The martensite transition temperature
Abstract
Ni41Co9Mn31.5Ga18.5 is a magnetic Heusler alloy, which indicates metamagnetic transition at the reverse martensite transition. In this paper, caloric measurements were performed and discussed about magnetocaloric effect. We also performed magnetization measurements around Curie temperature TC in the martensite phase and analyzed by means of the spin fluctuation theory of itinerant electron magnetism. From the differential scanning calorimetry (DSC) measurements in zero fields, the value of the latent heat λ was obtained as 2.63 kJ/kg, and in magnetic fields the value was not changed. The entropy change ΔS was − 7.0 J/(kgK) in zero fields and gradually increases with increasing magnetic fields. The relative cooling power (RCP) was 104 J/kg at 2.0 T, which was comparable with In doped Ni41Co9Mn32Ga16In2 alloy.
Keywords
- shape memory alloys
- differential scanning calorimetry
- magnetocaloric effect
- magnetization
- itinerant electron magnetism
1. Introduction
Recently, ferromagnetic shape memory alloys (FSMA) have been studied extensively as candidates for highly functional materials. Between FSMA, Ni2MnGa is the most renowned alloy [1]. The alloy has a cubic
New alloys in the Ni–Mn–In, Ni–Mn–Sn, and Ni–Mn–Sb Heusler alloy systems that are expected to be ferromagnetic shape memory alloys have been studied [7, 8]. A metamagnetic transition from paramagnetic martensite phase to ferromagnetic austenite phase was observed, and reverse martensite transition induced by magnetic fields was occurred under high magnetic fields [9, 10]. These alloys are promising as a metamagnetic shape memory alloys with a magnetic field‐induced shape memory effect (MSIF) and as magnetocaloric materials. Ni–Co–Mn–In alloys, in which Co is substituted for Ni in Ni–Mn–In alloys to increase the Curie temperature, indicate shape memory behaviors in compressive
The substitution of Co for Ni or Ga atoms in Ni2MnGa type alloys has turned the magnetic ordering of the parent phase from partially antiferromagnetic or paramagnetic to ferromagnetic, resulting in a large magnetization change across the transformation, which dramatically enhances the magnetic field driving force [12–40]. The phase diagram in the temperature‐concentration plane is determined on the basis of the experimental results. The determined phase diagram is spanned by a paramagnetic austenite (Para‐A) phase, paramagnetic martensite phase, ferromagnetic austenite phase, ferromagnetic martensite (Ferro‐M) phase of
Albertini
We studied about the physical properties and magnetism of Ni50-
The effects of Co addition on the properties of Ni8-
In this paper, caloric measurements were performed. On the basis of the experimental results, magnetocaloric effect was discussed. We also studied about the itinerant electron magnetic properties of Ni41Co9Mn31.5Ga18.5. We performed the magnetization measurements by means of the pulsed magnetic fields. The
2. Experimental procedures
The sample used in this study was synthesized at Yamagata University. The Ni41Co9Mn31.5Ga18.5 alloy was prepared by arc melting 4N Ni, 4N Co, 4N Mn, and 6N Ga in an argon atmosphere. The sample annealed at 1123 K for three days to homogenize the sample in a double evacuated silica tube, and then quenched in cold water. The obtained sample was polycrystalline. DSC measurements were performed by means of Helium‐free magnet at High Field Laboratory for Superconducting Materials, Institute for Materials Research, Tohoku University. The bore of this magnet is
Magnetization measurements were performed by means of the pulsed field magnet at Ryukoku University. The absolute value was adjusted by Ni. The diamagnetism of the sample was also concerned to analyze the field dependence of the magnetization.
3. Results and discussions
3.1. Crystallography of Ni41Co9Mn31.5Ga18.5
From X‐ray powder diffraction shown in Figure 1, the sample was confirmed as a single phase with a tetragonal
The final compositions of the grown sample were verified by energy dispersive spectroscopy and were close to the nominal values with a deviation of <1%.
