Achieving integrated soft magnetic-catalytic functionalities in Fe-based amorphous ribbons via glassy matrix and self-spalling oxide layer

doi:10.1016/j.metadv.2026.01.010

Abstract

Abstract:

This study comprehensively explores the correlation between microstructural evolution/surface characteristics and the dual functional performance of soft magnetism and catalytic degradation in Fe-based amorphous alloys. The magnetic properties and methyl orange (MO) degradation performance of as-spun Fe₈₀P₅C₁₅₋_xB_x ribbons (x = 0 and 10), produced at various roller speeds (R_s) ranging from 10 to 45 s⁻¹, were carefully analyzed. The soft magnetic properties and MO degradation performance of the ribbons are synergistically enhanced with increasing R_s and boron (B) doping. This enhancement can be ascribed to matrix modification, specifically the formation of the Fe₂₃(C,B)₆ crystalline phase and a fully glassy phase, along with the formation of a self-spalling oxide layer on the surface. Specifically, the kinetic rate constant (k) for all ribbons shows a clear positive correlation with both saturation magnetization (B_s) and logarithmic magnetic permeability at the frequency of 1000 kHz (lnμ_hf), highlighting the role of magnetic-catalytic synergy in accelerating the reaction rate. This work presents a novel strategy for designing Fe-based amorphous alloys with integrated soft magnetic and catalytic functionalities, offering promising potential for application in reusable wastewater treatment systems.

Key words: Fe-based amorphous, Fe₂₃(C,B)₆ crystalline phase, Glassy matrix, Self-spalling oxide layer, Magnetic-catalytic synergy

Zhi-Gang Qi, Qi Chen, Zhao-Xuan Wang, Zi-Wei Guo, Zi-Qi Song, Yan-Xu Li, Xin-Long Lu, Mehran-Khan Alam, Su-Juan Cheng, Bo-Xuan Cao, Xi-Hua Zhang, Wei-Min Wang. Achieving integrated soft magnetic-catalytic functionalities in Fe-based amorphous ribbons via glassy matrix and self-spalling oxide layer[J]. Metals Advances, 2026, 40: 88-100.

Figures/Tables 13

Fig. 1. Microstructure of as-spun Fe80P5C15−xBx ribbons (x = 0 and 10, labeled as B0 and B10) with the roller speeds (Rs) of 10, 17.5, 25, and 45 s−1, labeled as B0-10, B0-17.5, B0-25, and B0-45, and B10-10, B10-17.5, B10-25, and B10-45 ribbons, respectively. XRD curves of (a) B0 and (b) B10 ribbons; DSC curves of (c) B0 and (d) B10 ribbons at a heating/cooling rate of 20 min−1; (e) BFTEM image of B0-10 ribbon, the inset gives the corresponding particle grain size distribution; (f) HRTEM image for red square in BFTEM image (e) and the corresponding FFT pattern region for white square in HRTEM image; (g) BFTEM image of B0-45, the inset gives the corresponding SAED pattern; (h) BFTEM image of B10-10 ribbon, the inset gives the corresponding particle grain size distribution; (i) HRTEM image for red square in BFTEM image (h) and the corresponding FFT pattern region for white square in HRTEM image; (j) BFTEM image of B10-45, the inset gives the corresponding SAED pattern.

Table 1. Thermal properties of as-spun Fe80P5C15−xBx ribbons (x = 0 and 10, labeled as B0 and B10) with the roller speeds (Rs) of 10, 17.5, 25, and 45 s−1 (labeled as B0-10, B0-17.5, B0-25, and B0-45, and B10-10, B10-17.5, B10-25, and B10-45 ribbons, respectively) deduced from the DSC curves, including the glass transition temperature Tg, crystallization temperatures Tx1, Tx2 and Tx3, onset melting temperature Tm, offset melting temperature Tl, solidification temperature Ts and reduced crystallization temperature Trx (Tx1/Tl).

