Accepted Manuscript

Annealing effect on the magnetic properties of cobalt-based amorphous alloys

Sumin Kim, Yong Jin Kim, Young Keun Kim, Haein Choi-Yim

PII: S1567-1739(17)30031-7
DOI: 10.1016/j.cap.2017.01.025
Reference: CAP 4435

To appear in: Current Applied Physics

Received Date: 11 October 2016

Revised Date: 11 January 2017
Accepted Date: 30 January 2017

Please cite this article as: S. Kim, Y.J. Kim, Y.K. Kim, H. Choi-Yim, Annealing effect on the magnetic
properties of cobalt-based amorphous alloys, Current Applied Physics (2017), doi: 10.1016/
j.cap.2017.01.025.

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Annealing Effect on the Magnetic Properties of Cobalt-based

Amorphous Alloys

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Sumin Kima, Yong Jin Kimb, Young Keun Kimb and Haein Choi-Yima*

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a
Department of Physics, Sookmyung Women’s University, Seoul 04310, Republic of Korea
b
Department of Materials Science and Engineering, Korea University, Seoul 02814, Republic of Korea

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The annealing effects on the magnetic properties of the Co72B19.2Si4.8Cr4 and Co64.8Fe7.2B19.2Si4.8Cr4

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alloy systems are reported. Ribbon samples with 2 mm width and 20-30 µm thickness for both
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compositions were synthesized by melt spinning. The as-spun samples were subjected to annealing at

various temperatures below their glass transition temperatures for 15 min in a vacuum. The annealed
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systems tended to have improved soft magnetic characteristics, including higher saturation
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magnetization and lower coercivity values, while maintaining their amorphous phase. A high saturation
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magnetization of 87.8 emu g-1 and low coercivity of 0.084 Oe were obtained for Co64.8Fe7.2B19.2Si4.8Cr4

after annealing at 400 °C, which is a significant improvement in comparison to the magnetic properties
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of the as-spun ribbons.

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Keywords: Annealing, Co-based, Amorphous, Soft magnetic, Ferromagnetic

*Corresponding author

E-mail: haein@sm.ac.kr, tel: +82-2-710-9239, fax: +82-303-0799-0362

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1. Introduction

Amorphous alloys play an increasingly important role in industry due to their significant

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technological potential as a result of their low material cost and high corrosion resistance [1,2]. In

particular, ferromagnetic amorphous alloys with excellent soft magnetic properties are being developed

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for use in motors, distribution transformers, electromagnetic shielding applications, and sensors [3-5].

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Among these materials, Co-based amorphous alloys have nearly zero magnetostriction [6,7], a suitable

characteristic for magnetic cores [8]. However, their amorphous phase is structurally in a metastable

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state owing to rapid quenching, so further heat treatments are necessary to optimize magnetic
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properties for applications. The coercivity (Hc), which indicates applicability for practical use, is a

primary property of ferromagnetic materials. Annealing treatments have previously been investigated
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for a number of amorphous alloy systems [9-11] and been found to cause a reduction of Hc and losses

[12]. Hence, from a technological point of view, it is important to investigate the effects of the
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annealing process on the amorphous structure of alloys with respect to their magnetic properties.
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We previously studied Co- and Fe-based amorphous alloys [13] and published the effects of variable

Fe and Co contents on the thermal and magnetic properties of (Co1-xFex)72B19.2Si4.8Cr4 (0 ≤ x ≤ 1)

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systems [14], and identified eleven alloys of amorphous nature among the specimens. In addition, Co-
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Fe-B-Si-Cr glassy ribbons exhibited soft magnetic properties with high saturation magnetization (Ms)
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values. With an increase in the Fe content ratio, x, the Ms gradually increased and reached its highest

value of 1.22 T for the Co7.2Fe64.8B19.2Si4.8Cr4 (x = 0.9) alloy. The lowest value, on the other hand, was

0.65 T for the Co72B19.2Si4.8Cr4 (x = 0) alloy. Based on these previous results, the present investigation

addresses the effects of annealing on the magnetic properties of Co72B19.2Si4.8Cr4 and

Co64.8Fe7.2B19.2Si4.8Cr4 as-spun ribbons, including Hc and Ms, while maintaining their amorphous phase.

