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Cryogenic magnetic properties of Er60Ni30Co10 amorphous ribbon
Journal of Non-Crystalline Solids 484 (2018) 36–39
Contents lists available at ScienceDirect
Journal of Non-Crystalline Solids journal homepage: www.elsevier.com/locate/jnoncrysol
Cryogenic magnetic properties of Er60Ni30Co10 amorphous ribbon ⁎
⁎
T
Wenlin Gao, Xiangjie Wang , Lijuan Wang, Yikun Zhang , Jianzhong Cui Key Laboratory of Electromagnetic Processing of Materials (Ministry of Education), Northeastern University, Shenyang 110819, China
A R T I C L E I N F O
A B S T R A C T
Keywords: Er60Ni30Co10 amorphous ribbons Magneto-caloric effect Magnetic properties Glass forming ability
The glass forming ability, magnetism and magneto-caloric effect have been investigated in Er60Ni30Co10 meltspun alloy by using X-ray diffraction, differential scanning calorimetry and magnetization measurements. The amorphousized Er60Ni30Co10 exhibits a relatively wide supercooled liquid region of 40 K and a second-order ferromagnetic transition around Curie temperature of 11.5 K. Under ΔΗ (magnetic field change) of 0–5 T, the values of −ΔSMmax (maximum magnetic entropy change) and RCP (relative cooling power) are 12.1 J/kg K and 342 J/kg, respectively. Furthermore, the field dependence of the magnetic entropy change for Er60Ni30Co10 obeys the phenomenological universal curve and corresponds to a field independent exponent of n = 0.58 ± 0.03.
1. Introduction For saving energy and protecting environment, searching for an alternative refrigeration technology to replace the present gas compression refrigeration technology becomes a hot topic. Up to present, the magnetic refrigeration technology based on magneto-caloric effect (MCE) is considered to be one of the most promising candidates [1–5]. MCE is an intrinsic phenomenon of a material and it can be characterized by the heating or cooling of the material when the applied magnetic field changes. Its intensity is strongly dependent on the magnetic and thermodynamics properties of the selected material. Therefore, to find novel materials with special characteristics inducing a good reversible MCE is one of the challenges in the field of materials science and engineering. For this purpose, a number of magnetic materials have been developed in recent years, and some of them exhibit good or considerable magneto-caloric properties [6–20]. Besides materials with excellent magneto-caloric performance, the amorphous alloys seem to be the good candidates and have reflected obvious advantages benefited from the structure disorder [21–29]. Compared with crystallized materials, the amorphous alloys can produce an ultrahigh relative cooling power (RCP) since the broadened temperature dependence of the magnetic entropy change (−ΔSM) curve directly induces a wide full width at half maximum peak of ΔSM. Furthermore, special attention has been focused on a series of rare earth (RE) based amorphous alloys because of their intrinsic large magnetic moments and profuse magnetic structures [23–29]. Some unique characteristics have been found in light RE-based amorphous alloys, such as Nd-based amorphous alloys have hard magnetic property [24],
⁎
and Ce-based amorphous alloys exhibit polymer-like thermoplastic behaviors [25], etc. For the heavy RE ones, most of the researches focus on the Gd-based amorphous alloys due to its higher TC [26–29]. Very recently, some other heavy RE-based amorphous alloys are found to have promising cryogenic magneto-caloric performance which may have some potential application for cryogenic magnetic refrigeration [26]. Thus, the Er-based melt-spun Er60Ni30Co10 amorphous alloy is developed and its glass forming ability, magnetism and magneto-caloric effect are systematically studied in the present paper. The results show that Er60Ni30Co10 has large values of relative cooling power (RCP) and could be a promising magnetic refrigerator in the field of cryogenic temperature magnetic refrigeration. 2. Experimental High purity elements (better than 99.9 at.%) of Er, Ni and Co were used for the preparation of pre-alloy ingot with a nominal composition of Er60Ni30Co10 by arc melting with a Ti-getter in Ar atmosphere. The ingot was melted 6 times to reach good homogeneity. The weight loss was within 0.1 wt% for Er60Ni30Co10 during the whole melting process. The ribbons of the sample were then produced using a single roller melt-spinning method with a surface Cu-wheel linear speed of about 30 m/s also under Ar atmosphere, having 2–3 mm in width, around 20 μm in thickness and several cm in length. The amorphous structural characterization was checked by X-ray diffraction (XRD) (Bruker D8 Advance) using the Cu Kα radiation in the angular interval of 20° ≤ 2θ ≤ 80° with a step increment of 0.02°. The calorimetric signals of phase transformations (glass transition, crystallization, melting and
Corresponding authors. E-mail addresses: [email protected] (X. Wang), [email protected] (Y. Zhang).
https://doi.org/10.1016/j.jnoncrysol.2018.01.010 Received 24 September 2017; Received in revised form 28 December 2017; Accepted 8 January 2018 Available online 19 January 2018 0022-3093/ © 2018 Elsevier B.V. All rights reserved.
