无机材料学报 ›› 2021, Vol. 36 ›› Issue (12): 1247-1255.DOI: 10.15541/jim20210126 CSTR: 32189.14.10.15541/jim20210126
所属专题: MXene材料专辑(2020~2021)
张霄1,2,3(), 李友兵2,3, 陈科2,3, 丁浩明2,3, 陈露2,3, 李勉2,3, 史蓉蓉1(), 柴之芳2,3, 黄庆2,3()
收稿日期:
2021-03-03
修回日期:
2021-03-24
出版日期:
2021-12-20
网络出版日期:
2021-06-01
通讯作者:
史蓉蓉, 副教授. E-mail: shirr@lzu.edu.cn;黄 庆, 研究员. E-mail: huangqing@nimte.ac.cn
作者简介:
张 霄(1996-), 男, 硕士研究生. E-mail: zhangxiao18@lzu.edu.cn
基金资助:
ZHANG Xiao1,2,3(), LI Youbing2,3, CHEN Ke2,3, DING Haoming2,3, CHEN Lu2,3, LI Mian2,3, SHI Rongrong1(), CHAI Zhifang2,3, HUANG Qing2,3()
Received:
2021-03-03
Revised:
2021-03-24
Published:
2021-12-20
Online:
2021-06-01
Contact:
SHI Rongrong, associate professor. E-mail: shirr@lzu.edu.cn;HUANG Qing, professor. E-mail: huangqing@nimte.ac.cn
About author:
ZHANG Xiao(1996-), male, Master candidate. E-mail: zhangxiao18@lzu.edu.cn
Supported by:
摘要:
三元层状化合物MAX相兼具金属与陶瓷优良的力学性质, 通常被认为是一类高安全结构材料。有研究显示, 通过熔盐法可以将副族元素插入到MAX相A位层间, 获得具有铁磁性能的V2(Sn, A)C (A =Fe、Co、Ni和Mn)材料。因而, 如何构建新的MAX相结构并对实现其磁性调控备受关注。本研究通过MAX相M位和A位双固溶的方式设计了四种新型MAX相(V, Nb)2(Sn, A)C (A =Fe、Co、Ni和Mn)。XRD、SEM、EDS结合TEM分析证实了上述新相的合成。超导量子磁强计(Superconducting quantum interference device magnetometer, SQUID)测试磁学性能发现, M位固溶后的MAX相的居里温度与其四方率(c/a)、元素组成有关。(V, Nb)2(Sn, Fe)C、(V, Nb)2(Sn, Ni)C、(V, Nb)2(Sn, Mn)C相较于M位固溶Nb元素之前的V2(Sn, A)C相, 其矫顽力Hc和剩余磁化强度Mr减小, 饱和磁化强度Ms增大。而V2(Sn, Co)C在M位固溶Nb元素之后磁性变化均与前述MAX相相反。通过以上结果, 揭示了M/A位双固溶对MAX相磁性的影响规律, 为调控MAX相磁性提供了新的思路。
中图分类号:
张霄, 李友兵, 陈科, 丁浩明, 陈露, 李勉, 史蓉蓉, 柴之芳, 黄庆. M位与A位双固溶MAX相的磁学性能研究[J]. 无机材料学报, 2021, 36(12): 1247-1255.
ZHANG Xiao, LI Youbing, CHEN Ke, DING Haoming, CHEN Lu, LI Mian, SHI Rongrong, CHAI Zhifang, HUANG Qing. Tailoring MAX Phase Magnetic Property Based on M-site and A-site Double Solid Solution[J]. Journal of Inorganic Materials, 2021, 36(12): 1247-1255.
