The Influence of Vanadium on Magnetism and Magnetocaloric Properties of Fe 8 0 − x V x B12Si8 (x = 8, 10, and 13.7) Amorphous Alloys A. Boutahar, A. Ettayfi, G. Alouhmy, H. Lassri, E. K. Hlil & D. Fruchart
Journal of Superconductivity and Novel Magnetism Incorporating Novel Magnetism ISSN 1557-1939 J Supercond Nov Magn DOI 10.1007/s10948-014-2619-8
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Author's personal copy J Supercond Nov Magn DOI 10.1007/s10948-014-2619-8
REVIEW PAPER
The Influence of Vanadium on Magnetism and Magnetocaloric Properties of Fe80−xVx B12Si8 (x = 8, 10, and 13.7) Amorphous Alloys A. Boutahar · A. Ettayfi · G. Alouhmy · H. Lassri · E. K. Hlil · D. Fruchart
Received: 19 May 2014 / Accepted: 30 June 2014 © Springer Science+Business Media New York 2014
Abstract Amorphous soft magnetic Fe80−x Vx B12 Si8 ribbons (0 ≤ x ≤ 14) have been fabricated by melt spinning technique, and their magnetic and magnetocaloric properties have been studied. The value of magnetocaloric effect has been determined from the measurements of magnetization as a function of temperature and an external magnetic field. The addition of vanadium to the ternary Fe80 B12 Si8 alloy results in a decrease of the Curie temperature of amorphous alloys, TC , from 473.5 to 335 K. With an increasing V content, the average magnetic moment of Fe atom and the magnetic entropy change also decrease. Fe66.3 V13.7 B12 Si8 alloy exhibits the highest refrigeration capacity of 93.7 J kg−1 and moderate peak magnetic entropy of 1.034 J kg−1 K−1 (TC = 335 K) under the maximum applied field of 2 T. The results from this work showed that V containing amorphous alloy 13.7 at. % is an interesting material and potential candidate for magnetic refrigerants working near room temperature. The observed −SM max values compare favorably with other amorphous Fe-based alloys. Keywords Amorphous alloys · Magnetization · Magnetocaloric effect
A. Boutahar () · A. Ettayfi · G. Alouhmy · H. Lassri LPMMAT, Facult´e des Sciences Ain Chock, Universit´e Hassan IICasablanca, BP 5366, Mˆaarif, Casablanca, Morocco e-mail:
[email protected] E. K. Hlil · D. Fruchart Institut N´eel, CNRS et Universit´e Joseph Fourier, BP 166, 38042 Grenoble CEDEX 9, France
1 Introduction Amorphous alloys of the transition metal-metalloid type have been the subject of intense research in various laboratories [1–3]. In particular, Fe-based alloys produced by melt spinning techniques hold promise for several applications such as magnetic shields, power and electronic transformers, and recording heads. Many efforts have been made to study the influence of the transition metal (M = Mn, Cr, V, Ti, Mo. . . ) substitution in Fe-based amorphous alloys [4–6]. Because of intrinsic disorder structure, Fe-based amorphous alloys show excellent soft magnetic properties (nearly zero magnetic hysteresis), high electrical resistivity, good corrosion resistance, and good mechanical properties (high strength and large elastic limit) [7–10]. Room-temperature (RT) magnetic refrigeration [11] based on the magnetocaloric effect (MCE) is currently attracting increasing interest because it offers an energyefficient and environment-friendly alternative to the usual vapor cycle refrigeration technology. In order to probe the magnetic refrigeration effectiveness, isothermal entropy alone is, however, not sufficient. The relative cooling power (RCP) is indeed considered to be the most important factor for assessing the usefulness of a magnetic refrigerant material [12, 13]. Recently, several promising materials with a firstorder magnetic transition (FOMT), like Gd5 (Si,Ge)4 [14], La(Fe,Si)13 [15], FeMnPAs [16], Ni2 (Mn,Ga) [17], and others [18], have attracted much attention as magnetic refrigeration because of their giant magnetic entropy change due to the rapid change of the magnetization in the fieldinduced magnetic phase transition accompanied by structural or volume transition. But these structural changes also present some drawbacks; they have very large thermal and
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2 Experimental Methods Amorphous Fe80−x Vx B12 Si8 ribbons with 0 ≤ x ≤ 14, all expressed in at wt %, were made by melt spinning in an inert atmosphere of Ar. The starting materials were of puritybetter than 4 N. The ribbon samples were about 30-μm thick with different widths varying from about 2 to 4 mm. X-ray diffraction (XRD) was used to verify the amorphous structure. The exact chemical composition of the samples was determined by electron probe microanalysis. The magnetization was studied from 4.2 to 700 K, in applied fields up to 5 T. The Curie temperature TC was determined from the evolution of the magnetization, in a weak field, versus temperature.
