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

8-10, 2008, Crete, Greece _____________________________________________________________________________________________

Sm-Co and Pr-Fe-B Magnets with Increased Electrical Resistivity M. Marinescu1, A. M. Gabay2, S. Kodat1, J. F. Liu1, G. C. Hadjipanayis2
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Electron Energy Corporation, Landisville, PA, USA Department of Physics and Astronomy, University of Delaware, Newark DE, USA

Abstract. Fully dense composite magnets produced by sintering blends of Sm(Co,Fe,Cu,Zr)z and CaF3 precursor powders had an electrical resistivity 30% higher than conventional Sm(Co,Fe,Cu,Zr)z magnets. The magnetic performance was only slightly altered with the addition of 2.5 wt% of CaF2: Br = 10.8 kG, Hci > 25 kOe, (BH)max = 27.1 MGOe. A much higher electrical resistivity of up to ~ 1000 cm was achieved in glass-bonded Sm(Co,Fe,Cu,Zr)z / B2O3 magnets produced by hot pressing at 475 oC. The low-temperature consolidation preserved the high intrinsic coercivity of the Sm(Co,Fe,Cu,Zr)z magnet powder, but the residual induction was decreased due to a lower density. Fully dense composite magnets based on Pr-Fe-B and other rare earth fluoride powders were produced by hot pressing and die upsetting the precursor blends. The overstoichiometric composition of Pr14.5Fe79.5B6 powders from melt-spun precursors allowed, upon the thermal processing with NdF3, DyF3 and CaF2 fine powders, the formation of a morphology where the fluoride surrounded the Pr14.5Fe79.5B6 component in the magnet. The addition of fluorides increased the resistivity by more than 200% and improved the intrinsic coercivity to values above 15 kOe with a slight reduction of residual induction in the range of 10.5- 11 kG. Keywords: Sm-Co magnets, Pr-Fe-B magnets, electrical resistivity, die upsetting, fluorides, B2O3 Contact author: M. Marinescu, Electron Energy Corporation, 924 Links Ave, Landisville, PA 17538, USA; tel: 717 898 2294; fax: 717 898 0660; mmarinescu@electronenergy.com I. INTRODUCTION Eddy current losses represent one of the important considerations in the design of motors and high speed power generators. Reduction of eddy current losses in rotor permanent magnets is typically achieved by surface engineering, i.e. by segmenting the magnet elements. In a much simpler fashion, the increase of resistivity of permanent magnets could decrease the eddy current losses through a simple inverse proportionality1. Bonded magnets have high resistivity due to the insulation effect of polymer binders, but the operating temperature is dramatically limited by the polymer softening above 200 oC while the magnetic flux is reduced due to the low density. Besides polymers, other insulators such as fluorides and oxides of Li, Na, Mg, Ca, Ba and Sr were shown2 to increase the electrical resistivity of the rare earth (RE) magnets to a level sufficient for practical use in regard to their magnetic performance. A recent article3 reported a high electrical resistivity (1.4 mcm) of isotropic hot pressed Nd-Fe-B magnets synthesized from Nd-Fe-B powders coated with a 200 nm Nd fluoride layer grown using a fluoride solution. Sm-Fe-N / ferrite composite magnets with a resistivity of 4 mcm were produced from ferrite plated Sm-Fe-N powders4 and consolidated to almost full

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

density by die pressing and explosive consolidation technique. This work presents our results on Sm-Co and Pr-Fe-B permanent magnets with increased electrical resistivity by the addition of boron oxide, calcium fluoride, neodymium fluoride and dysprosium fluoride. II. EXPERIMENT Sm-Co based powders with a particle size of about 2.5 m were prepared by milling the precursor alloys cast by induction melting from pure elements. The final composition was controlled and optimized with respect to the loss of Sm through oxidation and evaporation by mixing Sm-Co powders with two stoichiometries: one mix consisting of Sm(Co0.70Fe0.21Cu0.06Zr0.03)7.4 and Sm(Co0.66Fe0.24Cu0.07Zr0.03)4.9 and a second mix consisting of and Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.7 Sm(Co0.62Fe0.30Cu0.06Zr0.02)4.9. CaF2 powder was added to the Sm-Co mixed powder by simple blending in amounts of 2.5 and 5 wt%. The Sm(Co,Fe,Cu,Zr)z / CaF2 blends were consolidated into blocks by isostatic pressing. The green compacts were subjected to the conventional thermal processing consisting of sintering in H2 at 1195 oC, solution treatment at 1175 oC and aging at 840 oC. Some Sm(Co,Fe,Cu,Zr)z anisotropic powder with already developed hard magnetic properties produced by milling EEC 2:17-27 and EEC 24-T400 nonsaturated magnets5 were blended with B2O3 powder in amounts of 2.5, 5 and 10 wt%. The blends were aligned and hot pressed at 475 oC, slightly above the melting point of B2O3 (450 oC). Pr14.5Fe79.5B6 melt-spun ribbons were ground and blended with 5 wt% of CaF2, NdF3 and DyF3 powders. The blends were consolidated by hot pressing at 650oC and die-upset at 750oC.