Journal of Non-Crystalline Solids 484 (2018) 36–39
W. Gao et al.
Fig. 2. The magnetization (M, left scale) and the reciprocal susceptibility (1/χ, left scale) as a function of temperature under the magnetic field H = 1 T for Er60Ni30Co10 amorphous alloy. Inset shows the temperature dependence dMFC/dT (left scale) and temperature dependence zero-field cooling (ZFC) and field cooling (FC) magnetization (M) under the magnetic field of 0.2 T (right scale) for Er60Ni30Co10 amorphous alloy.
determined to be about 40 K and 0.527, respectively. This illustrates the Er60Ni30Co10 amorphous alloy has good thermal stability with respective to crystallization. Fig. 2 displays the magnetization M (left scale) and the reciprocal susceptibility 1/χ (right scale) as a function of temperature for the melt-spun Er60Ni30Co10 alloy in the temperature range of 3–300 K, measured under magnetic field H = 1 T. The reciprocal susceptibility (1/χ) shows linear temperature dependence at T > 50 K, which obeys Curie–Weiss law. The effective magnetic moment (μeff) is 9.00 μB/Er, and paramagnetic Curie temperature (θp) is 14 K for Er60Ni30Co10. The value of μeff is smaller than that of free ion value of Er3+ (9.58 μB) which is probably related to the absence of long range interaction of amorphous alloy. Inset of Fig. 2 presents M (right scale) as a function of temperature for Er60Ni30Co10 amorphous alloy measured under H = 0.2 T in the modes of zero field cooled (ZFC) and field cooled (FC). Together with the positive value of θp, Er60Ni30Co10 amorphous alloy is believed to undergo a paramagnetic (PM) to ferromagnetic (FM) transition around the Curie temperature (TC) of 11.5 K [defined as the minimum of the dM/dT-T curve (see inset of Fig. 2, left scale)]. Additionally, the ZFC and FC curves overlap each other without splitting at low temperatures with negligible thermal and magnetic hysteresis in the overall measurement temperatures, which is a beneficial to the application of magnetic refrigeration (MR). Moreover, the Curie temperature of TC of Er60Ni30Co10 alloy is far below its crystallization temperature Tx, which is good for application since one magnetic refrigerant is usually applied in the vicinity of TC. Therefore, we can say that from the engineering point of view the Er60Ni30Co10 amorphous alloy possesses high temperature stability. A set of the isothermal field dependence of magnetization M(H) curves was measured in the vicinity of TC for Er60Ni30Co10 amorphous alloy (as shown in Fig. 3). We can see that below TC the magnetization M increases abruptly at a rather low field H and then has a tendency of saturation, which further demonstrates that the Er60Ni30Co10 amorphous alloy is ferromagnetic. The magnetic entropy change ΔSM as one of characteristic parameters is generally used to characterize the magneto-caloric effect (MCE) of a material, which was calculated from a family of M(H) curves (as shown in Fig. 3) by using the Maxwell's thermo-dynamic equation as below,
Fig. 1. (a) XRD pattern and (b) DSC trace measured at a rate of 20 K/min of Er60Ni30Co10 amorphous alloy. The inset of (b) shows an enlargement of the DSC traces from 540 K to 680 K for Er60Ni30Co10 amorphous alloy.