Alloy	T_g (K)	T_x1 (K)	T_x2 (K)	T_x3 (K)	T_m (K)	T_l (K)	T_s (K)	T_l−T_s (K)	T_rx
B0-10	-	-	-	-	1227	1361	1328	33	-
B0-17.5	-	-	-	-	1227	1363	1336	27	-
B0-25	-	693	732	841	1227	1361	1328	33	0.509
B0-45	-	691	731	829	1227	1363	1341	22	0.507
B10-10	-	-	-	-	1253	1397	1349	48	-
B10-17.5	706	737	-	-	1253	1391	1348	43	0.530
B10-25	701	733	-	-	1253	1373	1321	52	0.534
B10-45	694	732	-	-	1248	1361	1316	45	0.538

Fig. 2. Soft magnetic properties of B0 and B10 ribbons. B-H hysteresis loops of (a) B0 and (b) B10 ribbons measured by the vibrating sample magnetometer (VSM), the insets give the enlarged part of the red and yellow squares in hysteresis loops; (c) B-H hysteresis loops of B0-25, B0-45, B10-17.5, B10-25 and B10-45 ribbons measured by DC B-H loop tracer, the inset gives the enlarged part of the red square in hysteresis loops; (d) the magnetic permeability curves at 1-1000 kHz of B0 and B10 ribbons; (e) the saturation magnetization Bs vs. Rs for B0 and B10 ribbons (NC: nanocrystallites, G: glassy phase); (f) the coercivity Hc vs. Rs for B0 and B10 ribbons.

Table 2. Saturation magnetization Bs, magnetic permeability at the frequency of 1000 kHz μhf and coercivity Hc for B0 and B10 ribbons.

Alloy	B_s (T)	μ_hf	H_c (Oe)	H_c (A m⁻¹)
B0-10	1.443	3.73	87.36	6951.89
B0-17.5	1.515	3.45	154.86	12323.37
B0-25	1.592	119.98	-	19.59
B0-45	1.625	143.97	-	26.18
B10-10	1.601	12.56	63.43	5047.60
B10-17.5	1.635	182.80	-	5.01
B10-25	1.642	271.20	-	6.18
B10-45	1.658	299.45	-	7.26

Fig. 3. MO degradation performance of B0 and B10 ribbons. The normalized concentration changes of MO solution using (a) B0 and (b) B10 ribbons; the ln(c0/ct)-tr curves for (c) B0 and (d) B10 ribbons; (e) the kinetic rate constant k vs. Rs for B0 and B10 ribbons (NC: nanocrystallites, G: glassy phase); (f) the kinetic rate constant k comparison of B10-25, B10-45 and the referenced ribbons.

Table 3. Current development of wastewater treatment using B10-25, B10-45 and the referenced ribbons.

Catalysts	Roller speed (m s⁻¹)	Organic pollutants	c_Dye (mg L⁻¹)	c_catalysts (g L⁻¹)	c_H2O2 (mM)	pH	k (min⁻¹)
B10-25 (This work)	25	MO	20	0.5	1	3	0.50
B10-45 (This work)	45	MO	20	0.5	1	3	0.71
Fe₇₈Si₉B₁₃[34]	30	MO	20	0.5	1	3.4	0.386
Fe_73.5Si_13.5B₉Cu₁Nb₃ [34]	30	MO	20	0.5	1	3.4	0.152
Fe₈₁B₁₀C₉[36]	35	MB	20	0.5	0.2	3	0.75
Fe₈₁B₁₀P₉[36]	35	MB	20	0.5	0.2	3	0.80
Fe_83.2CoP₁₀C₆Cu_0.8[37]	40	MB	100	0.5	1	3	0.34
Fe_79.2Co₄P₁₀C₆Cu_0.8[37]	40	MB	100	0.5	1	3	0.47
Fe_73.2Co₁₀P₁₀C₆Cu_0.8[37]	40	MB	100	0.5	1	3	0.23
Fe₈₀P₁₃C₇[38]	40	MB	100	0.5	1	3	0.56
Fe₈₀Si₁₀B₁₀[39]	40	MB	20	0.5	1	3	0.376
Fe₈₃Si₅B₈P₄[39]	40	MB	20	0.5	1	3	0.514