The Scanning Electron Microscope (SEM) image of Ni41Co9Mn31.5Ga18.5 at 298 K by means of FE‐SEM (JSM6300F, JEOL Co. Ltd.) shown in Figure 3 indicates that there are macroscopic twin variants on a scale of a few micrometers. The twins were arranged neatly in the domains. A single martensite phase characterized by typical lamellar twin substructures was observed, agreeing well with the X‐ray diffraction results. This result is well agree with the optical micrographs of microstructure of Ni56-
The calorimetric measurements, which allowed for the estimation of the latent heat and magnetocaloric analysis, were performed with factory‐made differential scanning calorimeter able to work up to 6 T. This setup exploits Peltier cells in order to measure heat flow of the sample. Calorimetric measurements of Ni41Co9Mn31.5Ga18.5 polycrystalline ferromagnetic shape memory alloy (FSMA) were performed across the
3.2. Magnetocaloric effect of Ni41Co9Mn31.5Ga18.5
The thermodynamic properties of the presented sample in magnetic fields were studied experimentally by measuring the heat flow by means of the DSC equipment. The four panels of Figure 4 show the heat flow of Ni41Co9Mn31.5Ga18.5 in zero and magnetic fields. The endothermic reaction was occurred around the reverse martensite temperature
Figure 7 shows the entropy change
We also performed the DSC measurement of Ni52.5Mn24.5Ga23 in zero and magnetic fields by means of the water‐cooled electromagnet in Ryukoku University. Figure 9a shows the heat flow of Ni52.5Mn24.5Ga23 in a heating process. The endothermic reaction was occurred around
Table 1 shows the
Sample | RCP (J/kg) | Reference | |||
---|---|---|---|---|---|
Ni52.6Mn23.1Ga24.3 | 297 | -6 | 1.8 | 11 | [48] |
Ni52.5Mn24.5Ga23 | 348 | -6.1 | 8.0 | 48 | This work |
Ni55.4Mn20Ga24.6 | 313 | -41 | 1.1 | 45 | [49] |
Ni45Co5Mn38Sb12 | 264 | 26 | 2.8 | 73 | [50] |
Ni50Mn35In14Si1 | 288 | 36 | 2.6 | 94 | [51] |
Ni43Co7Mn31Ga19 | 420 ( |
13.3 (5 T) | – | 188 (5 T) | [24] |
Ni41Co9Mn32Ga18 | 421 ( |
17.8 (5 T) | 12 (5 T) | 156 (5 T) | [24] |
Ni45Co5Mn37.5In12.5 | 355 | 7 | 16 | 112 | [52] |
Ni41Co9Mn31.5Ga18.5 | 348 ( |
7.2 | 14 | 104 | This work |
The magnetostructural transformation in this system can be described, in the frame of a simple geometrical model, by a relation linking the field‐induced adiabatic temperature change Δ
Here, Δ
In order to obtain an adiabatic temperature change Δ
Entel et al. studied about Ni50-
Sample | Reference | |||||
---|---|---|---|---|---|---|
Ni50Mn30Ga20 | 6.90 | -3.7 | +0.9 | 370 | +0.8 (1.8 T) | [47] |
Ni52.5Mn24.5Ga23 | 6.78 | -4.6 | +1.5 | 348 | +1.0 (1.5 T) | This work |
Ni41Co9Mn32Ga16In2 | 2.30 | 4.5 | -11.3 | 320 | -2.3 (1.8 T) | [42, 47] |
Ni41Co9Mn31.5Ga18.5 | 2.34 | 7.2 | -8.6 | 348 | -4.5 (2.0 T) | This work |
3.3. Itinerant electron magnetic properties of Ni41Co9Mn31.5Ga18.5
We performed the magnetization measurements by means of the pulsed magnetic fields in order to investigate the itinerant electron magnetic properties of Ni41Co9Mn31.5Ga18.5. Takahashi proposed a spin fluctuation theory of itinerant electron magnetism [44, 45]. The induced magnetization
where,
In most cases, the critical temperature dependence was determined using the Arrott plot. The analysis is based on the implicit assumption that the linearity is always satisfied. Takahashi suggested that the Arrott plot is not applicable in much itinerant d‐electron ferromagnets and the revision is necessary in the itinerant electron magnetism [45].
Figure 11 shows the magnetization process of Ni41Co9Mn31.5Ga18.5 around the
where
Eq. (2) can be written as the formula of,
and
where
Figure 12 shows the logarithm plot of Eq. (5). The gradient of the X‐Y plots indicate the critical index
Figure 13 shows the
Table 4 indicates the values of
Critical index |
Standard deviation (%) | |
---|---|---|
258 | 5.80 | 0.950 |
260 | 5.77 | 0.208 |
262 | 5.42 | 0.169 |
263 | 5.25 | 0.119 |
264 | 4.95 | 0.187 |
265 | 4.60 | 0.210 |
The value
Compound | Reference | |||
---|---|---|---|---|
Ni | 0.6 | 623 | 1.76 × 104 | [55] |
MnSi | 0.4 | 30 | 2.18 × 103 | [45] |
Co2CrGa | 3.01 | 488 | 1.0 × 104 | [44] |
Ni2MnGa | 4.5 | 363 ( |
4.63 × 102 | [55] |
Ni52.5Mn24.5Ga23 | 3.75 | 350 ( |
6.45 × 102 | [6, 57] |
URhGe | 0.32 | 9.6 | 8.56 × 102 | [45] |
UGe2 | 1.44 | 53.5 | 4.93 × 102 | [45] |
Ni41Co9Mn31.5Ga18.5 | 1.74 | 263 ( |
7.03 × 102 | This work |
4. Conclusions
We studied about the magnetocaloric properties of Ni41Co9Mn31.5Ga18.5 by means of differential scanning calorimetry (DSC) measurements. Magnetocalorimetric measurements and magnetization measurements of Ni41Co9Mn31.5Ga18.5 polycrystalline ferromagnetic shape memory alloy (FSMA) were performed across the TR, at atmospheric pressure. When heating from the martensite phase, a steep increase in the thermal expansion due to the reverse martensite transition at TR was observed by the thermal expansion measurements. These transition temperatures decreased gradually with increasing magnetic field. The field dependence of the reverse martensite transition temperature,
In order to investigate the itinerant electron magnetic properties of Ni41Co9Mn31.5Ga18.5, we performed the magnetization measurements by means of the pulsed magnetic fields. The
Acknowledgments
The authors thank to Dr. M. Mori for helping SEM microscope experiment. DSC measurements in steady magnetic fields were performed at High Field Laboratory for Superconducting Materials, Institute for Materials Research, Tohoku University, Japan.
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