liquidus temperatures) were monitored by means of differential scanning calorimeter (DSC) at a heating rate of 20 K/min with the help of Netzsch STA 449C under a continuous flow of Ar atmosphere. The magnetic characterizations were carried out by using a commercial VSM (vibrating sample magnetometer) of PPMS-9 (Quantum Design) with the accuracy better than 1 ∗ 10−5 emu. 3. Results and discussion The XRD pattern at room temperature for melt-spun Er60Ni30Co10 ribbon is shown in Fig. 1(a). A broad halo pattern centered at around 2θ = 35° with no appreciable diffraction peaks of crystalline phases can be observed, which is characteristic of typical fully amorphous structure. Then, the amorphous feature of the Er60Ni30Co10 alloy is further confirmed by the DSC trace at a heating rate of 20 K/min, as shown in Fig. 1(b). The DSC curve shows a weak endothermic glass phenomenon [see inset of Fig. 1(b)] followed by an obvious crystallization peak, which illustrates one crystallization transition. The values of glass transition temperature (Tg), onset of first crystallization temperature (Tx), melting temperature (Tm) and liquidus temperature (Tl) are marked and determined to be 596, 636, 1100 and 1132 K for Er60Ni30Co10 alloy, respectively. Accordingly, the two important parameters, for vitrifying and charactering the amorphous forming ability [30], i.e. the temperature interval of undercooled liquid ΔTx(=Tx − Tg) and the reduced glass transition temperature Trg(=Tg / Tl), are
ΔSM (T , ΔH ) = 37
∫0
H max
(∂M (H , T )/ ∂T )H dH .
(1)
Journal of Non-Crystalline Solids 484 (2018) 36–39
W. Gao et al.
(−ΔSMmax) shifts gradually to higher temperatures with the increase of magnetic field change (ΔH). The −ΔSMmax values of 7.5, 12.1 and 15.2 J/kg K are obtained for Er60Ni30Co10 amorphous alloy under the magnetic field changes (ΔH) of 0–2, 0–5 and 0–7 T, respectively. The magnetic entropy change under ΔH of 0–5 T is comparable with that of previously reported some amorphous materials, for examples, Tb55Co20Al25 (7.5 J/kg K) [31], Ho30Y26Al24Co20 (9.77 J/kg K) [32], Er60Al16Co20Ni4 (12.9 J/kg K) [33], Gd20Tb20Dy20Ho20Tm20 (8.6 J/ kg K) [23] etc., indicating the present Er60Ni30Co10 amorphous alloy is belonging to a class of good MCE materials. To further understand the field dependence of ΔSM, the power law relationship between −ΔSM and field ΔH at a given temperature is presented [34]: ΔSM ∝ ΔHn, where the exponent n depends on the magnetic state of the alloy and can be locally calculated from the slope of ln|ΔSM| vs. lnΔH, i.e. d ln | ΔS | n = d ln ΔHM . The temperature dependence of the exponent n for Er60Ni30Co10 amorphous alloy is displayed in Fig. 4(b). The n first decreases slightly with a decrease in the temperature and has the minimum value at around the Curie temperature TC, and then it increases rapidly with the further increase of temperature. The value of n is 0.58 ± 0.03 at around TC for the present Er60Ni30Co10 amorphous alloy which is lower than the value for mean field model (0.667), indicating the occurrence of short range magnetic ordering [35]. A phenomenological universal curve for the field dependence of ΔSM has been proposed and successfully applied to some ferromagnetic magneto-caloric materials [36, 37]. It is recognized to be a much more evident way to check the order of magnetic phase transition. It is constructed by a phenomenological procedure using obtained experimental data, and firstly normalizing ΔSM with respect to their respective maximum values ΔSMmax, i.e. ΔS′ = ΔSM(T) / ΔSMmax, and rescaling the temperature axis below and above the critical temperature. So, a new variable θ is produced as follows [36, 37]:
Fig. 3. The magnetization (M) as a function of magnetic field (increasing only) for Er60Ni30Co10 amorphous alloy at some selected temperatures.
− (T − TC)/(Tr1 − TC), T ≤ TC θ=⎧ , ⎨ ⎩ (T − TC)/(Tr2 − TC), T > TC
(2)
where the Tr1 and Tr2 are the temperatures of reference points for each curve that usually corresponds to x × ΔSMmax (x = 0.4–0.7). The phenomenological construction of the universal curve for the studied Er60Ni30Co10 amorphous alloy is constructed by using the value of x = 0.6, and the rescaled curves are illustrated in Fig. 5. It can been noted that all the rescaled ΔSM curves for Er60Ni30Co10 amorphous alloy are field-independent and nearly overlap on a single master curve
Fig. 4. (a) The magnetic entropy change −ΔSM as a function of temperature with the magnetic field changes from 0 to 1 to 0–7 T for Er60Ni30Co10 amorphous alloy. (b) Temperature dependence of the exponent n for Er60Ni30Co10 amorphous alloy.
