IEEE TRANSACTIONS ON MAGNETICS, VOL. 44, NO.

11, NOVEMBER 2008

Sintered Sm2 Co17 -Based Magnets With Small Additions of Indium

Alexander M. Gabay1 , Melania Marinescu2 , JinFang Liu2 , and George C. Hadjipanayis1
Department of Physics and Astronomy, University of Delaware, Newark, DE 19716 USA Electron Energy Corporation, Landisville, PA 17538 USA
In an attempt to develop anisotropic high-temperature permanent magnets consisting of Sm2 (Co,Fe)17 grains separated by thin layers of a nonmagnetic phase, small amounts of Ag, C, Ga, In, and Sn were added to the Sm2 Co17 -based alloys and sintered magnets. Grain-boundary phase(s) with the melting temperature of 9851070 C was obtained by adding 0.51.5 at. % In to SmCo, SmCoFe, and SmCoMn alloys with the Sm content slightly enriched compared to the 2 : 17 stoichiometry. Iron, manganese and, apparently, oxygen tend to decrease the melting temperature of the grain-boundary phase(s). Due to this low-melting-temperature phase, sintering of the milled Sm2 Co17 -based alloys becomes possible at temperatures as low as 10251075 C. This phase is also believed to be responsible for the coercivity of 68 kOe observed in the SmCoFeMnIn alloys. The coercivity was found to be critically sensitive to the postsintering heat treatment: it dramatically deteriorates when the magnets are annealed below the melting temperature of the grain boundary phase(s). Index TermsCoercive force, indium, permanent magnets, samarium alloys.

N the best currently used high-temperature SmCo permanent magnets, the coercivity is developed in the bulk state through a multiphase cellular nanostructure. To assure this, some excess of Sm and 710 at. % of Cu and Zr must be added to the alloy, which then decreases the amount of high-magphase. The earlier attempts to obtain netization Sm Co,Fe pure 2 : 17 magnets were not very successful [1], [2], although a maximum energy product of 28 MGOe has been reported for magnets containing Mn [3]. Coercivity of magnets fabricated via sintering of anisotropic micron-size powders critically depends on the state of their grain boundaries. In particular, the high performance of sintered NdFeB magnets is assured by the Nd-rich phase, which magnetically insulates the Nd Fe B grains and inhibits nucleation of reversed magnetic domains [4], [5]. Due to its low melting temperature, this phase also serves as a sintering aid. In the ternary SmCoFe system, the Sm Co,Fe phase is in equilibrium with other ferromagnetic phases [6]; the desired insulating phase may, therefore, be induced only via doping. In our efforts to induce insulating grain-boundary phases in the Sm Co , Sm Co,Fe , and Sm Co,Fe,Mn alloys, we explored small additions of Ag, C, Ga, In, Sn, and some of their combinations. Additions of indium were found to be promising for both the powder metallurgy and hard magnetic properties of the Sm Co -based alloys. This paper gives a detailed account of our experiments with In-added alloys and sintered magnets; it also briey summarizes the results obtained for the other elements. II. EXPERIMENT Sn

The Sm Co Fe Mn C, Ga, In, Sn, Ag C , Ag , , and

Digital Object Identier 10.1109/TMAG.2008.2001540

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I. INTRODUCTION arc-melting in argon from pure elements and a CoC master alloy. The ingots were remelted at least four times to assure their homogeneity; appropriate excesses of Sm and Mn were added to compensate evaporation losses of these elements during arcmelting. Some of the ingots were additionally homogenized at 900 C. For sintering, the ingots were crushed to less than 0.3 mm and ball-milled with a rotary mill for 15 h in toluene. After drying, the powders were pressed in a magnetic eld of 17 kOe. The obtained green compacts were degassed by step heating in vacuum to 650 C and then sintered in argon for 1 h at 9751075 C. After sintering, the samples were pulled out of the furnace (still under argon) for air cooling. Additional postsintering heat treatment consisted of a one-hour annealing under argon at 9001050 C followed by quenching in water. The ingots and sintered magnets were characterized by: 1) powder x-ray diffraction (XRD) with a Philips diffractometer operating at the Cu-K radiation, 2) scanning electron microscopy (SEM) with a JEOL JSM-6335F instrument, 3) energy dispersive spectrometry (EDS) with an IXRF Systems instrument and software, and 4) differential thermal analysis (DTA) with a PerkinElmer Pyris Diamond TG/DTA instrument. Magnetic properties were measured on cube-shaped specimens with a vibrating sample magnetometer. Densities of the ingots and sintered magnets were measured by a water immersion technique or, in the case of too porous specimens, derived from their outer dimensions. III. RESULTS A. Small Additions of Silver, Carbon, Gallium and Tin M alloys with M Ag, , , were prepared by alloys with small addiIn the Sm Co and Sm Co,Fe tions of Ag, C, Ga, and Sn, the grain-boundary phases were observed for Ag, C, and Sn, whereas Ga was found to be dissolved by the magnetic SmCo phases. The Sm Ag phase in the SmCoAg alloys, though nonmagnetic and with the melting temperature of 935 C, was found not to wet the Sm Co grains. The grain-boundary phases in SmCoSn and SmCoAgSn alloys were found to have high melting temperatures. Grain boundaries in the alloys with carbon featured eutectic mixture of the carbide phase and the ferromagnetic
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IEEE TRANSACTIONS ON MAGNETICS, VOL. 44, NO. 11, NOVEMBER 2008

