction. in the areas adjacent to the triple junctions between the R-Fe-B particles, most likely due to the abundant supply of the (liquid) R-rich phase. By the end of the hot deformation, almost all the added 1:5 phase transformed into the "R'-rich" [in this case, R'(Co0.9Fe0.1)2] phase. Thus, the major reason for the observed improvement of magnetic properties was the increased amount of the rare-earth-rich phases leading, in particular to a better texture in hot-deformed magnet. One would expect the Sm2Co17 addition, which can accommodate any amount of Fe, to be more resistant to the above transformation. Indeed, in the (Pr,Dy)-(Fe,Co)-B/Sm2Co17 composite magnet deformed at the same 800 oC, the 2:17 phase was found to be mostly intact [Fig. 8(c)]. However, the Sm2Co17 addition did not improve the magnetic properties of the composite magnet: its own properties were not high enough and it could not develop texture via hot deformation [15] [in fact, as Fig. 8(c) shows, the 2:17 phase was not even deformed].

Fig. 7. Demagnetization curves of hotdeformed magnets made from single melt-spun (Pr0.85Dy0.15)14Fe72Co7.5Ga0.5B6 alloy (1) and its blend with 10 wt. % Pr0.75Sm0.25Co5 high-energy milled alloy. 5

Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece __________________________________________________________________________________________________

3. Hard-soft magnets based on Sm2Fe17Nx The Sm2Fe17Nx compound has a saturation magnetization almost as high as Nd2Fe14B, but a significantly higher Curie temperature and a stronger magnetocrystalline anisotropy. However, because it is less stable than the mixture of SmN and Fe, the Sm2Fe17Nx can only be obtained via nitrogenization of Sm2Fe17 and it cannot be exposed to a temperatures greater than 600 oC. In reference [12], we pointed out that in composite magnets made from Sm2Fe17Nx and a soft magnetic phase, the latter may simultaneously serve as a metal binder. The hotpressed Sm2Fe17Nx/Fe0.65Co0.35 composites indeed showed considerably higher absolute and relative densities. We have found that certain Co-substituted Fe nitrides may provide nitrogen for synthesis of Sm2Fe17Nx in such composites during consolidation. The thermal gravimetric (TG) scans in Fig. 9 show that decomposition of the Sm2.1Fe17N2.7 alloy starts at 600 oC (Sm2Fe17N3 releases 1/3 of its N atoms when it dissociates into SmN and Fe), whereas the (Fe0.65Co0.35)89N11 alloy releases N at 450 oC (the Co-free Fe89N11 does this only at 670 oC). Thus, in the Sm2Fe17/(Fe0.65Co0.35)89N11 composite, the N atoms released during decomposition of (Fe0.65Co0.35)89N11 can interstitially modify the Sm2Fe17 compound. Fig. 10 shows the microstructures of the Sm2Fe17Nx/Fe-Co composite obtained through

Fig. 10. BSE SEM micrograph of Sm2Fe17Nx / Fe65Co35 composite consolidated at 570 oC from blended Sm2.1Fe17 and (Fe0.65Co0.35)89N11 powders. Location of nitrogen was found with XRD and TMA. the in situ nitrogenization. The more ductile FeCo phase fills the space between the hard Sm2Fe17Nx particles, resulting in a dramatic increase of the density [12]. Of course, this merely demonstrates the concept; a much finer microstructure and a textured hard phase are required for the development of advanced permanent magnets. 4. Nano-assembled composite magnets 4.1. Coating hard magnetic particles with highmagnetization nanoparticles It is rather difficult to form thin continuous layers of a soft magnetic phase by simply blending the hard magnetic powders with the much finer soft particles: distribution of the smaller particles will be determined by the voids between the larger particles. The natural solution to this problem would be to form the desired thin layers in advance, by coating the particles while they are still separate. Different coating techniques have been suggested for the fabrication of nanocomposite magnets [11,1820]. We focus our efforts on coating the hard magnetic particles with the Fe(B) nanoparticles synthesized by chemical reduction of FeCl2 with NaBH4 [20]. To perfect the coating technique we used the model systems of Cu particles coated with the Fe nanoparticles. Cu powders with particle sizes ranging from 1 to 100 m were immersed in the reaction bath during the synthesis of Fe 6

Fig. 9. TG (heating) scans for ground Sm-FeN alloy and mechanically alloyed Fe-N and Fe-Co-N powders.

Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece __________________________________________________________________________________________________

Fig. 11. BSE SEM micrographs of model hotpressed composites made from (a) coarse and (b) fine Cu powders coated by Fe nanoparticles. Also shown are Fe elemental maps for marked areas. nanoparticles. The best results were achieved after the dried-up powder was additionally agitated. The large Cu particles (~ 100 m) were uniformly coated by Fe nanoparticles after a few minutes of the "low-energy" hand shaking, but the high-energy agitation in a SPEX-8000 mixer was necessary for the Cu particles of a few microns. Fig. 11 shows the microstructures of two model composites obtained by consolidation of the Cu-core/Fe-shell powders at 500 oC. Following the above procedure, the Sm(Co0.757Fe0.1Cu0.11Zr0.033)7 sintered magnet was finely milled and the powder was dispersed in the FeCl2 solution prior to the reduction. As a result, the Sm-Co particles were only partially coated with Fe particles, Fig. 12(a). A followed high-energy agitation for 1 h led to complete and seemingly uniform coating, Fig. 12(c). These Fe-coated Sm-Co particles were consolidated at 500 oC into a composite magnet with the uniform submicron Fe layers, Fig. 12(c). 4.2. Anisotropic Sm-Co nanoparticles by surfactant-assisted milling The high-performance nano-assembled composite magnets will require anisotropic hard 7

Fig. 12. Particles of milled Sm(Co,Fe,Cu,Zr)7 magnet (a) coated with Fe nanoparticles and (b) additionally shaken with SPEX mixer. (C) BSE SEM micrograph of composite magnet made from the shaken core/shell powder. magnetic particles not much greater than the soft particles, with a size no more than few tens of nanometers. At this moment, the surfactantassisted milling seems to be the only technique capable for producing so small metallic nanoparticles with the rare-earths [21,22]. The very promising results have been obtained recently at the University of Delaware [23]. The homogenized Sm2(Co0.8Fe0.2)17 and SmCo5 alloys were subjected to a high-energy ball milling in heptane with a small amount of oleic acid. After several hours of milling the powders preserved their crystal structure and were anisotropic (Fig. 13). The high-resolution transmission electron microscopy (TEM, Fig. 14) revealed a very narrow particle size distribution with the average size of 5.5 nm. Due to the uniform size, the particles were selfassembled into a two-dimensional lattice. Evolution of the particles coercivity with the milling time (Fig. 15) resembles that for the low-energy milling: the coercivity inversely follows the particle size rather than going through a maximum followed by amorphization. The surfactant-milled anisotropic nanoparticles may serve as a perfect hard magnetic component in nano-assembled composite magnets. Acknowledgements This work was supported by DOD, DARPA,

Original manuscript, Proceedings of 20th International Workshop on RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece __________________________________________________________________________________________________

ONR, DOE and NSF.

Fig. 15. Coercivity of Sm2(Co0.8Fe0.2)17 and SmCo5 powders vs. time of surfactant-assisted high-energy ball milling. Fig. 13. XRD scans of Sm2(Co0.8Fe0.2)17 alloy after homogenization (1), surfactant-assisted high-energy ball milling for 4 h (2) and additional orientation by magnetic field (3).

Fig. 14. Bright field TEM image of Sm2(Co0.8Fe0.2)17 powder after 4 h of surfactant-assisted high-energy ball milling.

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