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Unveiling the Magnetic and Structural Properties of (X2YZ; X = Co & Ni, Y = Fe & Mn and Z = Si) Full Heusler Alloy Microwires with Fixed Aspect Ratio

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24 September 2023

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26 September 2023

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Abstract
We studied Ni2FeSi, Co2FeSi and Co2MnSi -based full Heusler alloy glass-coated microwires with the same geometric aspect ratio ρ ≈ 0.50 ± 0.01 prepared using Taylor-Ulitovsky method. The fabrication of X2YZ; (X = Co & Ni, Y = Fe & Mn and Z = Si) based glass coated microwires with fixed aspect ratio is a quite challenging due to the different samples preparation conditions. The XRD analysis shows nanocrystalline microstructure for all the samples. Space group Fm3¯m (FCC) with disordered B2 and A2-types for Ni2FeSi and Co2FeSi and ordered L21-type for Co2MnSi are observed. The change in the positions of Ni, Co and Mn, Fe in X2YSi resulted in a variation in the lattice cell parameters and the average grain size of the sample. Room temperature magnetic behavior shows a dramatic change depending on the chemical composition, where Ni2FeSi-MWs shows the highest coercivity (Hc) compared to Co2FeSi-MWS and Co2MnSi-MWs. The Hc –value of Ni2FeSi-MWs is 16 times higher than that of Co2MnSi-MWs and 3 times higher than that of Co2FeSi-MWS. Meanwhile, the highest reduced remanence is reported for Co2FeSi-MWS (Mr =0.92), , being about 0.33 and 0.22 for Ni2FeSi-MWs and Co2MnSi-MWs, respectively. From the analysis of the temperature dependence of the magnetic properties (Hc and Mr) of X2YZ-MWs we deduced that Hc shows a stable tendency for Co2MnSi-MWs and Co2FeSi-MWs, meanwhile two flipped points are observed for Ni2FeSi-MWs where the behavior of Hc changes with temperature. For Mr monotonic increase by decreasing the temperature is observed for Co2FeSi-MWs and Ni2FeSi-MWs and roughly stable for Co2MnSi-MWs. The thermomagnetic curves at low magnetic field show irreversible magnetic behavior for Co2MnSi-MWs and Co2FeSi-MWs and regular ferromagnetic behavior for Ni2FeSi-MWs. The current result illustrates the ability to tailor the structure and magnetic behavior of X2YZ-MWs at a fixed internal stresses, i.e., with fixed aspect ratio. Additionally, a different behavior was revealed in X2YZ-MWs depending on the degree of ordering and elements distribution. The tunability of magnetic properties of X2YZ-MWs makes them suitable for sensing applications.
Keywords: 
Subject: Chemistry and Materials Science  -   Materials Science and Technology

