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Fe-B-Si-Zr bulk metallic glasses with ultrahigh compressive strength and excellent soft magnetic properties
Materials Letters 181 (2016) 282–284
Contents lists available at ScienceDirect
Materials Letters journal homepage: www.elsevier.com/locate/matlet
Fe-B-Si-Zr bulk metallic glasses with ultrahigh compressive strength and excellent soft magnetic properties Jiajia Si a, Jinna Mei b, Rongshan Wang b, Xiaohua Chen a, Xidong Hui a,n a b
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China Suzhou Nuclear Power Research Institute, Suzhou 215004, China
art ic l e i nf o
a b s t r a c t
Article history: Received 30 November 2015 Received in revised form 31 May 2016 Accepted 11 June 2016 Available online 14 June 2016
A series of quaternary Fe-B-Si-Zr bulk metallic glasses (BMGs) with high Fe content were prepared by minor addition of Zr into Fe-Si-B alloy using copper-mold casting method. The proper adjusting in B, Si and Zr contents leads to significant improvement in glass forming ability (GFA). The thermal, mechanical and soft magnetic properties for this kind of BMGs were investigated. The strong interactions among constituent elements render Fe77.7B15.5Si5Zr1.8 BMG ultrahigh compressive strength of 4167 MPa. The BMGs with low Zr content exhibit high saturation magnetization (Ms) of over 1.5 T. Especially, high Ms of 1.60 T and low coercive force (Hc) of 4.3 A/m have been detected in Fe77.5B15.5Si5.5Zr1.5 BMG. & 2016 Elsevier B.V. All rights reserved.
Keywords: Amorphous materials Magnetic materials Thermal properties
1. Introduction Fe-base metallic glasses (MGs) have attracted great attention due to their excellent mechanic properties, soft magnetic properties, corrosion resistance and low cost [1–4]. Owing to the amorphous structure, Fe-based MGs possess high Ms, low Hc and high electrical resistivity, which make them applicable for soft magnetic devices [5]. In the last half century, seeking Fe-based amorphous soft magnetic materials with high Ms, low Hc and high GFA has been a hot topics in the field of amorphous alloys [6,7]. Since the first soft magnetic Fe73Al5Ga2P10C4B4Si2 BMG was developed [8], numerous progresses have been achieved in the Febased BMGs with high Ms. Efforts have been done for Fe-based BMGs to reduce the content of nonferromagnetic metallic elements and to adjust the varieties and contents of metalloid elements to achieve high Ms. Shen et al. [9] developed a Fe79P10C4B4Si3 BMG with the critical diameter (Dc) of 1 mm, and Ms of 1.53 T. Gao et al. [10] developed a Fe75.3C7.0Si3.3B5.0P8.7Cu0.7 BMG with the Dc of 3 mm and Ms of 1.61 T. Liu et al. [11] found that the Ms of Fe81Mo1P7.5C5.5B2Si3 BMG reached up to 1.64 T. Meng et al. [12] synthesized a (Fe90Co10)82P6C7B3Si2 BMG with high Ms of 1.65 T. For the latter two BMGs, purification technique was used to improve the GFA. Based on the previous studies, it seems necessary to adjust the metalloid elements to develop Fe-based BMGs with Ms above 1.6 T. n
Corresponding author. E-mail address: [email protected] (X. Hui).
http://dx.doi.org/10.1016/j.matlet.2016.06.052 0167-577X/& 2016 Elsevier B.V. All rights reserved.
In this paper, we present quaternary Fe-B-Si-Zr BMGs with ultrahigh compressive strength and excellent soft magnetic properties. Ultrahigh compressive strength of 4167 MPa has been detected in Fe77.7B15.5Si5Zr1.8 BMG, and high Ms of 1.60 T and low Hc of 4.3 A/m have been detected in Fe77.5B15.5Si5.5Zr1.5 BMG.