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2. Experiments

Alloy ingots with compositions of Co72B19.2Si4.8Cr4 and Co64.8Fe7.2B19.2Si4.8Cr4 were prepared by arc-

melting mixtures of high purity Co (99.95 %), Fe (99.95 %), B (99.5 %), Si (99.999 %) and Cr

(99.99 %) under a Ti-gettered argon atmosphere. All ingots were re-melted four times to properly mix

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the elements constituting the materials. Amorphous alloys were subsequently produced in the form of

ribbons, typically 20-30 µm thick and 2 mm wide, by using melt spinning under an argon atmosphere

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at a roll speed of 39.3 m s-1. Annealing treatments of as-spun samples were performed at various

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temperatures below their Tg values for 15 min in a vacuum. The structures of as-spun and annealed

samples were examined by X-ray diffraction (XRD) with Cu-Kα radiation. Thermal properties

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associated with the Tg and crystallization temperature (Tx) values were investigated by differential
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scanning calorimetry (DSC) and thermomechanical analysis (TMA) under argon flow, using constant

heating at a heating rate of 0.34 K s-1. The Tg values were determined by TMA from the intersection of
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two tangential lines in the dimensional change versus temperature profiles. The hysteresis loops of as-

spun and annealed samples were measured at room temperature with a vibrating sample magnetometer
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(VSM) under an in-plane applied magnetic field ranging from -19,000 to 19,000 Oe. The field
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resolution of the VSM was 1 mOe.

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3. Results and Discussion

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DSC and TMA under a flowing argon atmosphere were necessary to determine the annealing
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temperatures below Tg. The DSC curves of as-spun Co72B19.2Si4.8Cr4 and Co64.8Fe7.2B19.2Si4.8Cr4

ribbons are shown in Fig. 1. For Co64.8Fe7.2B19.2Si4.8Cr4 alloy, it is interesting to observe the gradual

change in its thermal response. The endothermic transformation, defined as the Tg, occurred around

763 K. However, for the Co72B19.2Si4.8Cr4 alloy, Tg could not be identified by the DSC curves. A

number of papers have reported the determination of Tg using TMA [15,16]. In this study, TMA was

used to obtain a Tg of 637 K for the Co72B19.2Si4.8Cr4 as-spun ribbons. As the heating temperature
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increased, an exothermic transformation corresponding to the Tx was observed for the as-spun ribbons

of both compounds. As a result, the as-spun Co72B19.2Si4.8Cr4 and Co64.8Fe7.2B19.2Si4.8Cr4 ribbons were

annealed for 15 min in a vacuum at 250, 300, and 350 °C, and at 350, 400, and 450 °C, respectively.

The Tg and Tx values are marked by arrows in Fig. 1, and the determined values are summarized,

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including used annealing conditions in Table 1.

Figs. 2 (a) and (b) show the XRD patterns for the as-spun and annealed ribbons of Co72B19.2Si4.8Cr4

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and Co64.8Fe7.2B19.2Si4.8Cr4, respectively. Each pattern consists of a broad halo hump, indicating the

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formation of an amorphous phase. No sharp diffraction peaks corresponding to a crystalline phase

could be observed for any alloy. Even though the as-spun ribbons underwent isothermal heat treatments,

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they maintained their amorphous phases without crystallization, which indicates that the annealing
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treatments at temperatures below Tg had no substantial influence on the alloy structures.