1. Introduction

Heusler alloys, characterized by their typical X2YZ (full-Heusler) or XYZ (half-Heusler) compositions, represent a category of multifunctional materials [1,2,3,4,5]. Extensive research has been devoted to investigating the properties of Heusler alloys due to their diverse range of properties, such as the shape memory effect, substantial magnetic field-induced strain (MFIS), half metallic behavior, giant magnetocaloric effect (MCE), and exchange bias [3,4,5,6,7,8,9]. Heusler alloys are suitable for a variety of applications owing to their characteristics, especially in the fields of magnetic cooling, actuators, and energy harvesting [10,11,12]. Numerous bulk Heusler alloys have been successfully synthesized over time, and extensive study has been done on their structural and physical characteristics.
Arc melting, followed by additional thermal treatment, is the main technique used for producing Heusler alloys [2,3,10]. This method makes it possible to produce Heusler alloys in bulk form. However, miniaturization has been investigated as an alternative approach to improve the aforementioned characteristics of Heusler alloys [10]. The performance of Heusler alloys can be improved noticeably by minimizing the dimensions of the alloys. For instance, in the context of magnetic cooling applications, the surface-to-volume ratio can be enhanced to significantly improve the heat-exchange rate by using low-dimensional Heusler alloys.
In recent years, growing attention has been paid to the synthesis and investigation of different families of Heusler alloys with reduced dimensions, such as thin micro/nanowires, ribbons, nanoparticles and thin films [13,14,15]. However, the inherent brittleness of Heusler compounds, including Co, Fe and Ni-based full-Heusler alloys, poses a challenge for their fabrication using conventional metallurgical techniques. Consequently, significant efforts have been directed towards the development of novel fabrication methods for producing Heusler alloys in different physical forms for a specified application. These endeavors aim to overcome the limitations imposed by brittleness and explore the potential of low-dimensional Heusler alloys. Additionally, the preparation of composites incorporating Heusler alloys has emerged as a promising approach to address the aforementioned brittleness issue, becoming a topic of considerable interest in the development of this family of functional materials [3,10].
Rapid melt quenching has been recognized by scientists since the 1960s as a commonly used method for producing innovative materials with a variety of morphological characteristics, including amorphous or crystalline (micro-/nanocrystalline) structures, as well as metastable phases with reduced dimensions [16,17]. Using this technology, it is possible to obtain alloys with specified chemical compositions using rapid solidification, obtaining materials with more effective mechanical, magnetic, and corrosion properties [18,19,20]. Rapid melt quenching techniques have been developed for producing ribbons, wires, flakes, microwires, composite microwires, and other materials. The chosen alloy's phase diagram, the quenching conditions, and the geometry of the prepared materials are only a few of the specific fabrication features that are critical in determining the final structure of the materials that are produced.
As previously mentioned, crystalline rapidly quenched materials generally exhibit inferior mechanical properties compared to their amorphous counterparts [20]. However, other properties relevant to various applications, such as enhanced corrosion resistance and biocompatibility, are desirable [21]. Furthermore, the miniaturization of rapidly quenched materials has emerged as a challenge for numerous applications. Consequently, the development of preparation methods capable of meeting these expectations has garnered significant attention in recent years.
One particularly promising technology aiming the miniaturization of rapidly quenched materials while simultaneously improving magnetic, corrosion, and mechanical properties is the Taylor-Ulitovsky technique [22]. This technique enables the fabrication of thin metallic microwires (typically ranging from 0.02 to 100 μm in diameter) coated with a layer of glass [23,24,25,26,27,28,29,30]. The resulting thin glass-coated microwires, with either amorphous or nanocrystalline structures, can exhibit excellent magnetic softness. Additionally, the thin glass coating imparts new functionalities, including enhanced mechanical and corrosion properties, favourable adhesion with polymeric matrices, and biocompatibility [31,32,33]. In this regard, a few successful endeavors have been made to fabricate wires using either the in-rotating water technique [30] or glass-coated microwires employing the Taylor-Ulitovsky technique from Heusler alloys [33,34,35,36,37,38,39,40,41]. These advances represent a significant progress in the preparation of Heusler alloys in low-dimensional forms and have opened up opportunities for further exploration.
One of the peculiarities of the Taylor-Ulitovsky technique is that it allows preparation of metallic microwires coated with insulating glass by simultaneous rapid solidification from the melt. This manufacturing method is intrinsically linked with internal stresses arising from the difference in the thermal expansion coefficients of glass coating and metallic alloys, which is the main source of internal stresses [18,42,43,44]. Moreover, the internal stresses magnitude, σi, correlates with the aspect ratio, ρ, between the metallic nucleus diameter, dmetal, and total diameter, Dtotal. In this way, the σi can be modified by changing the ρ –ratio [42,44].
In this study, we present an endeavor to produce a set of glass-coated microwires based on the X2ZY composition. These microwires were designed with a fixed aspect ratio and a high Curie temperature exceeding 900 K. The objective was to examine the impact of the uniform internal stress induced by the glass layer coating on the magnetic and structure behavior of the samples, utilizing the Taylor-Ulitovsky process. The selection of this fabrication method was driven by the intriguing magneto-structural characteristics exhibited by glass-coated microwires derived from Heusler alloys, along with the advantageous functional properties associated with such microwires. We chose a series of Heusler alloys, i.e., Ni2FeSi, Co2FeSi and Co2MnSi, with high Curie temperature, which have a significant contribution in advanced spintronic applications due to their unique physical, electronic and magnetic properties [2,12,14,17]. Strong dependence of the magnetic and structure properties of X2YZ-based glass-coated microwires with fixed geometrical aspect ratio is observed and reveals the sensitivity of the internal stress on the microstructure ordering and the chemical composition of the metallic nuclei of X2YZ-based glass-coated microwires.