Following the equation, the error in determining ΔSM can be estimated within 5%. The temperature dependence of −ΔSM for Er60Ni30Co10 amorphous alloy under the magnetic field changes ΔH from 0 to 1 to 0–7 T is demonstrated in Fig. 4(a). The value of −ΔSM increases gradually and the position of the maximum magnetic entropy change
Fig. 5. Normalized magnetic entropy change ΔS′ (=ΔSM/ΔSMmax) as a function of the rescaled temperature θ in the present temperature range for Er60Ni30Co10 amorphous alloy.
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Journal of Non-Crystalline Solids 484 (2018) 36–39
W. Gao et al.
(around and above TC). Such behaviour indicates a second-order ferromagnetic transition happens in Er60Ni30Co10 amorphous alloy. Besides ΔSM, the relative cooling power (RCP) is usually taken into account to judge the potential suitability of the MCE materials as a magnetic refrigerant [4]. RCP can identify the amount of heat transfer for one thermodynamic cycle, which equals the production of −ΔSMmax and the full width at half maximum (δTFWHM), RCP = −ΔSM × δTFWHM. The disordered structure in the Er60Ni30Co10 amorphous alloy broadens the magnetic entropy change curves, and the δTFWHM as large as 16, 28 and 33 K are obtained for the magnetic field changes (ΔH) of 0–2, 0–5 and 0–7 T, respectively. Accordingly, the considerable values of δTFWHM together with −ΔSMmax produce large RCP values of 121, 342 and 498 J/kg. Such large values of RCP are more preferred over the magnetic refrigeration applications with Ericson cycle. Thus, the additions of Ni and Co into Er as well as the formation of the amorphous structure make an improvement of magneto-caloric property for Er60Ni30Co10 alloy.
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4. Conclusions A ferromagnetic Er60Ni30Co10 amorphous ribbon was successfully prepared by melt spinning method, and its glass forming ability, magnetism, magnetic entropy change and relative cooling power were reported. The values of ΔTx(=Tx − Tg) and Trg(=Tg / Tl) are determined to be about 40 K and 0.526, respectively. Excellent magneto-caloric properties were observed in Er60Ni30Co10 amorphous alloy due to a second order magnetic phase transition (PM to a FM state) around its Curie temperature of 11.5 K. The values of −ΔSMmax values of 7.5 and 15.2 J/kg K are obtained for Er60Ni30Co10 amorphous alloy under ΔH of 0–2 and 0–7 T, respectively. The corresponding values of RCP that were achieved are 121 and 498 J/kg. Acknowledgements This work was supported by the National Key Research and Development Program of China (2016YFB0300901), the National Natural Science Foundation of China (U1708251, 51574075, U1608252), and the Fundamental Research Funds for the Central Universities (N150904001, N160913001). References [1] N.A. de Oliveira, P.J. von Ranke, Theoretical aspects of the magnetocaloric effect, Phys. Rep. 489 (2010) 89–159. [2] V. Franco, J.S. Blazquez, B. Ingale, A. Conde, The magnetocaloric effect and magnetic refrigeration near room temperature: materials and models, Ann. Rev. Mater. Res. 42 (2012) 305–342. [3] B.G. Shen, J.R. Sun, Hu FX, H.W. Zhang, Z.H. Cheng, Recent progress in exploring magnetocaloric materials, Adv. Mater. 21 (2009) 4545–4564. [4] L.W. Li, Review of magnetic properties and magnetocaloric effect in the intermetallic compounds of rare earth with low boiling point metals, Chin. Phys. B 25 (2016) 037502. [5] K.A. Gschneidner Jr., V.K. Pecharsky, A.O. Tsokol, Recent developments in magnetocaloric materials, Rep. Prog. Phys. 68 (2005) 1479–1539. [6] Y.K. Zhang, Y. Yang, X. Xu, L. Hou, Z. Ren, X. Li, G. Wilde, Large reversible magnetocaloric effect in RE2Cu2In (RE = Er and Tm) and enhanced refrigerant capacity in its composite materials, J. Phys. D. Appl. Phys. 49 (2016) 145002. [7] Y.K. Zhang, H.D. Li, J. Wang, X. Li, Z.M. Ren, G. Wilde, Structure and cryogenic magnetic properties in Ho2BaCuO5 cuprate, Ceram. Int. 44 (2018) 1991–1994. [8] L.W. Li, Y. Yuan, Y. Qi, Q. Wang, S.Q. Zhou, Achievement of a table-like magnetocaloric effect in the dual-phase ErZn2/ErZn composite, Mater. Res. Lett. 6 (2018) 67–71. [9] L.W. Li, M. Kadonaga, D. Huo, Z. Qian, T. Namiki, K. Nishimura, Low field giant magnetocaloric effect in RNiBC (R = Er and Gd) and enhanced refrigerant capacity in its composite materials, Appl. Phys. Lett. 101 (2012) 122401.