Fig. 4. Degradation mechanism and reusability analysis of B0-45 and B10-45 ribbons. (a) EPR spectra of DMPO-·OH in MO solution generated by B0-45 and B10-45 ribbons after 11 min; (b) the total spin number (spins) of DMPO-·OH generated by B0-45 and B10-45 ribbons in MO solution vs. time; (c) ICP-MS analysis result of Fe ions concentration in MO solution after 9 min degradation by B0-45 and B10-45 ribbons; the normalized concentration change of MO solution during the degradation process of (d) B0-45 and (e) B10-45 ribbons in the reusability test; (f) the degradation efficiency η17 (= 1 − ct/c0 × 100%, tr = 17 min) and kinetic rate constant k vs. reaction cycles for B0-45 and B10-45 ribbons; the surface morphologies of (g)-(i) 0th, 1 st, and 4th reacted B0-45 ribbons, and (j)-(n) 0th, 1 st, 4th, 8th, and 12th reacted B10-45; (o) Fe 2p3/2 and (p) B 1 s XPS spectra in binding energy regions for 0th, 4th, 8th and 12th reacted B10-45 ribbons.

Table 4. General compositions (at.%) of B0-45 and B10-45 ribbons and their corresponding reacted ribbons after reusability test by EDS analysis.

Cycles	B0-45				B10-45
Cycles	c_Fe	c_P	c_C	c_O	c_Fe	c_P	c_C	c_O	c_B
0th	69.74	4.29	24.31	1.66	58.47	4.58	13.91	1.99	21.05
1st	36.80	4.47	36.03	22.70	32.09	3.79	31.32	23.81	8.99
4th	32.26	4.79	32.17	30.79	25.46	4.22	25.01	37.17	8.13
8th	-	-	-	-	32.98	5.49	17.47	38.86	5.19
12th	-	-	-	-	32.13	4.85	18.38	41.01	3.62

Fig. 5. Surface analysis of B0-45 and B10-45 ribbons. XPS spectra of Fe 2p3/2, P 2p, C 1s and O 1s in binding energy regions for (a)-(d) B0-45 and (e)-(h) B10-45 ribbons after etching at 0, 30, 60 and 90 s; (i) polarization curves of B0-45 and B10-45 ribbons in MO solution; (j) Nyquist curves and relative fitting results by equivalent circuit R(C(R(QR))); (k) and (l) the Bode plots and corresponding fitting results.

Table 5. Fitting results of EIS data: Rso, solution resistance; Cdl, capacitance of electric double layer; Rtr, transfer charge resistance; Qdi and Rdi, diffusion resistance; Rtotal, total resistance.

Alloy	R_so (Ω cm²)	C_dl (10⁻⁸ Ω⁻¹ cm⁻²)	R_tr (Ω cm²)	Q_di		R_di (Ω cm²)	R_total (Ω cm²)
Alloy	R_so (Ω cm²)	C_dl (10⁻⁸ Ω⁻¹ cm⁻²)	R_tr (Ω cm²)	Y_di (10⁻³ Ω⁻¹ s⁻ⁿ cm⁻²)	n	R_di (Ω cm²)	R_total (Ω cm²)
B0-45	21.14	3.62	307.20	1.34	0.70	316.20	644.54
B10-45	8.06	4.27	255.00	1.09	0.67	199.60	462.66

Fig. 6. Crystalline structures of single unit cells for (a) Fe3C, (b) Fe23C6 and (c) Fe23C3B3, as well as the (d) total magnetic moment (ms) and average ms per Fe atom for Fe3C, Fe23C6 and Fe23C3B3.

Fig. 7. Magnetic-catalytic synergy of B0 and B10 ribbons. (a) lnμhf vs. Bs, (b) lnμhf vs. lnHc, (c) k vs. Bs, and (d) k vs. lnμhf and their polynomial fittings for all the ribbons. (μhf: the magnetic permeability μ at 1000 kHz; Bs: saturation magnetization; Hc: coercivity; k: kinetic rate constant).