Fig. 1. Heating DTA curves of ingots and sintered magnets: 1Sm Co , Co In , 3Sm (Co Fe Mn ) In , 2Sm Fe Mn ) . T and T indicate the Curie 4Sm (Co temperature and solidus temperature, respectively.

SmCo phase, which do not make these boundaries magnetic insulators.

B. Effect of Indium Addition on Microstructure

SEM and EDS examination of the Sm Co In alloys and revealed a phase enwith riched with samarium and indium. The approximate composition of this phase was found to be Sm Co In . Inclusions of this indium-rich phase, as well as those of the minor SmCo phase, which contained only traces of indium, stretched along the boundaries of the indium-free Sm Co grains. The DTA scan shown in Fig. 1 (curve 2) indicates the appearance of a liquid phase at 1070 C in the alloy with indium, in contrast with the single-phase Sm Co alloy (curve 1). The Fe substitution for Co (not shown in Fig. 1) and the combined (Fe, Mn) substitution (curve 3) decrease the solidus temperature; the same effect is also caused by sintering (curve 3 ). The most likely way the milling/sintering could inuence the phase equilibrium is by introducing oxides. The presence of indium, however, is still necessary for the low-melting-temperature phase(s): the solidus temperature of the indium-free sintered magnet exceeds 1150 C (Fig. 1, curve 4). The XRD data shown in Fig. 2 conrm that milling and sintering had modied the phase structure of the Sm Co,Fe,Mn In alloy: the minor SmCo phase of the as-cast alloy is now replaced by Sm O . The XRD analysis, however, does not reveal the indium-rich phase: the scans for sintered magnets with and without indium are virtually identical. The In-rich and oxide phases can be clearly seen in the SEM image of a fractured surface shown in Fig. 3(a); in the backscattered electrons (BSE) mode, these two phases appear bright. Comparing the SEM image with the EDS elemental maps for indium and oxygen presented in Fig. 3(b) and (c), one can see that the indium-rich grains and the oxide grains of similar size 0.51.3 m are located next to each other along the boundaries of the larger Sm Fe,Co,Mn grains. It seems quite probable

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Fig. 3. (a) BSE SEM image of a fractured surface of (Co Fe Mn ) In magnet sintered at 1075 C and (b) Sm indium and (c) oxygen elemental maps for the selected area.

Fig. 2. Powder XRD scans of (a) as-cast Sm (Co Fe Mn ) In alloy, (b) sintered Sm (Co Fe Mn ) In magnet, and (c) sintered Sm (Co Fe Mn ) magnet. 2 : 17 and 1 : 5 denote reections of Th Zh -type and CaCu -type structures, respectively.

that the indium-rich and oxide phases crystallized from a liquid grain-boundary phase via a eutectic reaction. C. Effect of Indium Addition on Densication

As it might be expected, the liquid grain-boundary phase dramatically facilitates sintering. Fig. 4(a) presents densities of the indium-added sintered magnets. The magnet with only 0.5 at.% In exhibits a density of 0.98 times that of the ingot after sintering at 1075 C, which is more than 100 lower than the usual sintering temperature of the 2 : 17 magnets. Moreover, the density data for the different sintering temperatures shown in the inset suggest that the critical temperature for densication

