Structure and Magnetic Properties of Bulk Synthesized Mn2−xFexP1−ySiy Compounds from Magnetization, 57Fe Mössbauer Spectroscopy, and Electronic Structure Calculations
Abstract
:1. Introduction
- -
- A local structure distortion index which can affect the tetrahedral site in which the sensitive Fe-metal (weak-ferro versus strong-ferro character), possibly linking the magnetic correlations with magnetoelastic couplings;
- -
- Optimized route to process intermetallic materials, comprising amounts of phosphorous, easily and safely, to deliver bulk samples with high magnetocaloric performances;
- -
- Better understanding the magnetic properties from correlated Mössbauer spectroscopy and electronic structure calculations.
2. Materials and Methods: On Synthesis Routes
3. Results
3.1. Structure Analysis
3.1.1. Structure Characterization at Room Temperature
3.1.2. Structure Characterization versus Temperature
3.1.3. Local Structure Distortion Index and Magnetic Polarization
3.2. Magnetization Properties and MCE Characteristics of Bulk Synthesized Mn2−xFexP1−ySiy Compounds
3.2.1. Tc Determination and Isothermal Magnetization Measurements
3.2.2. MCE Characterizations
3.3. 57Fe Mössbauer Spectroscopy Analysis
3.3.1. Results
3.3.2. Data Analysis
3.4. Electronic Structure Analysis
3.4.1. Computational Details
3.4.2. Site Preference
- (i)
- 0.9 Fe and 0.1 Mn on 3f, 0.5 Fe and 0.5 Mn on 3g;
- (ii)
- 1.0 Fe on 3f, 0.4 Fe and 0.6 Mn on 3g;
- (iii)
- fully random distribution of TM elements, i.e., 0.5 Fe and 0.5 Mn on 3f and 3g sites.
- (i)
- 0.75 P and 0.25 Si on 2c, 1.0 Si on 1b;
- (ii)
- 0.25 P and 0.75 Si on 2c, 1.0 P on 1b;
- (iii)
- fully random distribution of both metalloids, i.e., 0.5 P and 0.5 Si on 2c and 1b sites.
3.4.3. Magnetic Properties of Mn2−xFexP1−ySiy
4. Conclusions and Perspectives
Author Contributions
Funding
Conflicts of Interest
Appendix A
Interatomic Distances at 290 K [Å] | ||
---|---|---|
MnFeP0.5Si0.5 | Mn0.6Fe1.4P0.6Si0.4 | |
Mn-Mn | 3.267 x4 | 3.233 x4 |
Mn-Fe | 2.716 x2 2.740 x4 | 2.619 x2 2.737 x2 |
Mn-P,Si Mn-P | 2.509 x4 2.499 x1 | 2.503 x4 2.461 x1 |
Fe-P,Si Fe-P | 2.371 x2 2.267 x2 | 2.268 x2 2.339 x2 |
Fe-Fe | 2.673 x2 | 2.642 x2 |
300 K (F) | 465 K (P) | |
---|---|---|
Mn-Mn | 3.262 x4 | 3.203 x4 |
Mn-Fe | 2.691 x2 2.758 x4 | 2.689 x2 2.763 x4 |
Mn-P | 2.505 x2 2.505 x2 2.528 x1 | 2.533 x2 2.534 x2 2.455 x1 |
Fe-P | 2.371 x2 2.267 x2 | 2.291 x2 2.335 x2 |
Fe-Fe | 2.689 x2 | 2.712 x2 |
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Sites | Sample I | x | y | z | Sample II | x | y | z |
---|---|---|---|---|---|---|---|---|
3g | 100% Mn | 0.5967(1) | 0.0 | 0.5 | 56% Mn + 44% Fe | 0.598(8) | 0.0 | 0.5 |
3f | 100% Fe | 0.2491(2) | 0.0 | 0.0 | 100% Fe | 0.268(6) | 0.0 | 0.0 |
2c | P,Si | 0.33333 | 0.66666 | 0.0 | 100% P | 0.33333 | 0.66666 | 0.0 |
1b | P,Si | 0.0 | 0.0 | 0.5 | 33.3% P + 66.6% Si | 0.0 | 0.0 | 0.5 |
Compounds | % Fe2P-Type (P-62m) | % Mn5Si3-Type (P63/mcm) | Cell Parameters (Å) |
---|---|---|---|
Mn1.40Fe0.60P0.30Si0.70 | 91 | 9 | a = 6.139, c = 3.425 |
Mn1.30Fe0.70P0.35Si0.65 | 96 | 4 | a = 6.053, c = 3.355 |
MnFeP0.50Si0.50 | 96 | ~4% MnFe2Si | a = 6.196, c = 3.309 |
Mn0.70Fe1.30P0.65Si0.35 | 99 | <1 | a = 6.101, c = 3.347 |
Mn0.60Fe1.40P0.60Si0.40 | 99 | <1 | a = 6.123, b = 3.334 |
Compound | Fe/Mn | Si/P | Transition Order | TC (K) | MS (µB) | ∆T hys (K) | −∆Smmax (J/kg K) 2 T–5 T | ∆Tad (K) 2 T–5 T |
---|---|---|---|---|---|---|---|---|
Mn1.40Fe0.60P0.30Si0.70 | 2.333 | 2.333 | F→P 1–2nd (?) | 260 | 4.17 | 0 | 4.63–8.3 | - |