2. Experimental The alloy ingots were prepared by arc melting pure Fe (99.9%), Zr (99.95%), Si (99.9%) and ferroboron alloy (impurities o0.5%) in a Ti-gettered pure argon atmosphere. 1-mm diametric samples were prepared by a copper-mold suction casting method. Amorphous ribbons with 20–30 mm in thickness and 2 mm in width were prepared by single-roller melt spinning. The structures of these specimens were examined by X-ray diffraction (XRD) using Mo Kα radiation. The thermal properties of the as-cast BMGs and ribbons were investigated by differential scanning calorimetry (DSC) at a heating rate of 20 K/min. The hysteresis loops of as-spun ribbons were measured at room temperature with a vibrating sample magnetometer (VSM) under an applied field of 800 kA/m. The densities of the alloys were measured by the Archimedean method. The coercivities were measured with a DC B-H loop tracer under a field of 1 kA/m. Uniaxial compression tests were conducted at ambient temperature using a mechanical testing machine at a strain rate of 1 10 4 s 1. The test samples with an aspect ratio of 2:1 were cut from the as-cast 1-mm diametric rods.
J. Si et al. / Materials Letters 181 (2016) 282–284
283
3. Results and discussion Fig. 1 shows the XRD patterns of Fe-B-Si-Zr rods with 1 mm in diameter. The patterns exhibit similar halo shapes without visible crystal diffraction peaks, indicating that an amorphous structure has formed, respectively. The previous studies [6,13] have shown that Fe75B15Si10 alloy had the highest GFA in Fe-B-Si ternary system, and minor addition of 1 at% Zr into Fe75B15Si10 alloy increased the Dc of (Fe0.75B0.15Si0.1)99Zr1 to 0.75 mm. But the further addition of Zr caused the significant decrease in GFA. This phenomenon was explained by the strong bonding nature between Zr and other elements so that crystal phases were likely to precipitate. In this work, however, Fe-B-Si-Zr MGs with higher GFA and higher Fe content were obtained when 1.3–3 at% Zr was added. The enhancement of GFA in this Fe-Si-B-Zr system should be due to the large atomic radius of Zr and negative heats of mixing for Zr-Fe, Zr-B, and Zr-Si pairs, combining with proper compositional design [13,14]. Actually, amorphous structure can be formed in various methods. It is recently reported that high pressure torsion of crystalline alloys may induce the formation of amorphous state [15,16]. This is probably similar to the effect of mechanical alloying. Severe deformation can bring in numerous lattice defects and cause strong phase refining and transition, which may facilitate the generation of amorphous phases for certain multicomponent alloys. The DSC curves of five Fe-B-Si-Zr BMGs are presented in Fig. 2(a). All these DSC curves exhibit the glass transition and crystallization events, further confirming the glassy structure in these alloys. It is seen that the DSC curves of Fe75B18Si4Zr3, Fe77B15Si5Zr3 and Fe77B16Si4.5Zr2.5 BMGs exhibit clear and similar glass transition and crystallization events, while Fe77B16Si5Zr2 BMG shows unclear supercooled liquid region (SLR). Generally, with the decrease of Zr content in these alloys, the Curie temperature (TC) shows downtrend, and the SLR becomes unapparent. The crystallization events change significantly and multiple crystallization peaks overlap when the Zr content is below 2 at%. It is observed that when Fe is slightly substituted by 0.2 at% Zr in Fe77.2B16Si5Zr1.8 alloy, the thermal properties of Fe77B16Si5Zr2 BMG exhibit obvious changes, indicating that the thermal properties are sensitive to Zr content. Fig. 2(b) and (c) shows the DSC curves of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, Fe77.5B15.5Si5.5Zr1.5 and Fe77B14 Si7.7Zr1.3 amorphous ribbons. It is seen that the SLRs are invisible in the curves, which is the reflection of the reduction in stability of supercooled liquid. Despite the slight compositional variations, the crystallization and melting events of the MGs show significant changes.
Fig. 1. XRD patterns of as-cast Fe-B-Si-Zr rods.
Fig. 2. (a) DSC curves of Fe75B18Si4Zr3, Fe77B15Si5Zr3, Fe77B16Si4.5Zr2.5, Fe77B16Si5Zr2 and Fe77.2B16Si5Zr1.8 BMGs. (b) and (c) DSC curves of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, Fe77.5B15.5Si5.5Zr1.5 and Fe77B14Si7.7Zr1.3 glassy ribbons.