GABAY et al.: SINTERED Sm Co

-BASED MAGNETS WITH SMALL ADDITIONS OF INDIUM

Fig. 4. Effect of indium content on relative density and intrinsic Fe Mn ) In (a) and coercivity of Sm (Co Sm (Co Fe Mn ) In (b) magnets sintered at 1075 C and annealed at 10001050 C. Inset shows density of Fe Mn ) In magnets sintered at different temperaSm (Co tures.

is around 1000 C, just above the solidus temperature revealed in this magnet by DTA (see curve 3 in Fig. 1). D. Effect of Indium Addition on Coercivity

The addition of indium also led to a signicant increase in the intrinsic coercivity . Fig. 4(b) presents the highest values for as-sintered and heat-treated samples (typically, the coercivity of the magnets sintered at 1075 C slightly improved after the postsintering annealing at 10001025 C). Fig. 5 shows the coercivity as a function of Sm and Mn concentrations. Alare not very concluthough the results for the Sm effect of on sive, they may suggest that there exists an optimum samarium concentration. Such optimum concentrations of both indium and samarium may have a simple explanation: at a given indium content, the grain-boundary phase can accommodate only certain amount of samarium, and vise versa. As for the Mn, it had matrix phase in the very bebeen added to the Sm Co,Fe ginning of this study in order to enhance its magnetocrystalline anisotropy [3], [7]. As one can see in Fig. 5(b), the magnets matrix do not develop any signicant with the Sm Co,Fe coercivity even though they also had reached the density of 97.5%98%. E. Effect of Postsintering Annealing

Postsintering annealing below certain temperature dramatof the sintered SmCoFeMnIn magically decreases coinnets. Fig. 6 shows that the temperature critical for cides with the solidus temperature of the sintered magnet. It is reasonable to assume that the more chemically homogeneous grain-boundary phase achieved by freezing the liquid phase is a better magnetic insulator than multiple phases produced by a eutectic crystallization. Indeed, the grain-boundary regions of

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Fig. 5. Effects of Sm and Mn contents on intrinsic coerFe Mn ) In and (b) civity of (a) Sm (Co Sm (Co Fe Mn ) In magnets sintered at 1075 C and annealed at 10001050 C. Fig. 6. Heating DTA curve of Sm (Co Fe Mn ) In magnet sintered at 1075 C and coercivity of this magnet versus temperature of postsintering annealing. T indicates the Curie temperature.

the high-coercivity sample quenched from 1000 C, which is shown in Fig. 7(a), appear to be more uniform than those of the low-coercivity sample quenched from 950 C [Fig. 7(b)]. The black spots in Fig. 7 correspond to a CoFeMn phase. This soft magnetic phase might appear as a result of inhomogeneous oxidation during milling and/or sintering and it is not necessarily involved in the above grain-boundary transformation. In any case, this phase must be harmful for the coercivity. IV. DISCUSSION AND CONCLUSION

Permanent magnets with high-temperature capabilities and room-temperature energy product greater than 50 MGOe promised by the intrinsic properties of the Sm Co,Fe compound [2] still remain an attractive target. During the last decade, the pure 2 : 17 magnets were mostly sought via nonequilibrium techniques such as mechanical alloying [8], [9] and melt-spinning [10][12]. This work shows that even the old-fashioned powder sintering, which has the undeniable advantage of delivering anisotropic massive magnets, may not yet run out of options. We are still far away from the ultimate goal: the coercivity of the magnets we report is hardly sufcient even for room-temperature applications, and their remanence[AU: Remanence