Fig. 3 (a) depicts the hysteresis loops for the Co72B19.2Si4.8Cr4 ribbons, both as-spun and after
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annealing at 250, 300, and 350 °C for 15 min. Fig. 3 (b), likewise, depicts the hysteresis loops for the

Co64.8Fe7.2B19.2Si4.8Cr4 ribbons, as-spun and after annealing at 350, 400, and 450 °C for 15 min. Figs. 4
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(a) and (b) are magnifications of figs. 3(a) and (b), respectively, near their origins to show their Hc,
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because of their soft magnetic characteristic as low Hc. The typical Hc values of fully amorphous

ribbons were less than 1 Oe. Fortunately, the Hc of the specimens could be resolved by VSM. The
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Co72B19.2Si4.8Cr4 and Co64.8Fe7.2B19.2Si4.8Cr4 as-spun ribbons could thus be identified as ferromagnetic

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materials. In addition, both as-spun ribbon materials exhibited good soft magnetic properties, having
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low Hc values of 0.182 and 0.126 Oe, respectively, and high Ms values of 66.0 emu g-1 and 73.8 emu g-
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respectively. Hc is an extrinsic property that is sensitive to residual stresses induced during rapid

quenching therefore heat treatment of the amorphous phase is necessary to obtain better properties than

those of as-spun ribbons. For the Co72B19.2Si4.8Cr4 alloy, there was a distinct correlation between Ms

and Hc. With an increase in Ms, Hc gradually decreased. However, no correlation of the magnetic

properties, including Ms and Hc, with the annealing temperature was seen. At the lowest annealing
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temperature of 250 °C, the soft magnetic properties were worse than those of as-spun ribbons. As the

annealing temperature increased, however, samples showed progressively better soft magnetic alloy

characteristics. The final obtained values of Hc and Ms were 0.113 Oe and 71.1 emu g-1, respectively.

Consequently, the optimum heat treatment condition was determined to be 350 °C for 15 min in a

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vacuum for the Co72B19.2Si4.8Cr4 alloy. For the Co64.8Fe7.2B19.2Si4.8Cr4 alloy, it was found that annealing

caused a reduction in Hc and improvement in Ms. Annealing of the as-spun Co64.8Fe7.2B19.2Si4.8Cr4

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ribbons decreased Hc to 0.082 Oe, and increased Ms to 87.8 emu g-1. When comparing the annealing

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temperatures of 400 and 450 °C, there was a relatively small difference in Hc, but a great difference

between the values for Ms. Accordingly, heat treatment at 400 °C for 15 min in a vacuum was optimum

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annealing condition for Co64.8Fe7.2B19.2Si4.8Cr4 alloys.
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Figs. 5(a) and (b) show the trends for both Ms and Hc with an increase in the annealing temperature.

Details of the magnetic properties for all annealing conditions are listed in Table 1.
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From the above, annealing clearly resulted in an improvement is soft magnetic properties in the

various alloys. Nonetheless, annealing above Tg was not investigated yet and is currently under
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investigation.
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4. Conclusion
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The annealing effects on the magnetic behavior of soft magnetic amorphous ribbons of nominal
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composition Co72B19.2Si4.8Cr4 and Co64.8Fe7.2B19.2Si4.8Cr4 were studied. Through differential scanning

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calorimetry and thermomechanical analysis, we determined annealing temperatures below the Tg values

of the compounds without crystallization processes taking place. In the X-ray diffraction patterns, all

ribbons, with or without heat treatment, were identified as fully amorphous alloys. In addition,

hysteresis curves indicated their magnetic properties. We also confirmed that the annealing procedure

contributed to soft magnetic characteristics, leading to higher Ms and lower Hc values; optimum

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annealing conditions were thus obtained for the respective alloys. For example, the lowest value of Hc

for Co64.8Fe7.2B19.2Si4.8Cr4 was 0.082 Oe after annealing for 15 min at 450 °C.

Acknowledgements: This research was supported by the National Research Foundation of Korea

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(NRF) funded by the Ministry of Science, ICT and Future Planning (MSIP) (NRF-

2015R1A2A2A01005294) and the Commercializations Promotion Agency for R&D Outcomes

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(COMPA) funded by the MSIP.

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References

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[1] T. Masumoto, K. Suzuki, H. Fujimori, K. Hashimoto, Materials Science of Amorphous Metals,
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Ohm Publication, Tokyo, (1982), pp. 7–20.
[2] A. Inoue, A. Takeuchi, T. Zhang, Mater. Trans. 29 (1998) 1779-1793.
[3] T. D. Shen, R. B. Schwarz, Appl. Phys. Lett. 75 (1999) 49-51.
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[4] A. Inoue, B.L. Shen, C.T. Chang, Intermetallics 14 (2006) 936-944.