图1 酸处理后的(V, Nb)2(Sn, Fe)C表征结果
Fig. 1 Characterization results of (V, Nb)2(Sn, Fe)C after acid treatment (a) XRD pattern; (b) SEM image; (c) Corresponding energy-dispersive spectroscopy analysis; (d) Elemental mapping scanning on one particle; (e) Selected area electron diffraction pattern, showing the electron beam being paralleled to the [1$\bar{1}$00] direction; (f) HR-TEM image
图2 (a) (V, Nb)2(Sn, Co)C、(c) (V, Nb)2(Sn, Ni)C和(e) (V, Nb)2(Sn, Mn)C酸处理后的XRD谱图;(b) (V, Nb)2(Sn, Co)C、(d) (V, Nb)2(Sn, Ni)C、(f) (V, Nb)2(Sn, Mn)C元素分布图
Fig. 2 XRD patterns of (a) (V, Nb)2(Sn, Co)C, (c) (V, Nb)2(Sn, Ni)C, and (e) (V, Nb)2(Sn, Mn)C after acid treatment; SEM-EDS elemental mappings of (b) (V, Nb)2(Sn, Co)C, (d) (V, Nb)2(Sn, Ni)C, and (f) (V, Nb)2(Sn, Mn)C after acid treatment
MAX phase | Lattice parameter | Element percentage/% | Nb element in M site/% | Magnetic element in A site/% | |||||
---|---|---|---|---|---|---|---|---|---|
a/nm | c/nm | c/a | V | Nb | Sn | A | |||
V2(Sn, Fe)C[ | 0.2984 | 1.3345 | 4.4718 | 66.84 | - | 22.05 | 11.11 | - | 33.50 |
(V, Nb)2(Sn, Fe)C | 0.3014 | 1.3447 | 4.4622 | 54.32 | 13.38 | 25.03 | 7.27 | 19.76 | 22.51 |
V2(Sn, Co)C[ | 0.2989 | 1.3409 | 4.4864 | 66.36 | - | 22.44 | 11.19 | - | 33.28 |
(V, Nb)2(Sn, Co)C | 0.3016 | 1.3419 | 4.4493 | 56.41 | 11.23 | 24.60 | 7.76 | 16.60 | 23.98 |
V2(Sn, Ni)C[ | 0.2985 | 1.3357 | 4.4751 | 67.47 | - | 24.36 | 8.16 | - | 25.10 |
(V, Nb)2(Sn, Ni)C | 0.3021 | 1.3413 | 4.4402 | 56.87 | 13.00 | 21.66 | 8.47 | 18.61 | 28.10 |
V2(Sn, Mn)C[ | 0.2982 | 1.3403 | 4.4941 | 66.19 | - | 23.07 | 10.74 | - | 31.76 |
(V, Nb)2(Sn, Mn)C | 0.3026 | 1.3509 | 4.4646 | 57.10 | 10.84 | 23.50 | 8.56 | 15.96 | 26.70 |
表1 晶格参数和MAX相中元素的原子百分比
Table 1 Lattice parameters and atomic percentage of element in MAX phases
MAX phase | Lattice parameter | Element percentage/% | Nb element in M site/% | Magnetic element in A site/% | |||||
---|---|---|---|---|---|---|---|---|---|
a/nm | c/nm | c/a | V | Nb | Sn | A | |||
V2(Sn, Fe)C[ | 0.2984 | 1.3345 | 4.4718 | 66.84 | - | 22.05 | 11.11 | - | 33.50 |
(V, Nb)2(Sn, Fe)C | 0.3014 | 1.3447 | 4.4622 | 54.32 | 13.38 | 25.03 | 7.27 | 19.76 | 22.51 |
V2(Sn, Co)C[ | 0.2989 | 1.3409 | 4.4864 | 66.36 | - | 22.44 | 11.19 | - | 33.28 |
(V, Nb)2(Sn, Co)C | 0.3016 | 1.3419 | 4.4493 | 56.41 | 11.23 | 24.60 | 7.76 | 16.60 | 23.98 |
V2(Sn, Ni)C[ | 0.2985 | 1.3357 | 4.4751 | 67.47 | - | 24.36 | 8.16 | - | 25.10 |
(V, Nb)2(Sn, Ni)C | 0.3021 | 1.3413 | 4.4402 | 56.87 | 13.00 | 21.66 | 8.47 | 18.61 | 28.10 |