IEEE TRANSACTIONS ON MAGNETICS, VOL. 44, NO. 11, NOVEMBER 2008

ACKNOWLEDGMENT This work was supported by Air Force under STTR contract FA9550-07-C-0029. REFERENCES
[1] R. C. Carriker and A. S. Rashidi, Experiments in the liquid phase sintering of Sm Co , in AIP Conf. Proc., 1973, no. 10, pp. 608612. [2] R. S. Perkins, S. Gaif, and A. Menth, Permanent magnet properties of Sm (Co; Fe) , IEEE Trans. Magn., vol. 11, no. 5, pp. 14311433, Sep. 1975. [3] H. Nagel, Magnetic properties of sintered Sm TM magnets, in AIP Conf. Proc., 1976, no. 29, pp. 603604. [4] M. Sagawa, S. Fujimura, N. Togawa, H. Yamamoto, and Y. Matsuura, New material for permanent magnets on a base of Nd and Fe, J. Appl. Phys., vol. 55, pp. 20832087, Mar. 1984. [5] F. Vial, F. Joly, E. Nevalainen, M. Sagawa, K. Hiraga, and K. T. Park, Improvement of coercivity of sintered NdFeB permanent magnets by heat treatment, J. Magn. Magn. Mater., vol. 242245, pp. 13291334, Apr. 2002. [6] G. Schneider, E.-T. Henig, H. L. Lukas, and G. Petzow, Phase relations in the samarium-poor Sm-Co-Fe system, J. Less-Common Metals, vol. 110, pp. 159170, Aug. 1985. [7] R. S. Perkins, S. Strssler, and A. Menth, Upon inuencing the magnetocrystalline anisotropy of RE TM compounds, in AIP Conf. Proc., 1976, no. 29, pp. 610612. [8] P. A. I. Smith, J. Ding, R. Street, and P. G. McCormick, Mechanically alloyed Sm-(Co-Fe) permanent magnets, Scr. Mater., vol. 34, pp. 6166, Jan. 1996. [9] Z. M. Chen, X. Meng-Burany, H. Okumura, and G. C. Hadjipanayis, Magnetic properties and microstructure of mechanically milled Sm (Co,M) -based powders with M = Zr, Hf, Nb, V, Ti, Cr, Cu and Fe, J. Appl. Phys., vol. 87, pp. 34093414, Apr. 2000. [10] A. Yan, A. Bollero, K. H. Mller, and O. Guteisch, Inuence of Fe, Zr, and Cu on the microstructure and crystallographic texture of meltspun 2:17 Sm-Co ribbons, J. Appl. Phys., vol. 91, pp. 88258827, May 2002. [11] S. S. Makridis, G. Litsardakis, K. G. Efthimiadis, E. Pavlidou, I. Panagiotopoulos, G. C. Hadjipanayis, and D. Niarchos, Structural and magnetic properties of rhombohedral Sm (Co,Fe,Cr) B and Sm (Co,Fe,Mn) B compounds, IEEE Trans. Magn., vol. 39, no. 5, pp. 28722874, Sep. 2003. [12] C. H. Chen, S. Kodat, M. H. Walmer, S.-F. Cheng, M. A. Willard, and V. G. Harris, Effects of grain size and morphology on the coercivity of Sm (Co Fe ) based powders and spin cast ribbons, J. Appl. Phys., vol. 93, pp. 79667968, May 2003. [13] B. Zhang, J. R. Blachere, W. A. Soffa, and A. E. Ray, AEM studies of Sm:Co 2:17 permanent magnet alloys, J. Appl. Phys., vol. 64, pp. 57295731, Nov. 1988. [14] H. Kronmuller and D. Goll, Micromagnetic analysis of pinning-hardened nanostructured, nanocrystalline Sm Co based alloys, Scr. Mater., vol. 47, pp. 545550, Oct. 2002.

Fig. 7. BSE SEM images of Sm (Co Fe Mn ) In tered at 1075 C and annealed at (a) 1000 C and (b) 950 C.

correct word?], which typically does not exceed 9 kG, is disappointingly low. Nevertheless, the idea that motivated this study appears to be working: magnetic insulation can be magnets induced in the single-magnetic-phase Sm Co,Fe (we assume that the indium-rich grain boundary phase is nonmagnetic) and it leads to the magnetic hardness. The fact that the considerable coercivity was achieved only for the Mn-substituted magnets might suggest that there exists a threshold anisotropy eld for obtaining a magnetic hysteresis in ne 2 : 17 grains. However, the 2 : 17 magnets with the cellular structure demonstrate that the cell-interior Sm Co,Fe phase values containing 20 and more at. % Fe can exhibit very high if the cell size is sufciently small [13], [14]. Therefore, the further development of the proposed 2 : 17 magnets with the indium-rich grain-boundary phase may be sought in improvement of the comminuting technique to obtain ner particles with more uniform size distribution (fortunately, the low sintering temperatures made possible by the indium additions are favorable for the grain size control). Eventually, these efforts may allow us to increase the remanence by avoiding the Mn substitution and/or increasing that of Fe. Alignment of the milled powders with a pulsed eld will almost certainly provide the better texture and the higher remanence, and, of course, the effect of oxygen that is strongly suggested by some of our results requires a more focused study to gure out how it might be optimized. In conclusion, the small indium additions greatly facilitate sintering of the pure 2 : 17 magnets, but more effort is needed to obtain a high magnetic performance.

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magnet sinManuscript received March 3, 2008. Current version published (e-mail: gabay@physics.udel.edu).