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

8-10, 2008, Crete, Greece _____________________________________________________________________________________________

High (BH)max Permanent Magnets with Near-Zero Reversible Temperature Coefficient of Br M. Marinescu, K. McGinnis, J. F. Liu and M. H. Walmer Electron Energy Corporation, Landisville, PA, USA Abstract. Gd(Co0.67Fe0.24Cu0.07Zr0.02)7.16, Blends of Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.43, Er(Co0.74Fe0.14Cu0.09Zr0.03)7.03 and Sm(Co0.63Fe0.26Cu0.08Zr0.03)5.04 powders were consolidated and thermally processed into permanent magnets with different ratios of the rare earth elements Gd/Er/Sm and different ratios of the total transition metals to total rare earth elements. The optimized compositions and processing conditions resulted in reversible temperature coefficient of residual induction, , close to zero in the temperature range of -50 oC and 150 oC and maximum energy product, (BH)max, of 18-20 MGOe at room temperature. High Hk, in most of the cases over 20 kOe, makes these magnets useful in special applications such as traveling wave tubes, accelerometers, torquers, gyroscopes, etc. Keywords: temperature-compensated permanent magnets; reversible temperature coefficient of residual induction; Sm2Co17 permanent magnets. 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 and 250 oC are needed in applications such as traveling wave tubes, accelerometers, torquers, gyroscopes, especially for military and aerospace operations. Indirect methods1 of providing a more stable magnetic flux consist in the use of a soft magnetic temperature-compensated alloy, usually made of nickel-iron, as a thin film over the permanent magnet. This film controls the leakage flux in the shunt path such that, in the range of operating temperatures, the flux density in the air gap remains the same. However, a more convenient solution is the use of temperature compensated magnets typically based on RE-Co 1:5 and 2:17 phases (RE = rare earth). In RE-TM (TM = transition metal) compounds when the RE is a light rare earth element (such as Sm, Nd, Pr, Ce), the magnetization decreases with

I. INTRODUCTION While the irreversible change with temperature of the magnetic flux of a permanent magnet can be avoided by thermal stabilization, the reversible part may become critical in applications that require a constant magnetic flux while the service temperature varies. The rate of the reversible change of residual induction, Br, with temperature T, is given by the relation: Br 1 = 100% (1) Br T The typical values of for the major classes of permanent magnets are -0.2 %/oC for ferrites, -0.03 to -0.02 %/oC for Alnico, 0.11%/oC for Nd2Fe14B, -0.04 %/oC for SmCo5 and -0.035 %/oC for Sm2Co17-type magnets. Permanent magnets with very low over a temperature span between -50 oC

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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 _____________________________________________________________________________________________

increasing the temperature whereas when the RE is a heavy rare earth element (such as Gd, Tb, Dy, Ho, Er, Tm), the magnetization has a non-monotonous trend: over specific temperature range it can increase with the temperature rise until ultimately decreasing to zero. The explanation for this behavior is that the magnetic moments of light RE sublattice couples parallel to those of TM sublattice while for the heavy RE atoms the coupling is antiparallel. Therefore, by combining the two effects it is possible, within a certain temperature range, to achieve a near-zero reversible temperature coefficient of residual induction. Singular partial substitutions of Sm by 2,3 Gd , Er2,4,5, (Ho, Tm, Dy, Tb)5 were reported to provide values of the order of tens of ppm/oC for particular temperature ranges, with reasonable to good values of maximum energy products. However, most of the optimum compensated magnets with a high (BH)max had a low Hk (denotes the demagnetization field for which Br decreases by 10%) that constrains their practical use. Mathematical algorithms using polynomial functions that describe the variation of saturation magnetization with temperature for different RE2Tm17 systems were successfully applied to predict the temperature coefficient of magnetization in magnets with multiple RE elements6. For many years, Electron Energy Corporation has produced magnets with near zero temperature coefficient of Br in the temperature range of -50 oC to 150 oC. The best temperature compensated magnets available on the market are (SmxGd1x)(Co,Fe,Cu,Zr)z magnets with 0.001%/oC and (BH)max = 16 MGOe. An increase of (BH)max up to 18 MGOe can be achieved by shifting the Sm/Gd ratio towards more Sm content, which has in turn an adverse effect on that increases up to 0.02 %/oC.