[5] T. Miyazaki, K. Yamauchi, S. Arakawa, Y. Yoshizawa, S. Nakajima, Bulletin Japan Inst. Metals
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26 (1987) 299-301.
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[6] R.C. O’Handley, Solid State Commun. 21 (1977) 1119-1122.

[7] R.C. O’Handley, Magnetostriction of metallic glasses, In Amorphous Magnetism II, Springer US,
(1977), pp. 379-392.
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[8] H. Fujimori, M. Kikuchi, Y. Obi, T. Masumoto, Sci. Rep. RITU A-26 (1976) 36-47.
[9] H.S. Chen, J. Appl. Phys. 52 (1981) 1868-1870.
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[10] H.S. Chen, J. Non-Cryst. Solids 46 (1981) 289-305.

[11] H.S. Chen, A. Inoue, J. Non-Cryst. Solids 61&62 (1984) 805-810.
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[12] F.E. Luborsky, IEEE Trans. Magn. MAG-11 (1975) 1644.

[13] S. Kim, B.K. Han, D.T. Quach, D-H Kim, Y.K. Kim, H. Choi-Yim Curr. Appl. Phys. 16 (2016)
515-519.
[14] S. Kim, H. Choi-Yim, J. Korean. Phys. Soc. 67 (2015) 2120-2123.
[15] H. Osterwald, C.D. Eisenbach, K.H. Bauer, Acta Pharm. Technol. 29 (1982) 34-43.
[16] Y. Yamaoka, H. Ichikawa, Y. Takeuchi, T. Fukuda, Y. Osako, Chem. Pharm. Bull. 34 (1986)
4314-4321.
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Table 1. Thermal and magnetic properties of as spun and annealed Co72B19.2Si4.8Cr4 ribbons; and
as-spun and annealed Co64.8Fe7.2B19.2Si4.8Cr4 ribbons.

Thermal Properties Magnetic Properties

Annealing
Alloys
Condition Tg Tx Hc Ms
(K) (K) (Oe) (emu/g)
Co72B19.2Si4.8Cr4 As-spun 637 680 0.182 66.0

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250 1.169 62.8
300 0.163 69.2
0.113 71.1

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350
Co64.8Fe7.2B19.2Si4.8Cr4 As-spun 763 800 0.126 73.8
350 0.113 77.1

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400 0.084 87.8
450 0.082 79.7

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Figure Captions.
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Fig. 1. The differential scanning calorimetry curves of as-spun Co72B19.2Si4.8Cr4 ribbons and as-spun

Co64.8Fe7.2B19.2Si4.8Cr4 ribbons.
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Fig. 2. The X-ray diffraction patterns of (a) as-spun and annealed Co72B19.2Si4.8Cr4 ribbons; and (b)

as-spun and annealed Co64.8Fe7.2B19.2Si4.8Cr4 ribbons.

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Fig. 3. Hysteresis loops of (a) as-spun and annealed Co72B19.2Si4.8Cr4 ribbons; and (b) as-spun and
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annealed Co64.8Fe7.2B19.2Si4.8Cr4 ribbons.

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Fig. 4. Enlargement near the origin to show the coercivities of (a) as-spun and annealed

Co72B19.2Si4.8Cr4 ribbons; and (b) as-spun and annealed Co64.8Fe7.2B19.2Si4.8Cr4 ribbons.

Fig. 5. Variation of Ms and Hc in as-spun and annealed ribbons of (a) Co72B19.2Si4.8Cr4 and (b)

Co64.8Fe7.2B19.2Si4.8Cr4 with increasing annealing temperatures.

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1. We determined annealing temperatures below the Tg values of the compounds without

crystallization processes taking place.

2. As the annealing temperature increased, samples showed progressively better soft magnetic

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alloy characteristics.

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3. The lowest value of Hc for Co64.8Fe7.2B19.2Si4.8Cr4 was 0.082 Oe after annealing for 15 min at

450 °C.

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