The phase composition of the composite magnets was examined by powder X-ray diffraction (XRD) with the Cu-K radiation. The microstructure and microchemistry was investigated by scanning electron microscopy (SEM) with a JEOL JSM-6330F instrument equipped with an energy dispersive X-ray (EDX) detector. The magnetic measurements were done with a Lakeshore vibrating sample magnetometer (VSM) at room temperature and also at higher temperatures up to 240 oC for Sm-Co based magnets. Alignment and saturation of the composite magnets was done in fields of up to 100 kOe. The density of the composite specimens was calculated from the geometrical dimensions. The resistivity was measured by the four probe technique.

III. RESULTS AND DISCUSSION A. Fluoride-Added Sintered Sm-Co The optimum amount of Sm-rich powder Sm(Co0.66Fe0.24Cu0.07Zr0.03)4.9 needed to be added to base Sm(Co0.70Fe0.21Cu0.06Zr0.03)7.4 powder in order to achieve the best hard magnetic performance in the sintered magnets is about 7.5 wt%. In order to preserve a high Hci of 25 kOe after adding 2.5 - 5.0 wt.% CaF2, the amount of the Sm-rich powder had to be increased up to 19 wt.%, as it is shown in Fig. 1. By increasing the level of CaF2 addition to 5 wt.%, the remanence decreases below the theoretically expected 10.2 kG. The Sm-Co composition optimized by mixing Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.7 and 16 wt% of Sm(Co0.62Fe0.30Cu0.06Zr0.02)4.9 leads to very good magnetic properties when sintered with small amounts of CaF2, properties which are maintained at elevated temperatures as depicted in Fig. 2. The bestachieved magnetic properties at room temperature with 2.5 wt% CaF2 are: Br = 10.8 kG, Hci > 25 kOe, (BH)max = 27.1 MGOe.

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

Figure 1 Demagnetization curves of magnets synthesized from Sm(Co0.70Fe0.21Cu0.06Zr0.03)7.4 with different percentage of added Sm-rich Sm(Co0.66Fe0.24Cu0.07Zr0.03)4.9 and CaF2 powders.

fully dense Sm(Co,Fe,Cu,Zr)z magnets (8.4 g/cm3). Structure investigation showed that CaF2 does not dissociate during the thermal processing of the magnets. The X-ray diffraction patterns in Fig. 3 are identified and belong to the Th2Zn17 and CaF2 structure types. However, detailed compositional analyses by EDX (not shown) revealed that a small amount of Sm diffuses into the CaF2, effectively reducing the ratio z in the Sm(Co,Fe,Cu,Zr)z matrix and therefore extra amount of Sm was introduced with the Sm-rich powder. The resistivity of the composite Sm(Co,Fe,Cu,Zr)z / CaF2 magnets was found to increase up to slightly over 90 cm which is 30% more than that of the regular Sm(Co,Fe,Cu,Zr)z magnets.

Figure 3 X-ray diffraction analysis shows the existence of Sm2(Co,Fe)17 and CaF2 phases in Sm(Co,Fe,Cu,Zr)z / CaF2 composite magnet sintered at 1200 oC. Figure 2 Magnetic properties of optimized fully dense Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.7 + 16 wt% Sm(Co0.62Fe0.30Cu0.06Zr0.02)4.9 / CaF2 composite magnet with the resistivity increased 30% compared to the commercial Sm-Co 2:17 magnets. These magnets are able to operate at temperatures of 240 oC and above.

The density of the composite specimens was 97% of the theoretical value calculated from the density of CaF2 (3.18 g/cm3) and that of

B. Glass-Bonded Sm-Co A much more dramatic increase of electrical resistivity was obtained for composite magnets synthesized from blends of Sm(Co,Fe,Cu,Zr)z powders with already developed hard magnetic properties and B2O3 powder. The electrical resistivity for samples with 2.5 wt% of B2O3 exceeded 1000 cm, which is almost 12 times higher compared to the conventional

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

sintered counterparts. The larger the (BH)max of the precursor magnets, the more sensitive the powder is to milling with respect to preserving the hard magnetic properties. Only high-coercivity high-temperature Sm(Co,Fe,Cu,Zr)z bulk magnet specimens (EEC 24- T4005) were able to preserve a high coercivity upon milling to 10 m powder. Smaller particle size that may ensure a better packing factor and higher density of the composite compacts, could retain neither magnetization (due to the lattice distortions and increased surface to volume ratio and surface oxidation) nor intrinsic coercivity (due to the defects introduced into the cellular microstructure)6. EEC 24-T400 powders were also able to withstand temperatures of 475 oC employed in the hot-pressing process. However, these high temperature bonded magnets showed a low density and hence a lower residual induction of 5.85 kG (Fig. 4); the best achieved density was 6.10 g/cm3.

morphology that is beneficial for increasing the resistivity. Some Sm(Co,Fe,Cu,Zr)z / B2O3 specimens showed a resistivity as high as 6000 cm, due to a high porosity determined by a less efficient hot pressing procedure and larger particle size of magnet powder. Surprisingly, the addition of 5 or 10 wt% of B2O3 does not reduce the porosity.