Mn1.30Fe0.70P0.35Si0.65 | 1.858 | 1.858 | MET 1st | 282 | >2.87 | 0 | 11–15.5 | 3.6–6.8 |
MnFeP0.50Si0.50 * | 1.0 | 1.0 | MET 1st | 365 | 3.95 | 18 | 15–30 | 7.6–20 |
MnFeP0.50Si0.50 ** | 1.0 | 1.0 | MET 1st | 382 | 3.77 | 18 | 24–58 | 8–16.1 |
Mn0.70Fe1.30P0.65Si0.35 | 0.538 | 0.538 | MET 1st | 318 | >3.25 | 10 | 18.4–38 | 7.8–16.4 |
Mn0.60Fe1.40P0.60Si0.4 | 0.428 | 0.666 | F→P 1–2nd (?) | 394 | 4.05 | 6 | 4.1–8.5 | 1.1–2.5 |
T | <B> | σ | IS | QS | P | <B> | σ | IS | QS | P | <B> | σ | IS | QS | P |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
310 | 0 0 0 | 0 0 0 | 0.23 0.20 0.17 | 0.41 0.59 0 | 49 11 40 | 21.6 0 19.5 | 2.3 0 2.8 | 0.28 0.19 0.32 | −0.22 0 −0.13 | 49 11 40 | 16.2 13.9 0 | 3.3 3.6 0 | 0.29 0.36 0.28 | 0.25 0.23 0.30 | 64 18 18 |
250 | 15.6 0 0 | 4.0 0 0 | 0.29 0.24 0.17 | −0.18 0.58 0 | 50 10 40 | 22.6 0 20.8 | 2.4 0 2.6 | 0.31 0.23 0.37 | −0.22 0 −0.12 | 50 10 40 | 19.3 16.1 0 | 3.0 3.6 0 | 0.37 0.44 0.30 | 0.06 0.1 0.29 | 72 21 7 |
200 | 19.1 0 0 | 3.3 0 0 | 0.33 0.29 0.19 | −0.19 0.59 0 | 40 7 53 | 23.3 0 21.5 | 2.1 0 2.5 | 0.34 0.23 0.39 | −0.23 0 −0.14 | 40 7 53 | 20.3 18.7 | 2.9 2.7 | 0.40 0.47 | 0.15 0.10 | 77 23 |
150 | 20.6 0 0 | 3.0 0 0 | 0.36 0.29 0.19 | −0.19 0.59 0 | 43 10 47 | 23.8 0 21.9 | 2.1 0 2.5 | 0.37 0.29 0.42 | −0.23 0 −0.14 | 43 10 47 | 19.9 18.6 | 2.8 2.5 | 0.41 0.48 | 0.14 0.07 | 77 23 |
84 | 21.6 9.5 1.9 | 2.7 3.2 2.5 | 0.40 0.31 0.21 | −0.21 0.25 0.07 | 45 55 | 24.2 22.4 | 2.0 2.6 | 0.39 0.44 | −0.24 −0.14 | 45 55 | 21.3 19.5 | 2.9 2.6 | 0.45 0.52 | −0.15 0.07 | 77 23 |
Compound | VEC | Total (cal.) | Mn3f | Fe3f | Mn3g | Fe3g | Magn. (exp.) |
---|---|---|---|---|---|---|---|
Mn1.4Fe0.6P0.3Si0.7 | 19.0 | 4.25 | 1.76 | 1.48 | 2.82 | - | 4.17 |
Mn1.3Fe0.7P0.35Si0.65 | 19.05 | 3.98 | 1.48 | 1.40 | 2.69 | - | >2.85 * |
MnFeP0.5Si0.5 | 19.5 | 4.30 | - | 1.49 | 2.97 | - | 3.77–3.95 |
Mn0.7Fe1.3P0.65Si0.35 | 19.95 | 4.04 | - | 1.41 | 2.92 | 2.44 | >3.25 * |
Mn0.6Fe1.4P0.6Si0.4 | 20.0 | 3.99 | - | 1.43 | 2.91 | 2.42 | 4.05 |
Compound | VEC | Total (cal.) | Mn3f | Fe3f | Mn3g | Fe3g | Magn. (exp.) |
---|---|---|---|---|---|---|---|
MnFeAs (HP) [10] | - | >4.23 ** | - | 1.10 | 3.13 | - | 4.50 |
MnFeP0.5As0.5 | - | >3.80 ** | - | 1.20 | 2.60 | - | 4.13 |
MnFeP0.7As0.3 [14] | - | >4.27 ** | - | 1.25 | 3.02 | - | 4.10 |
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Fruchart, D.; Haj-Khlifa, S.; de Rango, P.; Balli, M.; Zach, R.; Chajec, W.; Fornal, P.; Stanek, J.; Kaprzyk, S.; Tobola, J. Structure and Magnetic Properties of Bulk Synthesized Mn2−xFexP1−ySiy Compounds from Magnetization, 57Fe Mössbauer Spectroscopy, and Electronic Structure Calculations. Crystals 2019, 9, 37. https://doi.org/10.3390/cryst9010037
Fruchart D, Haj-Khlifa S, de Rango P, Balli M, Zach R, Chajec W, Fornal P, Stanek J, Kaprzyk S, Tobola J. Structure and Magnetic Properties of Bulk Synthesized Mn2−xFexP1−ySiy Compounds from Magnetization, 57Fe Mössbauer Spectroscopy, and Electronic Structure Calculations. Crystals. 2019; 9(1):37. https://doi.org/10.3390/cryst9010037
Chicago/Turabian StyleFruchart, Daniel, Sonia Haj-Khlifa, Patricia de Rango, Mohamed Balli, Ryszard Zach, Wieslaw Chajec, Piotr Fornal, Jan Stanek, Stanislaw Kaprzyk, and Janusz Tobola. 2019. "Structure and Magnetic Properties of Bulk Synthesized Mn2−xFexP1−ySiy Compounds from Magnetization, 57Fe Mössbauer Spectroscopy, and Electronic Structure Calculations" Crystals 9, no. 1: 37. https://doi.org/10.3390/cryst9010037