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Contents lists available at ScienceDirect
Journal of Non-Crystalline Solids journal homepage: www.elsevier.com/locate/jnoncrysol
Cryogenic magnetic properties of Er60Ni30Co10 amorphous ribbon ⁎
⁎
T
Wenlin Gao, Xiangjie Wang , Lijuan Wang, Yikun Zhang , Jianzhong Cui Key Laboratory of Electromagnetic Processing of Materials (Ministry of Education), Northeastern University, Shenyang 110819, China
A R T I C L E I N F O
A B S T R A C T
Keywords: Er60Ni30Co10 amorphous ribbons Magneto-caloric effect Magnetic properties Glass forming ability
The glass forming ability, magnetism and magneto-caloric effect have been investigated in Er60Ni30Co10 meltspun alloy by using X-ray diffraction, differential scanning calorimetry and magnetization measurements. The amorphousized Er60Ni30Co10 exhibits a relatively wide supercooled liquid region of 40 K and a second-order ferromagnetic transition around Curie temperature of 11.5 K. Under ΔΗ (magnetic field change) of 0–5 T, the values of −ΔSMmax (maximum magnetic entropy change) and RCP (relative cooling power) are 12.1 J/kg K and 342 J/kg, respectively. Furthermore, the field dependence of the magnetic entropy change for Er60Ni30Co10 obeys the phenomenological universal curve and corresponds to a field independent exponent of n = 0.58 ± 0.03.
1. Introduction For saving energy and protecting environment, searching for an alternative refrigeration technology to replace the present gas compression refrigeration technology becomes a hot topic. Up to present, the magnetic refrigeration technology based on magneto-caloric effect (MCE) is considered to be one of the most promising candidates [1–5]. MCE is an intrinsic phenomenon of a material and it can be characterized by the heating or cooling of the material when the applied magnetic field changes. Its intensity is strongly dependent on the magnetic and thermodynamics properties of the selected material. Therefore, to find novel materials with special characteristics inducing a good reversible MCE is one of the challenges in the field of materials science and engineering. For this purpose, a number of magnetic materials have been developed in recent years, and some of them exhibit good or considerable magneto-caloric properties [6–20]. Besides materials with excellent magneto-caloric performance, the amorphous alloys seem to be the good candidates and have reflected obvious advantages benefited from the structure disorder [21–29]. Compared with crystallized materials, the amorphous alloys can produce an ultrahigh relative cooling power (RCP) since the broadened temperature dependence of the magnetic entropy change (−ΔSM) curve directly induces a wide full width at half maximum peak of ΔSM. Furthermore, special attention has been focused on a series of rare earth (RE) based amorphous alloys because of their intrinsic large magnetic moments and profuse magnetic structures [23–29]. Some unique characteristics have been found in light RE-based amorphous alloys, such as Nd-based amorphous alloys have hard magnetic property [24],
⁎
and Ce-based amorphous alloys exhibit polymer-like thermoplastic behaviors [25], etc. For the heavy RE ones, most of the researches focus on the Gd-based amorphous alloys due to its higher TC [26–29]. Very recently, some other heavy RE-based amorphous alloys are found to have promising cryogenic magneto-caloric performance which may have some potential application for cryogenic magnetic refrigeration [26]. Thus, the Er-based melt-spun Er60Ni30Co10 amorphous alloy is developed and its glass forming ability, magnetism and magneto-caloric effect are systematically studied in the present paper. The results show that Er60Ni30Co10 has large values of relative cooling power (RCP) and could be a promising magnetic refrigerator in the field of cryogenic temperature magnetic refrigeration. 2. Experimental High purity elements (better than 99.9 at.%) of Er, Ni and Co were used for the preparation of pre-alloy ingot with a nominal composition of Er60Ni30Co10 by arc melting with a Ti-getter in Ar atmosphere. The ingot was melted 6 times to reach good homogeneity. The weight loss was within 0.1 wt% for Er60Ni30Co10 during the whole melting process. The ribbons of the sample were then produced using a single roller melt-spinning method with a surface Cu-wheel linear speed of about 30 m/s also under Ar atmosphere, having 2–3 mm in width, around 20 μm in thickness and several cm in length. The amorphous structural characterization was checked by X-ray diffraction (XRD) (Bruker D8 Advance) using the Cu Kα radiation in the angular interval of 20° ≤ 2θ ≤ 80° with a step increment of 0.02°. The calorimetric signals of phase transformations (glass transition, crystallization, melting and
Corresponding authors. E-mail addresses: [email protected] (X. Wang), [email protected] (Y. Zhang).
https://doi.org/10.1016/j.jnoncrysol.2018.01.010 Received 24 September 2017; Received in revised form 28 December 2017; Accepted 8 January 2018 Available online 19 January 2018 0022-3093/ © 2018 Elsevier B.V. All rights reserved.