Fig. 8. Schematic diagrams illustrating the soft magnetic properties and MO degradation performance of B0 and B10 ribbons.

References 56

[1]	J.C. Qiao, Q. Wang, J.M. Pelletier, H. Kato, R. Casalini, D. Crespo, E. Pineda, Y. Yao, Y. Yang, Prog. Mater. Sci. 104 (2019) 250-329. DOI
[2]	S.L. Huang, Q.J. Chen, L. Ji, K. Wang, G.S. Huang, Acta Metall. Sin. -Engl. Lett. 37 (2024) 196-204.
[3]	X.S. Li, J. Zhou, L.Q. Shen, B.A. Sun, H.Y. Bai, W.H. Wang, Adv. Mater. 35 (2023) 2205863. DOI URL
[4]	Y.X. Geng, X. Lin, Y.X. Wang, J.B. Qiang, Y.M. Wang, C. Dong, Acta Metall. Sin. - Engl. Lett. 30 (2017) 659-664.
[5]	H.X. Li, Z.C. Lu, S.L. Wang, Y. Wu, Z.P. Lu, Prog. Mater. Sci. 103 (2019) 235-318. DOI
[6]	Q. Chen, L.Y. Guo, H.X. Di, Z.G. Qi, Z.X. Wang, Z.Q. Song, L.C. Zhang, L.N. Hu, W.M. Wang, Adv. Sci. 10 (2023) 2304045. DOI URL
[7]	F. Hu H.Y. Wang Y. Zhang X.C. Shen G.H. Zhang Y.B. Pan J.T. Miller K. Wang S.L. Zhu X.J. Yang C.M. Wang X.J. Wu Y.J. Xiong Z.M. Peng, Small 15 (2019) 1901020.
[8]	T.Q. Guo, L.D. Li, Z.C. Wang, Adv. Energy Mater. 12 (2022) 2200827. DOI URL
[9]	Z. Jia J.L. Jiang L.G. Sun L.C. Zhang Q. Wang S.X. Liang P. Qin D.F. Li J. Lu J.J. Kruzic, ACS Appl. Mater. Interfaces 12 (2020) 44789-44797. DOI URL
[10]	Z.G. Qi, Q. Chen, Y. Feng, H.Z. Liu, Z.X. Wang, Z.Q. Song, Z.C. Yan, L.Y. Guo, X.H. Zhang, W.M. Wang, J. Alloy. Compd. 953 (2023) 170135. DOI URL
[11]	H.Y. Zhou, J.L. Peng, J.Y. Li, J.J. You, L.D. Lai, R. Liu, Z.M. Ao, G. Yao, B. Lai, Water Res. 188 (2021) 116529. DOI URL
[12]	M.J. Shi, Z.Q. Liu, T. Zhang, J. Mater. Sci. Technol. 31 (2015) 493-497.
[13]	Y.L. Li, Z.X. Dou, X.M. Chen, K. Lv, F.S. Li, X.D. Hui, J. Alloy. Compd. 844 (2020) 155767. DOI URL
[14]	F. Miao, Q.Q. Wang, Q.S. Zeng, L. Hou, T. Liang, Z.Q. Cui, B.L. Shen, J. Mater. Sci. Technol. 38 (2020) 107-118.
[15]	J. Lentz, A. Röttger, W. Theisen, Acta Mater. 119 (2016) 80-91. DOI URL
[16]	J. Lentz, A. Röttger, W. Theisen, Mater. Charact. 135 (2018) 192-202. DOI URL
[17]	S.H. Xie, X. Liao, X.R. Zeng, H.P. Yang, L. He, Acta Metall. Sin. -Engl. Lett. 35 (2022) 1653-1664.
[18]	J.G. Long, P.R. Ohodnicki, D.E. Laughlin, M.E. Mchenry, T. Ohkubo, K. Hono, J. Appl. Phys. 101 (2007) 09N114.
