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# Scripta Materialia 130 (2017) 170–173

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Scripta Materialia

journal homepage: www.elsevier.com/locate/scriptamat

Regular article

**Magnetic entropy change in Gd95Fe2.8Al2.2
**

amorphous/nanocrystalline ribbons

Qiang Zheng a, Linlin Zhang a,b, Juan Du b,⁎

a

**School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315016, People's Republic of China
**

Key Laboratory of Magnetic Materials and Devices, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, 1219 Zhongguan West Road, Ningbo 315201,

People's Republic of China

b

a r t i c l e

i n f o

Article history:

Received 12 May 2016

Received in revised form 5 September 2016

Accepted 29 November 2016

Available online xxxx

Keywords:

Magnetic materials

Amorphous/nanocrystalline materials

Nanocomposites

Magnetocaloric effect

a b s t r a c t

The Gd95Fe2.8Al2.2 amorphous/nanocrystalline composite was obtained by melt spinning. A full width at half

maximum of entropy change −ΔSM (δFWHM) of 104 K, relatively large refrigerant capacity (RC) of ~551 J kg−1

together with −ΔSM of 7.8 J kg−1 K−1 have been achieved at 278 K under a ﬁeld change of 5 T. This RC value

is about 35% and 80% larger than those of crystalline Gd (~410 J kg−1) and Gd5Si2Ge2 (~306 J kg−1) alloy, respectively. The mechanism of the enhanced RC was discussed and would shed a light on searching for excellent magnetic refrigerants at near room temperature.

© 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

**Magnetic refrigeration based on magnetocaloric effect (MCE) has
**

attracted increasing attention because of its superior properties, such

as high energy efﬁciency and environmental friendliness. Therefore, it

is expected to replace traditional vapor-compression refrigeration in

the near future [1]. Currently, the large MCE has been extensively studied on various crystalline materials with a ﬁrst-order magnetic transition, such as La (Fe1 − x, Six)13 [2–3], Gd5Si2Ge2 [4], MnFe (P, As) [5],

Ni-Mn-X (X = Sn, In, Sb) [6–8], etc. The advantage of these crystalline

materials is their large magnetic entropy change. However, due to the

ﬁrst-order magnetic transition, the thermal and magnetic hysteresis is

intrinsically unavoidable. Also, the temperature range of full width at

half maximum (δFWHM) of the magnetic entropy change (ΔSmax

M ) peak

is only a few to a few tens Kelvin. Therefore, the refrigeration capacity

(RC) in crystalline materials is small.

Amorphous materials undergo second order magnetic transition

(SOMT) which will broaden magnetic entropy change (ΔSm) peaks

and result in high values of RC [9–13]. They also have some unique

properties that are superior to those of crystalline alloys, such as, no

thermal and magnetic hysteresis, large electrical resistivity, high

corrosion resistance, tailorable magnetic transition temperature, ﬁne

molding and processing behavior. The negative point of amorphous materials is their lower Curie temperatures and lower magnetic entropy

change compared to those of their crystalline counterparts.

Recently, many efforts have been devoted to improving Curie temperatures and magnetic entropy change of amorphous materials in

⁎ Corresponding author.

E-mail address: dujuan@nimte.ac.cn (J. Du).

**http://dx.doi.org/10.1016/j.scriptamat.2016.11.041
**

1359-6462/© 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Gd- systems [14–18]. Unfortunately, there are still no amorphous materials having a Curie temperature close to room temperature combined

with a high magnetic entropy change under a magnetic ﬁeld change

(5 T). Therefore, it is an open challenge to obtain both high Curie temperature and large magnetic entropy change. In this work, Gd-based

amorphous and nanocrystalline composites are designed based on the

idea of combination effect of amorphous and nanocrystalline in which

the amorphous part contributes to the wide temperature range of

δFWHM and the nanocrystalline part gives high magnetic entropy change

and high Tc. In this paper, magnetocaloric effect of Gd95Fe2.8Al2.2

ribbons has been developed. And, a high − ΔSm value of

~7.53 J kg−1 K−1 at 278 K, RC value of 551 J kg−1 and δFWHM of 104 K

were obtained under a ﬁeld change of 5 T. The mechanism of enhanced

RC was discussed and explained.