The thermal properties, including Curie temperature TC, glass transition temperature Tg, onset crystallization temperature Tx, melting temperature Tm, liquid temperature Tl and reduced glass transition temperature Tg/Tl (Trg) for the present MGs are listed in Table 1. The values of Tx/Tl are also shown in the table for comparison. It is found that the MGs without clear SLRs show relatively low Tx and Tx/Tl, which reflect the disadvantage in GFA. The compressive stress-strain curve of Fe77.7B15.5Si5Zr1.8 BMG is shown in Fig. 3. No obvious plastic deformation is observed in the curve, and the rod was compressed into fragments after compression. The BMG exhibits elastic strain of about 1.86% and compressive fracture strength of 4167 MPa, which is higher than the fracture strength of all the reported Fe-based BMGs with high Ms. It was reported in previous studies [6,17] that the Fe75B15Si10 amorphous wire exhibited tensile fracture strength of over 3200 MPa, and (Fe0.75B0.15Si0.10)96Nb4 BMG showed compressive fracture strength of 3200–3300 MPa together with small plastic strain. Compared with Nb, Zr has much larger atomic radius and negative heat of mixing with B, Si and Fe, respectively [14]. Hence, the strong atomic interactions in Fe77.7B15.5Si5Zr1.8 render the BMG ultrahigh fracture strength as well as the brittleness. The M-H hysteresis loops of four Fe-B-Si-Zr glassy ribbons are shown in Fig. 4 (in which the inset is part of magnified curves). The Ms of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, and Fe77B14Si7.7Zr1.3 alloys reach 1.56 T, 1.57 T, and 1.54 T, respectively, which are primarily attributed to the high Fe content (about 90 wt% Fe). Especially, Fe77.5B15.5Si5.5Zr1.5 alloy possesses high Ms of 1.60 T, demonstrating that multiple metalloid elements are not indispensable for Febased BMGs with high Ms. For most reported Fe-based BMGs with
284
J. Si et al. / Materials Letters 181 (2016) 282–284
Table 1 Thermal properties of Fe-B-Si-Zr MGs. Alloy
TC (K)
Tg (K)
Tx (K)
ΔTx (K)
Tm (K)
Tl (K)
Tl
Fe75B18Si4Zr3 Fe77B15Si5Zr3 Fe77B16Si4.5Zr2.5 Fe77B16Si5Zr2 Fe77.2B16Si5Zr1.8 Fe77.7B15.5Si5Zr1.8 Fe77B16Si5.5Zr1.5 Fe77.5B15.5Si5.5Zr1.5 Fe77B14Si7.7Zr1.3
582 581 611 619 620 628 646 636 653
810 802 810 796 813 – – – –
848 841 846 834 845 815 821 827 831
38 39 36 38 32 – – – –
1420 1404 1415 1401 1406 1418 1408 1406 1403
1471 1474 1470 1467 1472 1456 1494 1485 1460
51 70 55 66 66 38 86 79 57
Tm (K)
Trg
Tx/Tl
0.551 0.544 0.551 0.543 0.552 – – – –
0.576 0.571 0.576 0.569 0.574 0.560 0.550 0.557 0.569
Ms above 1.5 T, the addition of P element is needed to ensure the GFA. However, compared with B or Si, P in Fe-based MGs often plays a more disadvantageous role in Ms [18]. Thus the Fe77.5B15.5Si5.5Zr1.5 BMG exhibits high Ms. The Hc of as-spun glassy ribbons of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, Fe77.5B15.5Si5.5Zr1.5 and Fe77B14Si7.7Zr1.3 have been measured to be 15.7, 16.1, 4.3 and 14.5 A/m, respectively. Note that the Hc can be significantly affected by the sample quality, such as internal stress and structural defects despite the slight compositional variations. In this work, Fe77.5B15.5Si5.5Zr1.5 glassy ribbon still exhibits low Hc of 4.3 A/m although no relaxation treatment has been conducted.
4. Conclusions
Fig. 3. Compressive stress-strain curve of Fe77.7B15.5Si5Zr1.8 BMG.