3 Results and Discussions The temperature (T ) dependence of the magnetization (M) for Fe80−x Vx B12 Si8 ribbons with 0 ≤ x ≤ 14 (Fig. 1) reveals the presence of a ferromagnetic (FM) to paramagnetic (PM) transition at TC , defined as the inflection point of dM/dT (T) curve inset Fig. 1). The Curie temperature TC of amorphous Fe80−x Vx B12 Si8 alloys as a function of V concentration is
dM/dT (T)
M (T)
x=8 x=10 x=13.7
x=8 x=10 x=13.7
-1
70 -2
0 200
400
600
dM/dT (emu/g K)
0 140
M (emu/g)
magnetic field hysteresis, which can be reduced by substituting alternative elements, but only at the expense of a low SM [19]. Furthermore because of the structural transition, large volume changes and stresses between the coexisting phases appear, which make the sample very brittle [20]. The operating temperature range also tends to be very narrow and some of the proposed materials contain toxic elements. Materials with a second-order magnetic transition (SOMT) lack the very large (−SM max ), but they do have a very refrigeration capacity (RC), which is now recognized as the key parameter, because it is a better way by which to compare different magnetocaloric materials. The other positive characteristics of SOMT materials are low magnetic hysteresis, high electrical resistivity, enhanced corrosion resistance, good mechanical properties, and TC tunable by varying the composition [21, 22]. Fe-based amorphous magnetocalorics also have the advantage of generally being very cheap and easy to produce. In order to study the influence of the addition of V on the various magnetic and magnetocaloric properties of amorphous Fe-B-Si alloys such as the magnetic moment of Fe, Curie temperature, and magnetic entropy change SM , we have prepared amorphous Fe80−x Vx B12 Si8 alloys with 0 ≤ x ≤ 14. Their magnetic and magnetocaloric properties have been investigated by magnetization measurements were realized in Louis N´eel Laboratory of Grenoble
-3 800
T (K) Fig. 1 Temperature dependence of magnetization of Fe68 V12 Si8 B12 (x = 8 and x = 10) alloys measured in a field of 0.5 T
shown in Table 1. As seen from Table 1, TC decreases with increasing solute content. The decrease in TC is due to the decrease in the Fe content which also leads to a decrease in the coordination number ZFe−Fe [23]. Similar results also have been found in other Fe-B-based amorphous alloys systems [24–26]. It can be seen that the addition of 13.7 % vanadium to the ternary Fe80 B12 Si8 alloy results in a decrease of the Curie temperature TC of amorphous sample from 473.5 to 335 K, which is desirable for potential magnetic refrigeration applications near room temperature. The magnetic moments of (μFe ) as a function of V content are shown in Table 1. μFe decreases with the solute element concentration as it has already been found for T-MB-Si alloys where T = Fe, Co, and Ni and M = Cr, Mn, and V [1, 27, 28]. The decrease of the magnetic moment is essentially attributed to hybridization effects and the charge transfer phenomenon arising from B and Si, as suggested by Hassanain et al. [29] and H. Lassri et al. [23]. Figure 2 shows the magnetic applied field μ0 H dependence on the magnetization (M) measured at different temperatures (T) close to TC for Fe80−x Vx B12 Si8 alloys with x = 8, 10, and 13.7 which relates to the change from ferromagnetic (FM) to paramagnetic (PM) state above TC . On the other hand, the magnetic phase transition of Table 1 Summary of the iron magnetic moment at 300 K, the Curie temperature −Smax , and the RCP values for amorphous (x = 8, x = 10, and x = 13.7) alloys for an applied magnetic field of 2 T x
μFe (μB )
TC (K)
SM max (J kg−1 K−1 )
RCP (J kg−1 )
8 10 13.7
1.28 1.125 0.71
473.5 435.5 335
1.467 1.165 1.034
132.7 113.5 93.7
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90
x=8 x=10 x=13.7
x=8
60
M (emu/g)
M² (emu²/g²)
3000
30
0
0
2
4
Tc=473.5 K Tc=435.5 K Tc=335 K
2000
1000
6
0,05
µ 0 H (T)
0,10
µ 0 H/M (T g/emu)
356 362 368 374 383 386 389 392 395 398 401 404 407 410 413 419 422 425 428 431 434 437 440 443 446 449 452 458 467 470 473 476 479 482 485 488 491
90
M (emu/g)
60
(M2 versus μ0 H/M) above TC display an almost linear relation, which is typical for a second-order magnetic transition from ferromagnetic to paramagnetic state for all series. Based on the thermodynamically theory, the isothermal magnetic entropy change SM associated with a magnetic field variation is given by the following:
x=10
30
0
0
2
4
Fig. 3 Arrott plots close to the Curie temperature for Fe68 V12 Si8 B12 (x = 8, x = 10 and x = 13.7) alloys
HF
6
µ0H (T)
SM (T , H ) = 0
∂M ∂T
(1)
dH. H
M (emu/g)
220 230 240 250 260 265 270 275 280 285 290 295 300 302 304 306 308 310 312 314 316 318 320 322 324 326 328 330 332 334 336 338 340 342 344 346 348 350 355 360 365 370 375 380
90
60
In practice, an alternative formula is usually used for numerical calculation: SM (T , H ) = μ0
x=13.7
30
0
0
2
4
6
µ0H (T) Fig. 2 Isothermal magnetization curves measured at different temperatures around Curie temperature for Fe80−x Vx B12 Si8 alloys with x = 8, 10 and 13.7
Fe80−x Vx B12 Si8 alloys with x = 8, 10, and 13.7 is of the second order; this result is confirmed by the Arrott plots given in Fig. 3 around Curie temperature. The Arrott plots
Mi+1 − Mi Ti+1 − Ti
Hi .