[19]	P. Huang, Y.T. Shi, W. Zhang, S.D. Zhang, Y.L. Ren, K.Q. Qiu, J.Q. Wang, Acta Metall. Sin. -Engl. Lett. 36 (2023) 1502-1510.
[20]	A. Hirata, Y. Hirotsu, K. Amiya, N. Nishiyama, A. Inoue, Intermetallics 16 (2008) 491-497.
[21]	L.Q. Xing, J. Eckert, W. Löser, S. Roth, L. Schultz, J. Appl. Phys. 88 (2000) 3565-3569.
[22]	P. Rezaei-Shahreza, A. Seifoddini, S. Hasani, J. Alloy. Compd. 738 (2018) 197-205. DOI URL
[23]	L. Cai J.T. Huo P. Zou G.W. Li J. Liu W. Xu M. Gao S.Z. Zhang J.Q. Wang, ACS Appl. Mater. Interfaces 14 (2022) 15243-15249. DOI URL
[24]	Z.G. Qi, Q. Chen, Z.X. Wang, Z.Q. Song, K.B. Kim, J. Pang, X.H. Zhang, W.M. Wang, NPJ Mater. Degrad. 8 (2024) 28. DOI
[25]	G. Kresse, J. Furthmüller, Comput. Mater. Sci. 6 (1996) 15-50. DOI URL
[26]	M. Levy, J.P. Perdew, Phys. Rev. Lett. 51 (1983) 1884-1887. DOI URL
[27]	W.H. Zhang, Z.Q. Lv, Z.P. Shi, S.H. Sun, Z.H. Wang, W.T. Fu, J. Magn. Magn. Mater. 324 (2012) 2271-2276. DOI URL
[28]	Y.L. Yi, Q. Li, J.D. Xing, H.G. Fu, D.W. Yi, Y.Z. Liu, B.C. Zheng, Mater. Sci. Eng. A 754 (2019) 129-139. DOI URL
[29]	F.Q. Meng, J. Geng, M.F. Besser, M.J. Kramer, R.T. Ott, J. Appl. Phys. 116 (2014) 223505.
[30]	C.G. Jia, J. Pang, S.P. Pan, Y.J. Zhang, K.B. Kim, J.Y. Qin, W.M. Wang, Corros. Sci. 147 (2019) 94-107. DOI
[31]	Q.Y. Zhang, S.X. Liang, Z. Jia, W.C. Zhang, W.M. Wang, L.C. Zhang, J. Mater. Sci. Technol. 61 (2021) 159-168.
[32]	K. Wang, X.J. Wei, X.L. Li, Q.H. Feng, G.B. Shi, Y.F. Duan, Y.X. Wang, J.M. Li, H.G. Sun, L. Wang, J. Alloy. Compd. 994 (2024) 174723. DOI URL
[33]	K.Y. Wu, F. Chu, Y.Y. Meng, K. Edalati, Q.S. Gao, W. Li, H.J. Lin, J. Mater. Chem. A 9 (2021) 12152-12160.
[34]	Z. Jia J. Kang W.C. Zhang W.M. Wang C. Yang H. Sun D. Habibi L.C. Zhang, Appl. Catal. B-Environ. 204 (2017) 537-547.
[35]	L.C. Zhang, S.X. Liang, Chem. -Asian J. 13 (2018) 3575-3592. DOI URL
[36]	B.B. Wei, X.L. Li, H.G. Sun, K.K. Song, L. Wang, J. Non-Cryst. Solids 575 (2022) 121212.
[37]	L. Hou Q.Q. Wang X.D. Fan F. Miao W.M. Yang B.L. Shen, New J. Chem. 43 (2019) 6126-6135. DOI URL
[38]	Q.Q. Wang, M.X. Chen, P.H. Lin, Z.Q. Cui, C.L. Chu, B.L. Shen, J. Mater. Chem. A 6 (2018) 10686-10699.
[39]	M.Q. Zuo, S. Yi, J. Choi, J. Environ. Sci. 105 (2021) 116-127. DOI URL