Master alloy of Gd95Fe2.8Al2.2 (atomic percent) was prepared by arcmelting a mixture of pure Gd, Fe and Al metals in a titanium-gettered

argon atmosphere. The purities of all raw elements are better than

99.9%. The amorphous ribbons with a thickness of about 20 μm and a

width of about 2 mm were produced by melt-spinning technology on

a single-roller copper wheel with a speed of 40 m/s. The structure of

the as-quenched ribbons was examined by X-ray diffraction (XRD)

using Cu-Kα radiation. The thermal properties were investigated by differential scanning calorimetry (DSC) at a constant heating rate of

40 K/min under puriﬁed argon atmosphere. The magnetic properties

were measured by superconducting quantum interference device magnetometer (SQUID).

Fig. 1 shows the XRD patterns of Gd95Fe2.8Al2.2 ribbons. The as-spun

ribbons have sharp Gd peaks imposed on a broad diffused diffraction

Q. Zheng et al. / Scripta Materialia 130 (2017) 170–173

171

**Fig. 1. X-ray diffraction patterns of as-quenched Gd95Fe2.8Al2.2 ribbons. The inset shows
**

the DSC curves of Gd95Fe2.8Al2.2 ribbons at a heating rate of 40 K/min.

peak which indicates the amorphous/nanocrystalline composite structure in these ribbons. The amorphous base can be further proved by

the DSC results (the inset of Fig. 1). From the DSC curves, there is a

clear glass transition (Tg) before several exothermic crystallization reactions, which indicates the existing of amorphous material. The sharp Gd

peaks gives the evidence of nanocrystalline exists in the amorphous

base, and the grain size of Gd nanoparticles was approximately 20 nm

calculated by Debye-Scherrer formula.

Fig. 2 presents the temperature dependence of magnetization of

Gd95Fe2.8Al2.2 ribbons under an applied ﬁeld of 200 Oe. The Curie temperature (Tc), which is deﬁned as the temperature at the maximum of

dM/dT, where M is magnetization and T is temperature, is shown in

the inset of Fig. 2. There are obviously two maxima of dM/dT curve

which proves the appearance of multiple Curie temperatures. One maximum is located at 232 K, and the other is located at 278 K.

Fig. 3(a) displays the isothermal magnetization curves of

Gd95Fe2.8Al2.2 ribbons measured in a temperature range of 125–350 K

under a magnetic ﬁeld up to 5 T. From 265 to 290 K, the temperature

step is 5 K and in faraway regions of 125–265 K and 290–350 K, the temperature step is 20 K. The sweeping rate of the ﬁeld was slow enough to

ensure that the magnetization curves are obtained in an isothermal

process. To further understand the magnetic transitions, the Arrot

**Fig. 2. Temperature dependence of the magnetization of Gd95Fe2.8Al2.2 ribbons under an
**

applied ﬁeld of 200 Oe. The inset shows the derivative curves of dM/dT vs. T.

**Fig. 3. Isothermal magnetization curves between 125 and 350 K (a) and the Arrott plots for
**

as-quenched Gd95Fe2.8Al2.2 ribbons (b).

**plots (M2 versus H/M curves) were also analyzed and shown in Fig.
**

3(b). According to Banerjee criterion, a magnetic transition is considered as ﬁrst-order when the slope of Arrott plot is negative; otherwise,

it is expected to be second-order when the slope is positive [19]. The inﬂection or negative slope as an indication of metamagnetic transition

above Tc is not observed in Fig. 3(b). This proves the magnetic transition

at Tc for the Gd95Fe2.8Al2.2 alloy is a second order magnetic transition

(SOMT) for both the amorphous and nano-Gd parts.