In this work, a series of Fe-B-Si-Zr BMGs with high Fe content were synthesized. The variations in Zr content significantly affect the thermal properties. The addition of active Zr renders Fe77.7B15.5Si5Zr1.8 BMG ultrahigh compressive fracture strength of 4167 MPa. Moreover, high Ms above 1.5 T have been detected in the low Zr-containing BMGs. Especially, Fe77.5B15.5Si5.5Zr1.5 alloy exhibits high Ms of 1.60 T and low Hc of 4.3 A/m. Therefore, these Fe-B-Si-Zr BMGs are promising to be used as magnetic materials.
Acknowledgments The authors are grateful for the financial support of National Natural Science Foundation of China (Nos. 51271018, 51571016 and 5153100), and the proprietary program of the State Key Laboratory for Advanced Metals and Materials (2014-ZD04).
References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] Fig. 4. M-H hysteresis loops of Fe77.5B15.5Si5.5Zr1.5, Fe77B16Si5.5Zr1.5, Fe77.7B15.5Si5Zr1.8, and Fe77B14Si7.7Zr1.3 glassy ribbons. The inset exhibits part of magnified curves.
[17] [18]
M.E. Mchenry, M.A. Willard, D.E. Laughlin, Prog. Mater. Sci. 44 (1999) 291. A. Inoue, B.L. Shen, C.T. Chang, Intermetallics 14 (2006) 936. A. Inoue, A. Takeuchi, Acta Mater. 59 (2011) 2243. K. Hashimoto, Appl. Surf. Sci. 257 (2011) 8141. R. Hasegawa, Mater. Sci. Eng. A 375 (2004) 90. M. Hagiwara, A. Inoue, T. Masumoto, Metall. Trans. A 13 (1982) 373. Z. Li, S. Zhou, Y. Wang, R. Xiang, G. Zhang, Mater. Lett. 148 (2015) 99. A. Inoue, Y. Shinohara, J.S. Gook, Mater. Trans. JIM 36 (1995) 427. B. Shen, M. Akiba, A. Inoue, Appl. Phys. Lett. 88 (2006) 131907. J.E. Gao, H.X. Li, Z.B. Jiao, Y. Wu, Y.H. Chen, T. Yu, Z.P. Lu, Appl. Phys. Lett. 99 (2011) 052504. F.J. Liu, K.F. Yao, H.Y. Ding, Intermetallics 19 (2011) 1674. S. Meng, H. Ling, Q. Li, J. Zhang, Scr. Mater. 81 (2014) 24. A. Inoue, B.L. Shen, Mater. Trans. 43 (2002) 2350. A. Takeuchi, A. Inoue, Mater. Trans. 46 (2005) 2817. A.A. Mazilkin, G.E. Abrosimova, S.G. Protasova, B.B. Straumal, G. Schütz, S. V. Dobatkin, A.S. Bakai, J. Mater. Sci. 46 (2011) 4336. B.B. Straumal, A.R. Kilmametov, A.A. Mazilkin, S.G. Protasova, K.I. Kolesnikova, P.B. Straumal, B. Baretzky, Mater. Lett. 145 (2015) 63. A. Inoue, B.L. Shen, A. Yavari, A. Greer, J. Mater. Res. 18 (2003) 1487. J. Wang, R. Li, N. Hua, L. Huang, T. Zhang, Scr. Mater. 65 (2011) 536.
Contents lists available at ScienceDirect
Materials Letters journal homepage: www.elsevier.com/locate/matlet
Fe-B-Si-Zr bulk metallic glasses with ultrahigh compressive strength and excellent soft magnetic properties Jiajia Si a, Jinna Mei b, Rongshan Wang b, Xiaohua Chen a, Xidong Hui a,n a b
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China Suzhou Nuclear Power Research Institute, Suzhou 215004, China
art ic l e i nf o
a b s t r a c t
Article history: Received 30 November 2015 Received in revised form 31 May 2016 Accepted 11 June 2016 Available online 14 June 2016
A series of quaternary Fe-B-Si-Zr bulk metallic glasses (BMGs) with high Fe content were prepared by minor addition of Zr into Fe-Si-B alloy using copper-mold casting method. The proper adjusting in B, Si and Zr contents leads to significant improvement in glass forming ability (GFA). The thermal, mechanical and soft magnetic properties for this kind of BMGs were investigated. The strong interactions among constituent elements render Fe77.7B15.5Si5Zr1.8 BMG ultrahigh compressive strength of 4167 MPa. The BMGs with low Zr content exhibit high saturation magnetization (Ms) of over 1.5 T. Especially, high Ms of 1.60 T and low coercive force (Hc) of 4.3 A/m have been detected in Fe77.5B15.5Si5.5Zr1.5 BMG. & 2016 Elsevier B.V. All rights reserved.