Journal of Non-Crystalline Solids 484 (2018) 36–39
W. Gao et al.
Fig. 2. The magnetization (M, left scale) and the reciprocal susceptibility (1/χ, left scale) as a function of temperature under the magnetic field H = 1 T for Er60Ni30Co10 amorphous alloy. Inset shows the temperature dependence dMFC/dT (left scale) and temperature dependence zero-field cooling (ZFC) and field cooling (FC) magnetization (M) under the magnetic field of 0.2 T (right scale) for Er60Ni30Co10 amorphous alloy.
determined to be about 40 K and 0.527, respectively. This illustrates the Er60Ni30Co10 amorphous alloy has good thermal stability with respective to crystallization. Fig. 2 displays the magnetization M (left scale) and the reciprocal susceptibility 1/χ (right scale) as a function of temperature for the melt-spun Er60Ni30Co10 alloy in the temperature range of 3–300 K, measured under magnetic field H = 1 T. The reciprocal susceptibility (1/χ) shows linear temperature dependence at T > 50 K, which obeys Curie–Weiss law. The effective magnetic moment (μeff) is 9.00 μB/Er, and paramagnetic Curie temperature (θp) is 14 K for Er60Ni30Co10. The value of μeff is smaller than that of free ion value of Er3+ (9.58 μB) which is probably related to the absence of long range interaction of amorphous alloy. Inset of Fig. 2 presents M (right scale) as a function of temperature for Er60Ni30Co10 amorphous alloy measured under H = 0.2 T in the modes of zero field cooled (ZFC) and field cooled (FC). Together with the positive value of θp, Er60Ni30Co10 amorphous alloy is believed to undergo a paramagnetic (PM) to ferromagnetic (FM) transition around the Curie temperature (TC) of 11.5 K [defined as the minimum of the dM/dT-T curve (see inset of Fig. 2, left scale)]. Additionally, the ZFC and FC curves overlap each other without splitting at low temperatures with negligible thermal and magnetic hysteresis in the overall measurement temperatures, which is a beneficial to the application of magnetic refrigeration (MR). Moreover, the Curie temperature of TC of Er60Ni30Co10 alloy is far below its crystallization temperature Tx, which is good for application since one magnetic refrigerant is usually applied in the vicinity of TC. Therefore, we can say that from the engineering point of view the Er60Ni30Co10 amorphous alloy possesses high temperature stability. A set of the isothermal field dependence of magnetization M(H) curves was measured in the vicinity of TC for Er60Ni30Co10 amorphous alloy (as shown in Fig. 3). We can see that below TC the magnetization M increases abruptly at a rather low field H and then has a tendency of saturation, which further demonstrates that the Er60Ni30Co10 amorphous alloy is ferromagnetic. The magnetic entropy change ΔSM as one of characteristic parameters is generally used to characterize the magneto-caloric effect (MCE) of a material, which was calculated from a family of M(H) curves (as shown in Fig. 3) by using the Maxwell's thermo-dynamic equation as below,
Fig. 1. (a) XRD pattern and (b) DSC trace measured at a rate of 20 K/min of Er60Ni30Co10 amorphous alloy. The inset of (b) shows an enlargement of the DSC traces from 540 K to 680 K for Er60Ni30Co10 amorphous alloy.