Fig. 4(a) shows the −ΔSM-T curve of Gd95Fe2.8Al2.2 ribbons under a

ﬁeld change of 5 T. −ΔSM for Gd95Fe2.8Al2.2 ribbons was calculated by

using Maxwell relationships. Maximum − ΔSM, magnetic transition

temperature (Tc), RC for Gd95Fe2.8Al2.2 ribbons are summarized in

Table 1. For comparison, magnetocaloric properties of some typical

magnetic transition materials around room temperature including our

material are also included. As shown in Fig. 4(a), − ΔSM peak of

Gd95Fe2.8Al2.2 ribbon at 283 K are about 2.34 J kg−1 K− 1 under 1 T,

3.97 J kg−1 K−1 under 2 T, 5.29 J kg−1 K−1 under 3 T, 6.45 J kg−1 K−1

under 4 T and 7.53 J kg−1 K−1 under 5 T, respectively. For Gd95Fe2.8Al2.2

ribbon, the maximum value of ΔSM under 5 T is comparable to those of

many previously published results, such as Gd5Si2Ge1.9Fe0.1

(7 J kg−1 K−1, TC = 276 K) [20], La0.7Ca0.2Sr0.1MnO3 (7.45 J kg−1 K−1,

TC = 308 K) [21]. While, it is much lower than that of other crystalline

materials, such as La1.4Ca1.6Mn2O7 (16.8 J kg−1 K−1, TC = 270 K) [22],

Gd5Si2Ge2 (18.4 J kg−1 K−1, TC = 276 K) [4]. However, a large broadening of the −ΔSM (T) curves around room temperature can overcompensate for such a disadvantage, giving rise to a signiﬁcant RC

enhancement.

172

Q. Zheng et al. / Scripta Materialia 130 (2017) 170–173

**Fig. 4. The total −ΔSM (T) curve (solid square) of Gd95Fe2.8Al2.2 ribbons under a ﬁeld
**

change of 5 T (a). The ﬁtting results of the contribution of both amorphous (solid circle)

and nano-Gd parts (solid triangle) to the total −ΔSM(T) curve (solid square) are also

included in panel (a), and magnetic ﬁeld H dependence of RC and −ΔSM of the

Gd95Fe2.8Al2.2 ribbons (b). The dashed line in panel (b) is the ﬁtting results of −ΔSM ∝ Hn.

**From Fig. 4(a), it can be seen that the −ΔSM(T) curve (solid square)
**

is asymmetric and could be the result of the convolution of independent

processes for each contribution in the system, which, by the way, is what

can be seen in the thermal magnetization measurement of Fig. 2. The

contributions from both the amorphous (solid circle) and nano-Gd part

(solid triangle) in the composite by ﬁtting are displayed in Fig. 4(a).

Since two Tc temperatures have been observed in Fig. 2, two peaks of

−ΔSM were intended to obtain by ﬁtting −ΔSM (T) curve using the function of ﬁtting multi-peaks in origin 8.0. The initial two temperature Tc

peaks (two maxima in inset of Fig. 2) were selected for ﬁtting the contribution of amorphous and nano-Gd parts. For the ﬁtting curves, Gaussian

distribution was applied during the ﬁtting temperature range. The coefﬁcient of determination (COD) for ﬁnal ﬁtting results is 0.992, which means

a good ﬁtting result. And for the amorphous part, the −ΔSM is

4.0 J kg−1 K−1at 235 K, RC is 686 J kg−1, and δFWHM is 230 K. For nanoGd part, the −ΔSM is 6.3 J kg−1 K−1 at 288 K, RC is 331 J kg−1, and

δFWHM is 72 K. Therefore, the most important point of our research is to

proﬁt the combination effect of amorphous and nanocrystalline phases

on the MCE concerning its temperature range, magnetic entropy variation

and refrigeration capacity. Additionally, according to the characteristic

−ΔSM (T) curve of amorphous and crystalline materials, from the ﬁtting

results can explain these two maxima in the inset of Fig. 2. The former is

ascribed to the amorphous part, and the latter is due to the precipitated

nano sized Gd.

Also, it can be seen that in the inset of Fig. 4(a), the ΔS of nano-Gd is

about 6.3 J kg−1 K−1, which is lower than that value (ΔS =

~10 J kg−1 K−1) in bulk Gd under a magnetic change of 5 T. The reasons

are due to the ﬁnite size effect (e.g., a grain size of nanometer size) and

structural disorder at grain boundaries. The above-mentioned reasons

will result in the depressed magnetization (e.g., Magnetic moment)

and then reduced magnetic entropy in nanometer Gd compared to

bulk Gd. Two examples can be found in Ref. [24,25]. In Ref. [24], it was

reported that the delta S was 10.07, 7.73 and 4.47 J kg− 1 K−1 for

1000 nm, 100 nm and 15 nm Gd systems under a magnetic ﬁeld of

5 T, respectively. In Ref. [25], MCE was reported for single crystal Gd,

18 nm and 12 nm nano-Gd under 5 T, and the delta S for nano-Gd

was reduced by roughly a factor of 1.5 compared to that of single crystal

Gd (micrometer).