2. Materials and Methods

The experimental condition for preparation Ni2FeSi, Co2FeSi and Co2MnSi in bulk and glass-coating microwires is described in detail in our previous works [12,14,17]. The key point and the objective of the current study is to dress the samples with fix aspect ratio, to investigate the effect of the stress of covering glass layer on different series of X2YZ-full Heusler -based glass-coated microwires. The following procedures are used to prepare Ni2FeSi, Co2FeSi and Co2MnSi alloys by arc melting. The precursor elements for the Ni2FeSi, Co2FeSi and Co2MnSi alloys are weighed to fit with the nominal ratio (X)2:(Y)1:(Z)1) and deposited in a graphite crucible, containing Ni (99.99%), Co (99.99%), Fe (99.9%), Mn (99.99%), and Si (99.99%). The ingots of Ni2FeSi, Co2FeSi and Co2MnSi alloys (ingot) were created by combining the ingredients. For all alloys the melting process was repeated five times to make the alloys homogenous. The chemical compositions and the nominal ratio of the X2YZ alloys were tested before proceeding to the glass-covering process. By using the Taylor-Ulitovsky technique we can obtain a wide range of Heusler -based glass-coated microwires with proper dimensions and length depending on the application and the purpose of the investigations [37,41,42,43,44,45,46,47,48]. Controlling of the casting process rate of the melting ingot, i.e., Ni2FeSi, Co2FeSi and Co2MnSi is able us to obtain glass-coating microwires with fixed nuclei diameter and well controlling the thickness of the covering glass layer. Thus, fixed aspect ratio is easily obtained in the current alloys. After preparation of the Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs we estimated the geometrical parameters dmetal (µm), Dtotal (µm) then the aspect ratio (ρ = dmetal/ Dtotal) by using the optical microscope and Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) (JEOL-6610LV, JEOL Ltd., Tokyo, Japan) to determine the aspect ρ -ratio of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs samples and its related nominal chemical composition (See Table 1). After confirming the nominal ratio and the chemical compositions of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs the microstructure analysis was performed at room temperature by using X-ray diffraction (XRD) BRUKER (D8 Advance, Bruker AXS GmbH, Karlsruhe, Germany). The magnetic characterizations were performed as follow: first we have measured the hysteresis (M-H) loops at room temperature by applied magnetic field parallel and perpendicular to the metallic nuclei axis of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs samples to checked the magnetic anisotropy and confirmation the easy axis of the magnetization. Then we checked the magnetic behavior of the samples in a wide range of temperature (5-400 K) by measuring the M-H-loops parallel to the wire’s axis, i.e., easy magnetization axis. Finally, the thermal magnetization curves i.e., field cooling (FC) and field heating (FH) magnetizations curves at applied low external magnetic field to check the irreversibility behavior or magnetic phase transition in Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs. All magnetization curves were measured using a PPMS (Physical Property Magnetic System, Quantum Design Inc., San Diego, CA) vibrating-sample magnetometer.