Keywords: Amorphous materials Magnetic materials Thermal properties
1. Introduction Fe-base metallic glasses (MGs) have attracted great attention due to their excellent mechanic properties, soft magnetic properties, corrosion resistance and low cost [1–4]. Owing to the amorphous structure, Fe-based MGs possess high Ms, low Hc and high electrical resistivity, which make them applicable for soft magnetic devices [5]. In the last half century, seeking Fe-based amorphous soft magnetic materials with high Ms, low Hc and high GFA has been a hot topics in the field of amorphous alloys [6,7]. Since the first soft magnetic Fe73Al5Ga2P10C4B4Si2 BMG was developed [8], numerous progresses have been achieved in the Febased BMGs with high Ms. Efforts have been done for Fe-based BMGs to reduce the content of nonferromagnetic metallic elements and to adjust the varieties and contents of metalloid elements to achieve high Ms. Shen et al. [9] developed a Fe79P10C4B4Si3 BMG with the critical diameter (Dc) of 1 mm, and Ms of 1.53 T. Gao et al. [10] developed a Fe75.3C7.0Si3.3B5.0P8.7Cu0.7 BMG with the Dc of 3 mm and Ms of 1.61 T. Liu et al. [11] found that the Ms of Fe81Mo1P7.5C5.5B2Si3 BMG reached up to 1.64 T. Meng et al. [12] synthesized a (Fe90Co10)82P6C7B3Si2 BMG with high Ms of 1.65 T. For the latter two BMGs, purification technique was used to improve the GFA. Based on the previous studies, it seems necessary to adjust the metalloid elements to develop Fe-based BMGs with Ms above 1.6 T. n
Corresponding author. E-mail address: [email protected] (X. Hui).
http://dx.doi.org/10.1016/j.matlet.2016.06.052 0167-577X/& 2016 Elsevier B.V. All rights reserved.
In this paper, we present quaternary Fe-B-Si-Zr BMGs with ultrahigh compressive strength and excellent soft magnetic properties. Ultrahigh compressive strength of 4167 MPa has been detected in Fe77.7B15.5Si5Zr1.8 BMG, and high Ms of 1.60 T and low Hc of 4.3 A/m have been detected in Fe77.5B15.5Si5.5Zr1.5 BMG.
2. Experimental The alloy ingots were prepared by arc melting pure Fe (99.9%), Zr (99.95%), Si (99.9%) and ferroboron alloy (impurities o0.5%) in a Ti-gettered pure argon atmosphere. 1-mm diametric samples were prepared by a copper-mold suction casting method. Amorphous ribbons with 20–30 mm in thickness and 2 mm in width were prepared by single-roller melt spinning. The structures of these specimens were examined by X-ray diffraction (XRD) using Mo Kα radiation. The thermal properties of the as-cast BMGs and ribbons were investigated by differential scanning calorimetry (DSC) at a heating rate of 20 K/min. The hysteresis loops of as-spun ribbons were measured at room temperature with a vibrating sample magnetometer (VSM) under an applied field of 800 kA/m. The densities of the alloys were measured by the Archimedean method. The coercivities were measured with a DC B-H loop tracer under a field of 1 kA/m. Uniaxial compression tests were conducted at ambient temperature using a mechanical testing machine at a strain rate of 1 10 4 s 1. The test samples with an aspect ratio of 2:1 were cut from the as-cast 1-mm diametric rods.