Another question is why the transition temperature of nano-Gd

lower than that of bulk Gd combined Figs. 2 and 4(a)? Finite size of a

system (e.g., a grain of nanometer size) limits the divergence of ξ and

thereby causes a size-dependent shift in Tc to lower temperatures better

known as the ﬁnite-size scaling. For example, in Ref. [25], the Tc is

285.65 K, 287.25 K and 293 K for d = 12 nm, d = 18 nm and single crystal Gd by speciﬁc heat measurement.

For the SOMT materials, the relation of − ΔSM and H can be described as the following scaling law [26]: −ΔS ∝ Hn. The ﬁtting results

plotted in the Fig. 4(b) demonstrate that the value of n for the meltspun Gd95Fe2.8Al2.2 ribbon is about 0.708. This value is consistent to

the value of 2/3 corresponding to mean ﬁeld theory [27].

Refrigeration capacity (RC) is another important parameter characterizing the magnetocaloric effect. In this work, the RC values are determined by numerically integrating the area under the −ΔSM (T) curve

with a full width at half maximum of the peak as the integrating limits

[22]. As shown in Fig. 4(a), the δFWHM of −ΔSM is 104 K and 67 K for a

magnetic ﬁeld change of 5 T and 2 T, respectively. And, the RC values

of this composite are about 90 J kg−1 under 1 T, 196 J kg−1 under 2 T,

309 J kg−1 under 3 T, 425 J kg−1 under 4 T and 551 J kg−1 under 5 T,

Table 1

Maximum magnetic entropy changes (ΔSM), magnetic transition temperature (Tc), RC for our sample together with other magnetocaloric candidate materials at near room temperature

for comparison.

Material

Structure

Applied ﬁeld (T)

Transition temperature (K)

ΔSM

(J kg−1 K−1)

RC (J kg−1)

Reference

Gd95Fe2.8Al2.2

Gd50Co45Fe5

Gd48Co52

Gd

Gd5Si2Ge2

Gd5Si2Ge1.9Fe0.1

La0.7Ca0.2Sr0.1MnO3

La1.4Ca1.6Mn2O7

GdFeAl

a+c

a

a

a

c

c

c

c

c

5

5

5

5

5

5

5

5

5

232/278

289

282

294

276

176

308

270

265

7.53

3.8

4.23

10.2

18.6

7

7.45

16.8

3.7

551

521

750

410

306

360

–

–

420

This work

[13]

[18]

[1]

[1]

[20]

[21]

[22]

[23]

a and c stand for the amorphous and crystalline structure, respectively.

Q. Zheng et al. / Scripta Materialia 130 (2017) 170–173

**respectively. The maximum RC value is under 5 T is about 35% and 80%
**

larger than those of Gd (~410 J kg−1) [1] and Gd5Si2Ge2 (~306 J kg−1)

[1], respectively.

The Gd95Fe2.8Al2.2 amorphous/nanocrystalline composite was prepared by melt spinning. The Tc is 232 K and 278 K for the amorphous

and nano-Gd parts, respectively. Second-order magnetic transitions

are justiﬁed by the Arrott plot for this composite. The large magnetic entropy change of 7.53 J kg− 1 K− 1 under 5 T was obtained for

Gd95Fe2.8Al2.2 composites. The refrigeration capacity (RC) value is

551 J kg−1 under a magnetic ﬁeld change of 0–5 T. The large ΔSM and

high Tc makes Gd-based amorphous/nanocrystalline composites attractive candidate for magnetic refrigeration materials at near room

temperature.

This work has been supported by the Natural Science Foundation of

Zhejiang Province for Outstanding Youth (Grant No. LR12E01001), National Natural Science Foundation of China (Grant No. 51422106), the

Natural Science Foundation of Ningbo City (Grant No. 2015A610004)

and the start-up foundation of Ningbo University of Technology.

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