[40]	S.H. Xie, G.Q. Peng, X.M. Tu, H.X. Qian, X.R. Zeng, Acta Metall. Sin. -Engl. Lett. 31 (2018) 1207-1214.
[41]	Q. Chen, Z.C. Yan, L.Y. Guo, H. Zhang, L.C. Zhang, K.B. Kim, X.Y. Li, W.M. Wang, J. Alloy. Compd. 831 (2020) 154817. DOI URL
[42]	C.L. Qin, Q.F. Hu, Y.Y. Li, Z.X. Wang, W.M. Zhao, D.V. Louzguine-Luzgin, A. Inoue, Mater. Sci. Eng. C 69 (2016) 513-521. DOI URL
[43]	Q. Chen, H.X. Di, Z.G. Qi, Z.X. Wang, Z.Q. Song, Z.W. Guo, X.L. Lu, Y.X. Li, L.C. Zhang, W.M. Wang, J. Mater. Sci. Technol. 232 (2025) 1-13.
[44]	Y.D. Yao, N. Mahmood, L. Pan, G.Q. Shen, R.R. Zhang, R.J. Gao, F. Aleem, X. Yuan, X.W. Zhang, J.J. Zou, Nanoscale 10 (2018) 21327-21334.
[45]	Q. Chen, Z.G. Qi, Y. Feng, H.Z. Liu, Z.X. Wang, L.C. Zhang, W.M. Wang, J. Mol. Liq. 364 (2022) 120058. DOI URL
[46]	F. Rueda, J. Mendialdua, A. Rodriguez, R. Casanova, Y. Barbaux, L. Gengembre, L. Jalowiecki, J. Electron Spectrosc. Relat. Phenom. 82 (1996) 135-143. DOI URL
[47]	F. Zhang, W. Zhao, W.G. Zhang, Z.X. Liao, X.H. Xiang, H.J. Gou, Z.L. Li, H. Wei, X. Wu, Q. Shan, Ceram. Int. 49 (2023) 2638-2647. DOI URL
[48]	M.A. Amin, K.F. Khaled, S.A. Fadl-Allah, Corros. Sci. 52 (2010) 140-151. DOI URL
[49]	L.C. Wu, Y.H. Li, X.J. Jia, A.N. He, W. Zhang, Acta Metall. Sin. -Engl. Lett. 35 (2022) 235-242.
[50]	S. Zhang, Y.Z. Fan, Y. Li, W.Q. Li, H.J. Yi, H.L. Li, T. Wang, J.Q. Wang, F.S. Li, Intermetallics 141 (2022) 107395.
[51]	Z.Q. Lv, F.C. Zhang, S.H. Sun, Z.H. Wang, P. Jiang, W.H. Zhang, W.T. Fu, Comput. Mater. Sci. 44 (2008) 690-694. DOI URL
[52]	J. Sun P.F. Shen Q.Z. Shang P.Y. Zhang L. Liu M.R. Li L. Hou, W.H. Li, Acta Phys. Sin. 72 (2023) 26101.
[53]	G.H. Bai, J.Y. Sun, Z.H. Zhang, X.L. Liu, S. Bandaru, W.W. Liu, Z. Li, H.X. Li, N.N. Wang, X.F. Zhang, Nat. Commun. 15 (2024) 2238. DOI
[54]	T.F. Babuska, M.A. Wilson, K.L. Johnson, S.R. Whetten, J.F. Curry, J.M. Rodelas, C. Atkinson, P. Lu, M. Chandross, B.A. Krick, J.R. Michael, N. Argibay, D.F. Susan, A.B. Kustas, Acta Mater. 180 (2019) 149-157. DOI
[55]	T. Zhou, K. Feng, W. Xiang, Y.L. Lv, X.H. Wu, J. Mao, C. He, Chemosphere 193 (2018) 968-977.
[56]	S. Giannakis, M.I.P. López, D. Spuhler, J.A.S. Pérez, P.F. Ibáñez, C. Pulgarin, Appl. Catal. B-Environ. 198 (2016) 431-446. DOI URL