This article presents the results of our recent efforts on producing 2:17 RE-Co permanent magnets with enhanced (BH)max and a near-zero reversible temperature coefficient of Br by partial substitution of Sm with Er and Gd. The processing parameters to achieve optimum magnetic properties are also discussed. II. EXPERIMENT The precursor alloys were prepared by induction melting from pure elements. The final composition was adjusted by blending powders with different elemental constituents and stoichiometries to promote the densification by liquid phase sintering and compensate for the loss of the rare earth through evaporation and oxidation during thermal processing. The compositions of the powders were Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.43, Gd(Co0.67Fe0.24Cu0.07Zr0.02)7.16, Er(Co0.74Fe0.14Cu0.09Zr0.03)7.03 and Sm(Co0.63Fe0.26Cu0.08Zr0.03)5.04 The magnets were prepared by using the standard powder metallurgy process consisting of powder alignment and pressing, sintering for densification, solution for compositional homogenization and aging with slow cooling for development of hard magnetic properties. The blends of powder with average particle sizes of 2.5 micron were aligned and consolidated by isostatic pressing. Sintering was done in H2 in the temperature range of Tsinter = 1185- 1225 oC for 2h. Solution treatment was performed in Ar in the temperature range of Tsol = 11551200 oC for at least 10h. Aging was done in Ar partial pressure at Tage = 800 to 880 oC for 10h to 36h. The magnetic properties were tested with a KJS HG-700 hysteresisgraph in the temperature range of -50oC to 150oC. The rate of the reversible change of magnetic flux with temperature was determined using the relation (1) where

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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 _____________________________________________________________________________________________

Br was the closecircuit residual induction measured with the KJS hysteresisgraph. III. RESULTS AND DISCUSSION By completely substituting Sm with Gd or Er in 2:17 magnets with the typical Sm(Co,Fe,Cu,Zr)z stoichiometry, the reversible temperature coefficient of magnetization in an applied field of 10 kOe is positive (magnetization increases with increasing temperature) up to ~275oC and ~ 450oC, respectively5. However, the magnetization of the Er and Gd- completely substituted alloys has values lower than of the typical 2:17 Sm-Co permanent magnets over the entire temperature range. Therefore, the presence of all three elements may contribute for a specific property in magnets. The RE(Co,Fe,Cu,Zr)z composition of our new magnets was modified by blending the Sm-, Gd- and Erbased powders that gave different Gd/Er/Sm elemental ratios. The final z ratio was controlled via the Sm-rich alloy (z = 5.0) added in amounts varying from 2.5 wt% to 10 wt%. The equivalent calculated final z ratio was in the range of 6.84 to 7.03. The variation of the important hysteresis parameters with the solution temperature and aging temperature and time are shown in Fig. 1 for magnet specimens machined from the blocks having Gd/Er/Sm = 28/28/44. The residual induction is higher for higher ratio z alloys while Hk is higher for lower ratio z alloys. Higher Br contributes to the slightly increased (BH)max obtained for the specimens with higher ratio z. The highest (BH)max was 17.25 MGOe obtained for Tsinter = 1210 oC, Tsol= 1190oC for 8h and Tage=840 oC for 10h. The magnetic properties did not vary much as solution temperature changed from 1180oC to 1200oC. However, aging at a lower temperature (Tage = 815oC) for 36h resulted in the elimination of the slightly concave

Figure 1 Magnetic properties of (Sm,Gd,Er)(Co,Fe,Cu,Zr)z magnets with Gd/Er/Sm = 28/28/44 processed by sintering at 1210 oC, solution at different temperatures and aged at 840 oC for 10h. The arrows indicate the jump in the properties with aging temperature at 815 oC for 36h.

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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 _____________________________________________________________________________________________

region in the second quadrant of the demagnetization curve and a substantial increase of Hk field. The modified aging parameters had reduced effect on residual induction. The increase in Hk led to an enhanced (BH)max of up to 17.89 MGOe. A prolonged aging at 840 oC did not result in the same positive effect.Table 1 presents the results on three blends with optimized ratio z with respect to (BH)max and . The magnets were isostatically pressed, sintered at 1210 oC, solutioned at 1200 oC and aged at 815 oC for 36h. The increase of Sm content may be responsible for the slight increase of the maximum energy product, while the increase of Er content, as referenced to the total heavy rare earth content, may contribute to the slight decrease in the absolute value of .
Table 1 Maximum energy product (BH)max at room temperature and reversible temperature coefficient of Br, , for RE(Co,Fe,Cu,Zr)z with different ratio of RE elements, when the temperature changes from 22 o C to 150 oC.