3. Results

3.1. Chemical, nominal composition and microstructure analysis

As mentioned in previous section, the morphological and main geometrical parameters are evaluated using the optical microscope and SEM. Table 1 shows the estimation of the metallic nucleus, dmetal, and the total diameters, Dtotal, of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs. By calculating dmetal (µm) and Dtotal (µm) we can easily obtain the aspect ratio. The differences of the aspect ratios of all samples is around (± 0.1). The EDX analysis was used to confirm the chemical compositions of the samples .we used As shown in Table 1, all the samples achieved the stoichiometry 2:1:1 with slightly higher amount of Si is observed in Co2FeSi-MWs and Co2MnSi-MWs due to the additional a signal of Si comes from the covering glass-layer.
Figure 1 illustrates the microstructure investigation of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs measured by XRD at room temperature. The pattern starts from 2Ө = 23.8° to exclude the amorphous halo which comes from the covering glass layers. As shown in Figure 1, all the samples show crystalline structure with main peaks at 2Ө = 46.3° which distinctive for Heusler compounds. In spite that the samples have the same internal stress i.e., the same aspect ratio, change in the microstructure is observed. Ni2FeSi-MWs and Co2MnSi-MWs shared two peaks at 2Ө = 68.6° and 2Ө = 85.1° with (400) and (420) reflections, respectively. Due to the absence of (111) and (200) reflection the at Ni2FeSi-MWs, thus the FCC single phase microstructure with B2-type, i.e., (disordered) is supposed. Meanwhile, well defined FCC single phase with L21 ordered -type is found for Co2MnSi-MWs. However, the two super lattices diffraction (111) and (200) peaks are significantly weaker, compared to other elements belonging to the same period of the periodic table [49]. The intensities of these peaks may therefore be essentially undetectable, if the majority or all the elements in the presented alloys belong to the same period in elemental periodic table. For Co2FeSi-MWs the existence of two peaks only at 2Ө = 46.3° and 2Ө = 85.1° which corresponding with (220) and (420) reflections fit very well with FCC single phase with A2-type, i.e., disordered.
From detailed analysis of the XRD pattern of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs sample we find that the lowest lattice parameters is detected for Co2FeSi-MWs, where a = 2.81Å. The cell parameters for Ni2FeSi-MWs and Co2MnSi-MWs are very near, where a = 5.78 Å and 5.71 Å, respectively. However, the samples have the same space group, i.e., Fm3¯m (FCC) type, the crystallite size is different as illustrated in Table 2. The Co2FeSi and Co2MnSi glass-coated microwires have roughly similar crystallite size (≈ 37 nm) and reduced to ≈ 21 nm for Ni2FeSi-MWs. The values of crystallite size and the degree of microstructure ordered have a strong effect on the magnetic behavior of the samples.