J. Si et al. / Materials Letters 181 (2016) 282–284
283
3. Results and discussion Fig. 1 shows the XRD patterns of Fe-B-Si-Zr rods with 1 mm in diameter. The patterns exhibit similar halo shapes without visible crystal diffraction peaks, indicating that an amorphous structure has formed, respectively. The previous studies [6,13] have shown that Fe75B15Si10 alloy had the highest GFA in Fe-B-Si ternary system, and minor addition of 1 at% Zr into Fe75B15Si10 alloy increased the Dc of (Fe0.75B0.15Si0.1)99Zr1 to 0.75 mm. But the further addition of Zr caused the significant decrease in GFA. This phenomenon was explained by the strong bonding nature between Zr and other elements so that crystal phases were likely to precipitate. In this work, however, Fe-B-Si-Zr MGs with higher GFA and higher Fe content were obtained when 1.3–3 at% Zr was added. The enhancement of GFA in this Fe-Si-B-Zr system should be due to the large atomic radius of Zr and negative heats of mixing for Zr-Fe, Zr-B, and Zr-Si pairs, combining with proper compositional design [13,14]. Actually, amorphous structure can be formed in various methods. It is recently reported that high pressure torsion of crystalline alloys may induce the formation of amorphous state [15,16]. This is probably similar to the effect of mechanical alloying. Severe deformation can bring in numerous lattice defects and cause strong phase refining and transition, which may facilitate the generation of amorphous phases for certain multicomponent alloys. The DSC curves of five Fe-B-Si-Zr BMGs are presented in Fig. 2(a). All these DSC curves exhibit the glass transition and crystallization events, further confirming the glassy structure in these alloys. It is seen that the DSC curves of Fe75B18Si4Zr3, Fe77B15Si5Zr3 and Fe77B16Si4.5Zr2.5 BMGs exhibit clear and similar glass transition and crystallization events, while Fe77B16Si5Zr2 BMG shows unclear supercooled liquid region (SLR). Generally, with the decrease of Zr content in these alloys, the Curie temperature (TC) shows downtrend, and the SLR becomes unapparent. The crystallization events change significantly and multiple crystallization peaks overlap when the Zr content is below 2 at%. It is observed that when Fe is slightly substituted by 0.2 at% Zr in Fe77.2B16Si5Zr1.8 alloy, the thermal properties of Fe77B16Si5Zr2 BMG exhibit obvious changes, indicating that the thermal properties are sensitive to Zr content. Fig. 2(b) and (c) shows the DSC curves of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, Fe77.5B15.5Si5.5Zr1.5 and Fe77B14 Si7.7Zr1.3 amorphous ribbons. It is seen that the SLRs are invisible in the curves, which is the reflection of the reduction in stability of supercooled liquid. Despite the slight compositional variations, the crystallization and melting events of the MGs show significant changes.
Fig. 1. XRD patterns of as-cast Fe-B-Si-Zr rods.
Fig. 2. (a) DSC curves of Fe75B18Si4Zr3, Fe77B15Si5Zr3, Fe77B16Si4.5Zr2.5, Fe77B16Si5Zr2 and Fe77.2B16Si5Zr1.8 BMGs. (b) and (c) DSC curves of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, Fe77.5B15.5Si5.5Zr1.5 and Fe77B14Si7.7Zr1.3 glassy ribbons.