With the Gd-based alloy fixed at 22 wt%, we compared the effect of Er/Sm ratio in the following Gd/Er/Sm blends: 22/32/46; 22/33/45; 22/34/44 and 22/35/43. Fig. 2 shows the variation of Br, Hk and (BH)max for different values of ratio z. It can be noted that the residual induction decreases with decreasing Sm concentration levels while Hk decreases even more sharply. Typical values for ranged from -0.007 %/oC to a positive indicating an over-compensation effect. However, the low Hk obtained with increasing the Er content made the magnets useless for practical applications.

Figure 2 Magnetic properties of (Sm,Gd,Er)(Co,Fe,Cu,Zr)z magnets with different ratios of the RE elements processed by sintering at 1210 oC, solution at different temperatures and aged at 840 oC for 10h.

The experiments on compositional change set some limits for the Gd and Er content with respect to achieving good magnetic properties juxtaposed with a

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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 _____________________________________________________________________________________________

minimized reversible temperature coefficient of residual induction. These limits may be roughly defined as less than 33 wt% of Er-based alloy and more than 22 wt% of Gd-based alloy.
Table 2 Comparison of (BH)max and Hk at room temperature, Br at -50 oC and 150 oC and the respective calculated for RE(Co,Fe,Cu,Zr)z magnets with different ratios of the rare earth elements and ratio z produced with optimized process parameters.

wt% to 42 wt% led to slightly inferior values of (BH)max for both 26/32/42 and 38/20/42 blends. Fig. 3 presents typical demagnetization curves at temperatures in the range of -50 oC to 150 oC, for selected magnets with the magnetic parameters noted in Table 2.

Several blends, as noted in Table 2, were processed into magnets by isostatic pressing, sintering at 1210 oC, solution treatment at temperatures in the range of 1185- 1200 oC and aging at 815 oC for 36h. The solution treatment was performed for 22-25h to achieve a more homogeneous compositional distribution and therefore a better squareness of the demagnetization curve. As it can be seen in Table 2, (BH)max values of over 20 MGOe and high Hk values combined with very low of the order of tens of ppm/oC were obtained consistently within the entire investigated compositional range. The decrease of Sm-based alloy ratio from 44

Figure 3 Demagnetization curves at different temperatures for (Sm,Gd,Er)(Co,Fe,Cu,Zr)z magnets with two selected RE ratios and z= 6.9 (7.5wt% Smrich powder). The magnets were isostatically pressed, sintered at 1210 oC, solutioned at temperatures in the range of 1195- 1200 oC and aged at 815 oC for 36 h.

IV. CONCLUSION (Sm,Gd,Er)(Co,Fe,Cu,Zr)z temperature compensated magnets with (BH)max of 18-20 MGOe at room temperature, Hk of about 20 kOe and almost zero reversible temperature

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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 _____________________________________________________________________________________________

coefficient of Br between -50 oC and 150 oC have been developed. The optimum composition should contain less than 33 wt% of Er and more than 22 wt% of Gd in the total RE content. The optimum thermal processing consists in sintering at temperatures as high as 1210 oC, extended solution at 1185- 1200 oC and aging at 815 o C for 36h. References 1. K. R. Rajagopal, B. Singh, B.P. Singh, and N. Vedachalam, IEEE Trans. Magn., 37, 4 (2001) 1995

2. D. Li, E. Xu, J. Liu and Y. Du, IEEE Trans. Magn. 16, 5 (1980) 988 3. M. Gjoka, I. Panagiotopoulos, D. Niarchos, T. Matthias, J. Fidler, J. Alloys and Comp. 367 (2004) 262 4. H. F. Mildrum and J. B. Krupar, J. LessComm. Metals 93 (1983) 261 5. C. H. Chen, W. Gong and M. H. Walmer, S. Liu, and G. E. Kuhl, J. Appl. Phys. 91, 10 (2002) 8483 6. S. Liu, A.E. Ray and H. F. Mildrum, J. Appl. Phys. 67, 9 (1990) 4975

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