V2(Sn, Mn)C[ | 0.2982 | 1.3403 | 4.4941 | 66.19 | - | 23.07 | 10.74 | - | 31.76 |
(V, Nb)2(Sn, Mn)C | 0.3026 | 1.3509 | 4.4646 | 57.10 | 10.84 | 23.50 | 8.56 | 15.96 | 26.70 |
图3 在0.1 T下, V2(Sn, A)C和(V, Nb)2(Sn, A)C (A = Fe, Co, Ni和Mn)在2~100 K范围内随温度变化的磁化M-T曲线
Fig. 3 Temperature dependent magnetization M-T curves for (a) V2(Sn, A)C and (b) V2(Sn, A)C (A = Fe, Co, Ni and Mn) at 0.1 T in the range of 2-100 K
图4 V2(Sn, A)C和(V, Nb)2(Sn, A)C(A=Fe、Co、Ni和Mn)在-1~1 T范围内的磁滞回线
Fig. 4 Magnetic hysteresis loops of V2(Sn, A)C and V2(Sn, A)C (A=Fe, Co, Ni and Mn) at different temperatures in the range from -1 to 1 T, respectively Colourful figures are available on website
MAX phase | TC | 2 K | 20 K | 40 K | ||||||
---|---|---|---|---|---|---|---|---|---|---|
Hc | Mr | Ms | Hc | Mr | Ms | Hc | Mr | Ms | ||
V2(Sn, Fe)C | 63 | 458 | 0.59 | 1.73 | 305 | 0.42 | 1.53 | 152 | 0.18 | 1.08 |
(V, Nb)2(Sn, Fe)C | 63 | 238 | 0.48 | 1.79 | 174 | 0.37 | 1.67 | 73 | 0.14 | 1.24 |
V2(Sn, Co)C | 66 | 314 | 0.34 | 1.19 | 224 | 0.26 | 1.05 | 113 | 0.12 | 0.79 |
(V, Nb)2(Sn, Co)C | 53 | 378 | 0.49 | 1.11 | 240 | 0.33 | 1.00 | 134 | 0.17 | 0.71 |
V2(Sn, Ni)C | 60 | 276 | 0.30 | 1.54 | 191 | 0.23 | 1.42 | 94 | 0.10 | 1.12 |
(V, Nb)2(Sn, Ni)C | 53 | 140 | 0.29 | 2.07 | 96 | 0.19 | 1.83 | 45 | 0.07 | 1.34 |
V2(Sn, Mn)C | 56 | 780 | 0.26 | 0.98 | 545 | 0.21 | 0.84 | 206 | 0.07 | 0.63 |
(V, Nb)2(Sn, Mn)C | 57 | 117 | 0.06 | 0.97 | 75 | 0.04 | 0.90 | 32 | 0.01 | 0.67 |
表2 V2(Sn, A)C与(V, Nb)2(Sn, A)C(A = Fe、Co、Ni和Mn)的磁性参数
Table 2 Magnetic parameters of V2(Sn, A)C and (V, Nb)2(Sn, A)C (A = Fe, Co, Ni and Mn)
MAX phase | TC | 2 K | 20 K | 40 K | ||||||
---|---|---|---|---|---|---|---|---|---|---|
Hc | Mr | Ms | Hc | Mr | Ms | Hc | Mr | Ms | ||
V2(Sn, Fe)C | 63 | 458 | 0.59 | 1.73 | 305 | 0.42 | 1.53 | 152 | 0.18 | 1.08 |
(V, Nb)2(Sn, Fe)C | 63 | 238 | 0.48 | 1.79 | 174 | 0.37 | 1.67 | 73 | 0.14 | 1.24 |
V2(Sn, Co)C | 66 | 314 | 0.34 | 1.19 | 224 | 0.26 | 1.05 | 113 | 0.12 | 0.79 |
(V, Nb)2(Sn, Co)C | 53 | 378 | 0.49 | 1.11 | 240 | 0.33 | 1.00 | 134 | 0.17 | 0.71 |
V2(Sn, Ni)C | 60 | 276 | 0.30 | 1.54 | 191 | 0.23 | 1.42 | 94 | 0.10 | 1.12 |
(V, Nb)2(Sn, Ni)C | 53 | 140 | 0.29 | 2.07 | 96 | 0.19 | 1.83 | 45 | 0.07 | 1.34 |
V2(Sn, Mn)C | 56 | 780 | 0.26 | 0.98 | 545 | 0.21 | 0.84 | 206 | 0.07 | 0.63 |
(V, Nb)2(Sn, Mn)C | 57 | 117 | 0.06 | 0.97 | 75 | 0.04 | 0.90 | 32 | 0.01 | 0.67 |
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