liquidus temperatures) were monitored by means of differential scanning calorimeter (DSC) at a heating rate of 20 K/min with the help of Netzsch STA 449C under a continuous flow of Ar atmosphere. The magnetic characterizations were carried out by using a commercial VSM (vibrating sample magnetometer) of PPMS-9 (Quantum Design) with the accuracy better than 1 ∗ 10−5 emu. 3. Results and discussion The XRD pattern at room temperature for melt-spun Er60Ni30Co10 ribbon is shown in Fig. 1(a). A broad halo pattern centered at around 2θ = 35° with no appreciable diffraction peaks of crystalline phases can be observed, which is characteristic of typical fully amorphous structure. Then, the amorphous feature of the Er60Ni30Co10 alloy is further confirmed by the DSC trace at a heating rate of 20 K/min, as shown in Fig. 1(b). The DSC curve shows a weak endothermic glass phenomenon [see inset of Fig. 1(b)] followed by an obvious crystallization peak, which illustrates one crystallization transition. The values of glass transition temperature (Tg), onset of first crystallization temperature (Tx), melting temperature (Tm) and liquidus temperature (Tl) are marked and determined to be 596, 636, 1100 and 1132 K for Er60Ni30Co10 alloy, respectively. Accordingly, the two important parameters, for vitrifying and charactering the amorphous forming ability [30], i.e. the temperature interval of undercooled liquid ΔTx(=Tx − Tg) and the reduced glass transition temperature Trg(=Tg / Tl), are
ΔSM (T , ΔH ) = 37
∫0
H max
(∂M (H , T )/ ∂T )H dH .
(1)
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(−ΔSMmax) shifts gradually to higher temperatures with the increase of magnetic field change (ΔH). The −ΔSMmax values of 7.5, 12.1 and 15.2 J/kg K are obtained for Er60Ni30Co10 amorphous alloy under the magnetic field changes (ΔH) of 0–2, 0–5 and 0–7 T, respectively. The magnetic entropy change under ΔH of 0–5 T is comparable with that of previously reported some amorphous materials, for examples, Tb55Co20Al25 (7.5 J/kg K) [31], Ho30Y26Al24Co20 (9.77 J/kg K) [32], Er60Al16Co20Ni4 (12.9 J/kg K) [33], Gd20Tb20Dy20Ho20Tm20 (8.6 J/ kg K) [23] etc., indicating the present Er60Ni30Co10 amorphous alloy is belonging to a class of good MCE materials. To further understand the field dependence of ΔSM, the power law relationship between −ΔSM and field ΔH at a given temperature is presented [34]: ΔSM ∝ ΔHn, where the exponent n depends on the magnetic state of the alloy and can be locally calculated from the slope of ln|ΔSM| vs. lnΔH, i.e. d ln | ΔS | n = d ln ΔHM . The temperature dependence of the exponent n for Er60Ni30Co10 amorphous alloy is displayed in Fig. 4(b). The n first decreases slightly with a decrease in the temperature and has the minimum value at around the Curie temperature TC, and then it increases rapidly with the further increase of temperature. The value of n is 0.58 ± 0.03 at around TC for the present Er60Ni30Co10 amorphous alloy which is lower than the value for mean field model (0.667), indicating the occurrence of short range magnetic ordering [35]. A phenomenological universal curve for the field dependence of ΔSM has been proposed and successfully applied to some ferromagnetic magneto-caloric materials [36, 37]. It is recognized to be a much more evident way to check the order of magnetic phase transition. It is constructed by a phenomenological procedure using obtained experimental data, and firstly normalizing ΔSM with respect to their respective maximum values ΔSMmax, i.e. ΔS′ = ΔSM(T) / ΔSMmax, and rescaling the temperature axis below and above the critical temperature. So, a new variable θ is produced as follows [36, 37]:
Fig. 3. The magnetization (M) as a function of magnetic field (increasing only) for Er60Ni30Co10 amorphous alloy at some selected temperatures.
− (T − TC)/(Tr1 − TC), T ≤ TC θ=⎧ , ⎨ ⎩ (T − TC)/(Tr2 − TC), T > TC
(2)
where the Tr1 and Tr2 are the temperatures of reference points for each curve that usually corresponds to x × ΔSMmax (x = 0.4–0.7). The phenomenological construction of the universal curve for the studied Er60Ni30Co10 amorphous alloy is constructed by using the value of x = 0.6, and the rescaled curves are illustrated in Fig. 5. It can been noted that all the rescaled ΔSM curves for Er60Ni30Co10 amorphous alloy are field-independent and nearly overlap on a single master curve
Fig. 4. (a) The magnetic entropy change −ΔSM as a function of temperature with the magnetic field changes from 0 to 1 to 0–7 T for Er60Ni30Co10 amorphous alloy. (b) Temperature dependence of the exponent n for Er60Ni30Co10 amorphous alloy.
Following the equation, the error in determining ΔSM can be estimated within 5%. The temperature dependence of −ΔSM for Er60Ni30Co10 amorphous alloy under the magnetic field changes ΔH from 0 to 1 to 0–7 T is demonstrated in Fig. 4(a). The value of −ΔSM increases gradually and the position of the maximum magnetic entropy change
Fig. 5. Normalized magnetic entropy change ΔS′ (=ΔSM/ΔSMmax) as a function of the rescaled temperature θ in the present temperature range for Er60Ni30Co10 amorphous alloy.