3.2. Magnetic characterization

3.2.1. Room temperature magnetic properties

To check the magnetic behavior of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs at room temperature, we performed the magnetic measurements at two directions, axial, i.e., parallel to the metallic nuclei axis and out-of-plane, i.e., perpendicular to the wire axis by using PPMS magnetometer. The out-of-planes loops appeared linear with vanishing coercivity and reduced remanence, i.e., Hc and Mr ≈ zero (not shown). The vanishing Hc and Mr indicate that all the magnetization lies in the in-plane (axial) direction and the out-of-plane direction is the hard easy magnetization axis s for all MWs-samples.
Figure 2 shows M-H loops of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs at room temperature with an applied magnetic field parallel to the microwire axis, i.e., axial direction. Ni2FeSi-MWs and Co2FeSi-MWs show a squared hysteresis loops shape, meanwhile the hysteresis loop of Co2MnSi-MWs sample is not perfectly squared. For Co2MnSi-MWs, it appears that the easy magnetization axis is not perfectly axial and is possibly tilted with an angle away from the wire axis. Unfortunately, we do not have the possibilities to measure the angular magnetic behavior to determine accurately the magnetic anisotropy of the sample.
Ni2FeSi-MWs show hard magnetic behavior with coercivity 138 Oe which 16 times higher than Co2MnSi-MWs and 4 times higher than Co2FeSi-MWs (see Table 1). The increase in the coercivity and the in-plane anisotropy field of Ni2FeSi-MWs must be attributed to the different of microstructure. Surprisingly, the smallest value of crystallite size is observed in Ni2FeSi sample. Therefore, high coercivity of Ni2FeSi sample may be associated with the disordered microstructure of B2-type , which strongly affects the magnetization reversal process, domain structures and its movement.
In addition, the magnetocrystalline anisotropy play an important role for the overall magnetic behavior. Thus, the enhance coercivity detected inNi2FeSi-MWs and the high reduced remanent magnetization of Co2FeSi-MWs suggest the scenario, when the crystalline texture affects the magnetic anisotropy. In particular, easy magnetization axis can be aligned along the (220) and (420) reflections. However, the Co2MnSi-MWs sample shows a well-defined ordered structure with L21-type The lowest reduced remanence and coercivity observed in Co2MnSi-MWs sample can be due to the mismatching between the magnetocrystalline anisotropy and the crystalline structure. As demonstrated in our previous research, the magnetic anisotropy behavior of Heusler-based glass-coated microwires is primarily influenced by two main factors: uniaxial magnetic anisotropy and cubic magnetocrystalline anisotropy [14,17]. It has been reported elsewhere [18,19,20,21,30] that the ρ-ratio is directly related to the strength of internal stresses. Therefore, it is expected, that ρ-ratio affects the relative content of the crystalline phase and correlates with modifications in the magnetic properties. Specifically, cubic magnetocrystalline anisotropy emerges as the predominant factor governing magnetic anisotropy. Regrettably, at present, experimental measurement of this type of anisotropy remains unfeasible. However, the presence of a perfectly squared hysteresis loop strongly indicates its significant impact on the magnetic properties of the Ni2FeSi-MWs and Co2FeSi-MWs samples.
Table 3. The coercivity (Hc), reduced remanence (Mr) and in-plane anisotropy field (Hk) as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires. glass-coated microwires with fixed aspect ratio measured at room temperature.
Table 3. The coercivity (Hc), reduced remanence (Mr) and in-plane anisotropy field (Hk) as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires. glass-coated microwires with fixed aspect ratio measured at room temperature.
Sample Hc (Oe) Mr Hk (Oe)
Ni2FeSi 138 ± 0.5 0.33± 0.01 350 ± 0.5
Co2FeSi 45 ± 0.5 0.92 ± 0.01 88 ± 0.5
Co2MnSi 7 ± 0.5 0.22 ± 0.01 45 ± 2