(2)
Where μ0 is the vacuum permeability Mi and Mi+1 are the magnetization values measured at temperatures Ti and Ti+1 in a field change Hi [30]. The accuracy of the calculated SM depends on the accuracy of the measurements of magnetic moment, temperature, and magnetic field. Nevertheless, the Maxwell relation (1) must be used carefully since the adjacent isotherms reflect the temperature dependence of the isofield magnetization [31]. Figure 4 shows the temperature dependence of the magnetic entropy change measured for an applied magnetic field of –2 T for Fe80−x Vx B12 Si8 (x = 8, 10 and 13.7) alloys. From Table 1, one can find that the maximum peak value of (− SM ) decreases from 1.467 to 1.034 J kg−1 K−1 along with V content increasing from x = 8 to 13.7. This decrease of −SM max versus the V content has also been observed in FeBbased amorphous alloys doped with nonmagnetic atoms (Nb, Y), prepared by melt spinning [32].
Author's personal copy J Supercond Nov Magn Fig. 4 Magnetic entropy change for Fe80−x Vx B12 Si8 (8 ≤ x ≤ 14) versus temperature for a field change of μ 0 H = 2 T
1,5
x=8 x=10 x=13.7
- Δ S (J/Kg K)
µ0H=2 T 1,0
0,5
200
300
400
500
T (K) [39, 40], are presented in Table 2. Combined with the merit of remarkably low cost of the Fe-Bbased alloys, this family of amorphous alloys can be regarded as good candidates for refrigerant application at near roomtemperature.
On the other hand, we have calculated the relative cooling power (RCP) values for all samples using the following equation [33–35]: max × δT FWHM RCP = −SM
(3) 4 Conclusion
FWHM are the maximum of the Where −S max M and δT entropy variation and the full-width at half maximum in the temperature dependence of the magnetic entropy change (−SM ), respectively. The value of the saturation magnetization was improved by decreasing the V content (Table 1). This leads to a decrease in the magnetic entropy variation when the amount of V is shifted from 8 to 13.7 For our amorphous alloys, the RCP values decrease by increasing the V content (Table 1). For comparison, the magnetic and magnetocaloric properties of some typical near room-temperature refrigerants, such as some Fe-based amorphous alloys [22, 36, 37], prototype Gd pure metal [38] and other crystalline materials
In conclusion, we have prepared amorphous Fe80−x Vx B12 Si8 alloys and carried out magnetization studies at room temperature. The substitution of iron atoms in Fe80 B12 Si8 amorphous alloys by vanadium atoms causes changes in the magnetic moment of Fe, Curie temperatures, and the maximum of the magnetic entropy change. It was found that when the V content increases, the Curie temperature, the iron magnetic moment, and the maximum of the magnetic entropy change decrease. For the alloys with TC close to room temperature, the magnetic entropy change is max = 1.034 J kg−1 K−1 ) of comparable magnitude (−SM despite a large difference in Fe content.
Table 2 Magnetic and magnetocaloric properties under different applied field of present alloys and various crystalline and amorphous alloys with near room-temperature magnetocaloric effect. Composition
Structure
μ0 H (T)
TC (K)
SM max (J kg−1 K−1 )
RCP (J kg−1 )
Ref
Fe72 V8 B12 Si8 Fe70 V10 B12 Si8 Fe66.3 V13.7 B12 Si8 Fe88 Zr7 B4 Cu1 Fe80.5 Nb7 B12.5 Gd LaFe10.8 Si2.2 (Fe0.975 Ni0.025 2 )P
A A A A A C C C
2 2 2 1.5 0.7 2 2 1.97
473.5 435.5 335 287 363 294 240 313
1.467 1.165 1.034 1.32 0.72 5.5 2.3 2
132.7 113.5 93.7 166 – 214.5 137.7 80
This work This work This work [22] [36] [37] [38] [39]
A and C represent amorphous and crystalline structures, respectively
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