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(around and above TC). Such behaviour indicates a second-order ferromagnetic transition happens in Er60Ni30Co10 amorphous alloy. Besides ΔSM, the relative cooling power (RCP) is usually taken into account to judge the potential suitability of the MCE materials as a magnetic refrigerant [4]. RCP can identify the amount of heat transfer for one thermodynamic cycle, which equals the production of −ΔSMmax and the full width at half maximum (δTFWHM), RCP = −ΔSM × δTFWHM. The disordered structure in the Er60Ni30Co10 amorphous alloy broadens the magnetic entropy change curves, and the δTFWHM as large as 16, 28 and 33 K are obtained for the magnetic field changes (ΔH) of 0–2, 0–5 and 0–7 T, respectively. Accordingly, the considerable values of δTFWHM together with −ΔSMmax produce large RCP values of 121, 342 and 498 J/kg. Such large values of RCP are more preferred over the magnetic refrigeration applications with Ericson cycle. Thus, the additions of Ni and Co into Er as well as the formation of the amorphous structure make an improvement of magneto-caloric property for Er60Ni30Co10 alloy.
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4. Conclusions A ferromagnetic Er60Ni30Co10 amorphous ribbon was successfully prepared by melt spinning method, and its glass forming ability, magnetism, magnetic entropy change and relative cooling power were reported. The values of ΔTx(=Tx − Tg) and Trg(=Tg / Tl) are determined to be about 40 K and 0.526, respectively. Excellent magneto-caloric properties were observed in Er60Ni30Co10 amorphous alloy due to a second order magnetic phase transition (PM to a FM state) around its Curie temperature of 11.5 K. The values of −ΔSMmax values of 7.5 and 15.2 J/kg K are obtained for Er60Ni30Co10 amorphous alloy under ΔH of 0–2 and 0–7 T, respectively. The corresponding values of RCP that were achieved are 121 and 498 J/kg. Acknowledgements This work was supported by the National Key Research and Development Program of China (2016YFB0300901), the National Natural Science Foundation of China (U1708251, 51574075, U1608252), and the Fundamental Research Funds for the Central Universities (N150904001, N160913001). References [1] N.A. de Oliveira, P.J. von Ranke, Theoretical aspects of the magnetocaloric effect, Phys. Rep. 489 (2010) 89–159. [2] V. Franco, J.S. Blazquez, B. Ingale, A. Conde, The magnetocaloric effect and magnetic refrigeration near room temperature: materials and models, Ann. Rev. Mater. Res. 42 (2012) 305–342. [3] B.G. Shen, J.R. Sun, Hu FX, H.W. Zhang, Z.H. Cheng, Recent progress in exploring magnetocaloric materials, Adv. Mater. 21 (2009) 4545–4564. [4] L.W. Li, Review of magnetic properties and magnetocaloric effect in the intermetallic compounds of rare earth with low boiling point metals, Chin. Phys. B 25 (2016) 037502. [5] K.A. Gschneidner Jr., V.K. Pecharsky, A.O. Tsokol, Recent developments in magnetocaloric materials, Rep. Prog. Phys. 68 (2005) 1479–1539. [6] Y.K. Zhang, Y. Yang, X. Xu, L. Hou, Z. Ren, X. Li, G. Wilde, Large reversible magnetocaloric effect in RE2Cu2In (RE = Er and Tm) and enhanced refrigerant capacity in its composite materials, J. Phys. D. Appl. Phys. 49 (2016) 145002. [7] Y.K. Zhang, H.D. Li, J. Wang, X. Li, Z.M. Ren, G. Wilde, Structure and cryogenic magnetic properties in Ho2BaCuO5 cuprate, Ceram. Int. 44 (2018) 1991–1994. [8] L.W. Li, Y. Yuan, Y. Qi, Q. Wang, S.Q. Zhou, Achievement of a table-like magnetocaloric effect in the dual-phase ErZn2/ErZn composite, Mater. Res. Lett. 6 (2018) 67–71. [9] L.W. Li, M. Kadonaga, D. Huo, Z. Qian, T. Namiki, K. Nishimura, Low field giant magnetocaloric effect in RNiBC (R = Er and Gd) and enhanced refrigerant capacity in its composite materials, Appl. Phys. Lett. 101 (2012) 122401.
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