The thermal properties, including Curie temperature TC, glass transition temperature Tg, onset crystallization temperature Tx, melting temperature Tm, liquid temperature Tl and reduced glass transition temperature Tg/Tl (Trg) for the present MGs are listed in Table 1. The values of Tx/Tl are also shown in the table for comparison. It is found that the MGs without clear SLRs show relatively low Tx and Tx/Tl, which reflect the disadvantage in GFA. The compressive stress-strain curve of Fe77.7B15.5Si5Zr1.8 BMG is shown in Fig. 3. No obvious plastic deformation is observed in the curve, and the rod was compressed into fragments after compression. The BMG exhibits elastic strain of about 1.86% and compressive fracture strength of 4167 MPa, which is higher than the fracture strength of all the reported Fe-based BMGs with high Ms. It was reported in previous studies [6,17] that the Fe75B15Si10 amorphous wire exhibited tensile fracture strength of over 3200 MPa, and (Fe0.75B0.15Si0.10)96Nb4 BMG showed compressive fracture strength of 3200–3300 MPa together with small plastic strain. Compared with Nb, Zr has much larger atomic radius and negative heat of mixing with B, Si and Fe, respectively [14]. Hence, the strong atomic interactions in Fe77.7B15.5Si5Zr1.8 render the BMG ultrahigh fracture strength as well as the brittleness. The M-H hysteresis loops of four Fe-B-Si-Zr glassy ribbons are shown in Fig. 4 (in which the inset is part of magnified curves). The Ms of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, and Fe77B14Si7.7Zr1.3 alloys reach 1.56 T, 1.57 T, and 1.54 T, respectively, which are primarily attributed to the high Fe content (about 90 wt% Fe). Especially, Fe77.5B15.5Si5.5Zr1.5 alloy possesses high Ms of 1.60 T, demonstrating that multiple metalloid elements are not indispensable for Febased BMGs with high Ms. For most reported Fe-based BMGs with
284
J. Si et al. / Materials Letters 181 (2016) 282–284
Table 1 Thermal properties of Fe-B-Si-Zr MGs. Alloy
TC (K)
Tg (K)
Tx (K)
ΔTx (K)
Tm (K)
Tl (K)
Tl
Fe75B18Si4Zr3 Fe77B15Si5Zr3 Fe77B16Si4.5Zr2.5 Fe77B16Si5Zr2 Fe77.2B16Si5Zr1.8 Fe77.7B15.5Si5Zr1.8 Fe77B16Si5.5Zr1.5 Fe77.5B15.5Si5.5Zr1.5 Fe77B14Si7.7Zr1.3
582 581 611 619 620 628 646 636 653
810 802 810 796 813 – – – –
848 841 846 834 845 815 821 827 831
38 39 36 38 32 – – – –
1420 1404 1415 1401 1406 1418 1408 1406 1403
1471 1474 1470 1467 1472 1456 1494 1485 1460
51 70 55 66 66 38 86 79 57
Tm (K)
Trg
Tx/Tl
0.551 0.544 0.551 0.543 0.552 – – – –
0.576 0.571 0.576 0.569 0.574 0.560 0.550 0.557 0.569
Ms above 1.5 T, the addition of P element is needed to ensure the GFA. However, compared with B or Si, P in Fe-based MGs often plays a more disadvantageous role in Ms [18]. Thus the Fe77.5B15.5Si5.5Zr1.5 BMG exhibits high Ms. The Hc of as-spun glassy ribbons of Fe77.7B15.5Si5Zr1.8, Fe77B16Si5.5Zr1.5, Fe77.5B15.5Si5.5Zr1.5 and Fe77B14Si7.7Zr1.3 have been measured to be 15.7, 16.1, 4.3 and 14.5 A/m, respectively. Note that the Hc can be significantly affected by the sample quality, such as internal stress and structural defects despite the slight compositional variations. In this work, Fe77.5B15.5Si5.5Zr1.5 glassy ribbon still exhibits low Hc of 4.3 A/m although no relaxation treatment has been conducted.
4. Conclusions
Fig. 3. Compressive stress-strain curve of Fe77.7B15.5Si5Zr1.8 BMG.
In this work, a series of Fe-B-Si-Zr BMGs with high Fe content were synthesized. The variations in Zr content significantly affect the thermal properties. The addition of active Zr renders Fe77.7B15.5Si5Zr1.8 BMG ultrahigh compressive fracture strength of 4167 MPa. Moreover, high Ms above 1.5 T have been detected in the low Zr-containing BMGs. Especially, Fe77.5B15.5Si5.5Zr1.5 alloy exhibits high Ms of 1.60 T and low Hc of 4.3 A/m. Therefore, these Fe-B-Si-Zr BMGs are promising to be used as magnetic materials.
Acknowledgments The authors are grateful for the financial support of National Natural Science Foundation of China (Nos. 51271018, 51571016 and 5153100), and the proprietary program of the State Key Laboratory for Advanced Metals and Materials (2014-ZD04).
References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] Fig. 4. M-H hysteresis loops of Fe77.5B15.5Si5.5Zr1.5, Fe77B16Si5.5Zr1.5, Fe77.7B15.5Si5Zr1.8, and Fe77B14Si7.7Zr1.3 glassy ribbons. The inset exhibits part of magnified curves.
[17] [18]
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