Figure 5 (a) backscattered electron SEM micrograph and (b) EDX map for oxygen showing dielectric boron oxide and few samarium oxide inclusions within the EEC 24- T400 / B2O3 (2.5 wt%) glassbonded magnet.

Figure 4 Demagnetization curve of EEC 24- T400 / B2O3 glass-bonded magnets with electrical resistivity of 1138 cm: Br = 5.85 kG, Hci > 30 kOe, Hk = 7.67 kOe, (BH)max = 8.06 MGOe.

The specimens showed an improved mechanical strength which will be further investigated. The oxide was found to be distributed fairly uniformly around the magnet powder particles (Fig. 5),

C. Fluoride Added Die-Upset R-Fe-B Die-upset magnets made of blended Pr14.5Fe79.5B6 and CaF2 / NdF3 / DyF3 powders showed almost full density with values of 7.02, 7.40 and 7.37 g/cm3 for 5 wt.% of CaF2, NdF3 and DyF3, respectively. The accurate detection of fluorine itself with EDX was not possible since its major energy line is overlapped with one of the Fe lines. However, EDX analyses revealed that upon hot pressing and die upsetting, Ca, Nd and Dy are driven throughout the whole volume of the composite by the Pr-rich phase, which is in the molten state at the hot pressing and die upsetting temperature. A so called grain boundary diffusion process was also

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reported7 in which the rare earth atoms from their fluorides are able to diffuse through the Nd-rich phase from the surface of the NdFe-B magnets inside. A similar process happens in our case when the Pr-Fe-B powder is mixed with the fluoride powder. However, assuming that the fluorides do not decompose entirely, the morphology is beneficial for the electrical insulation of the conductive matrix. On the downside, the addition of CaF2 seems to lead to development of fine internal cracks during hot pressing, whereas the composites with DyF3 showed a certain tendency towards cleavage.

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

IV. CONCLUSION Composite sintered Sm(Co,Fe,Cu,Zr)z / CaF2 magnets were produced at almost full density with very good hard magnetic properties and the electrical resistivity is 30% higher compared to the metallic-only counterparts. Bonded Sm(Co,Fe,Cu,Zr)z / B2O3 magnets had a high electrical resistivity of ~ 1000 cm and high coercivity, but a residual induction of only 5.85 kG due to the reduced density. Pr-Fe-B / fluorides composite magnets prepared by hot pressing and die upsetting show an electrical resistivity twice as high as conventional Pr-Fe-B magnets, while maintaining a good hard magnetic performance. The addition of CaF2, NdF3 and DyF3 was found to enhance the intrinsic coercivity. NdF3 improves the squareness of the demagnetization curve of Pr-Fe-B magnets prepared by hot pressing and die upsetting. ACKNOWLEDGMENT This work was supported by US DoE grant DE-FG02-07ER86308. References: 1. D. Ishak, Z.Q. Zhu and D. Howe, IEEE Trans. Magn. 41, 9 (2005) 2462 2. US patent 5858124 (1999) 3. M. Komuro, Y. Satsu, Y. Enomoto and H. Koharagi, Appl. Phys. Lett. 91 (2007) 102503 4. N. Imaoka, Y. Koyama, T. Nakao, S. Nakaoka, T. Yamaguchi, E. Kakimoto, M. Tada, T. Nakagawa and M. Abe, J. Appl. Phys. 103 (2008) 07E129 5. EEC brochure available at www.electronenergy.com 6. Y. Zhang, Q. Zheng, G. C. Hadjipanayis, J. Appl. Phys. 97 (2005) 10H107 7. K. Hirota, H. Nakamura, T. Minowa, and M. Honshima, IEEE Trans. Magn. 42, 10 (2006) 2909

Figure 6 Demagnetization curves for die-upset magnets made of blended Pr14.5Fe79.5B6 and CaF2 / NdF3 / DyF3 powders. The fluoride additions increase the electrical resistivity of the magnets at least two times.

The Pr-Fe-B / fluorides composites have an electrical resistivity at least two times higher as compared to the 2:14:1 magnets. Values of 470 - 780, 290 - 310 and 680 780 cm were obtained for Pr-Fe-B / 5% CaF2, Pr-Fe-B / 5% NdF3 and Pr-Fe-B / 5% DyF3 samples, respectively. The addition of fluorides causes an increase in Hci, and NdF3, in particular, proves to be very favorable for improving the squareness of the demagnetization curve, as seen in Fig. 6.

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