3.2.2. Thermomagnetic properties

It is worth noting that the temperature stability of ferromagnetic materials is a crucial characteristic for their possible applications in spintronic and sensing devices. Hence, we investigated the magnetic behavior of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs with fixed ρ- ratio for a wide range of measurement temperatures, 5-400 K. The shape of the loops follows the same trend, observed at room temperature: non-squared for the Co2MnSi-MWs and quite squared for Ni2FeSi-MWs and Co2FeSi-MWs samples. In Figure 3 and Figure 4, the M-H loops, and the evolution of Hc and Mr with the temperature is shown. This behavior can be explained considering that for Ni2FeSi-MWs and Co2FeSi-MWs samples, cubic magnetocrystalline anisotropy prevails up to 400 K.
By analyzing M-H loops measured at temperature range, 5–400 K of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs with fixed ρ- ratio, an interesting magnetic behavior is found for the temperature dependence of Hc in Ni2FeSi-MWs. First Ni2FeSi-MWs show highest coercivity value at all temperature ranges compared to the Co2-based glass-coated samples with same aspect ratio. In addition, Hc temperature dependence does not show uniform behavior, where two flipped points at T = 200 K and 50 K is observed. At these points the tendency of Hc dramatically change with temperature (see Figure 4a). Meanwhile the temperature dependence of Hc for Co2FeSi-MWs and Co2MnSi-MWs shows a quite stable tendency with temperature. The improved coercivity stability observed at Co2MnSi-MWs is strongly related to the high ordered microstructure with L21-type (see Figure 1). However, both Ni2FeSi-MWs and Co2FeSi-MWs have disordered microstructure with B2-type and A2-type, respectively. The Co2FeSi-MWs show higher coercivity thermal stability due to A2-type microstructure show higher energy stability compared to B2-type [50,51,52]. Thus, Co2FeSi-MWs its Hc vs T appears more stable compared to Ni2FeSi-MWs. Additionally, Mr vs T tendency has regular ferromagnetic behavior with temperature, where monotonic increasing of Mr by decreasing T is observed (see Figure 4b). Both Ni2FeSi-MWs and Co2FeSi-MWs have higher Mr values for the all range of measuring temperatures compared to Co2MnSi-MWs. The higher values of Mr for Ni2FeSi-MWs and Co2FeSi-MWs suggested the dominant cubic magnetocrystalline anisotropy at a wide range of measuring temperatures.
Figure 5 shows the complete thermomagnetic behavior of Ni2FeSi-MWs, Co2FeSi-MWs and Co2MnSi-MWs with fixed ρ- ratio. We studied the FC and FH temperature dependence of magnetization to check any possible phase transition. Thus, the measurements were performed at low magnetic field 50 Oe. Ni2FeSi-MWs shows regular ferromagnetic behavior where the FC and FH curves increase by decreasing the temperature from 400 to 5 K. For Co2FeSi-MWs and Co2MnSi-MWs FC and FH magnetizations curves show non-homogonous behavior, besides an irreversible magnetic behavior at T = 125 K takes place. Among the factor that affect irreversible behavior of magnetization versus temperature are the induced martensitic transition and the changing in the internal stresses associated with the glass-coating layer with temperature. As illustrated in Figure 5, the FC and FH magnetizations. curves have a perfect matching and monotonic increasing by decreasing the temperature from 400 to 5 K in Ni2FeSi sample (see Figure 5a). Accordingly, we can assume that the internal stress induced by the covering glass-layer during the fabrications process have stable and uniformed effect on magnetic properties of Ni2FeSi sample. Meanwhile, for Co2FeSi-MWs and Co2MnSi-MWs, the internal stress does not show a uniform effect at all temperature range, where from 400 to 300 K FC and FH have a good matching behavior, by decreasing the temperature below 300 K the mismatching start appears. Due to the disordered microstructure nature of Co2FeSi-MWs FC and FH do not have a smoothing behavior with temperature compared to Co2MnSi-MWs.
The current outcome result reveals the influence of the internal stress induced by the glass coating layer is very sensitive to the chemical compositions and the microstructure ordering of X2YX-based glass-coated microwires. As a result, different magnetic and structure response is observed in glass-coated microwires with different metallic nucleus chemical compositions. In our previous work, we illustrated how the internal stress is strongly related to the geometric dimensions, and how important are the external applied field, annealing temperature/time condition and microstructure ordering of the host metallic alloys.

5. Conclusions

In summary, we succeeded in preparing of X2YZ-based glass-coated microwires with same aspect ratio. In such X2YZ-based glass-coated microwires we studied the effect of different chemical composition of magnetic materials, i.e., metallic nuclei, on the internal stress. Notable variation in magnetic and structured properties have been observed. For the microstructure investigation different microstructure features are detected varied between the disordered (A2-type and B2-Type) for Co2FeSi-MWs and Ni2FeSi-MWs, respectively. Meanwhile, well defined ordered L21-type is observed at Co2MnSi-based glass-coated microwires. The variation in the microstructure has a strong effect on the magnetic behavior of the samples, where a notable change in Hc, Hk, Mr, FC and FH tendency with temperature and magnetic field. The high coercivity thermal stability observed in Co2MnSi and Co2FeSi-based glass-coated microwires make them promising candidates for different industrial applications.

Author Contributions

Conceptualization, M.S. and A.Z.; methodology, V.Z.; validation, M.S., V.Z. and A.Z.; formal analysis, M.S.; investigation, M.S. and A.Z.; resources, V.Z. and A.Z.; data curation, M.I.; writing—original draft preparation, M.S. and A.Z.; writing—review and editing, M.S. and A.Z.; visualization, M.S. and M.I.; supervision, V.Z and A.Z.; project administration, V.Z. and A.Z.; funding acquisition, V.Z. and A.Z. All authors have read and agreed to the published version of the manuscript.

Funding

Please add: This research was funded by the Spanish MICIN, under PID2022-141373NBI00, by EU under “INFINITE” (Horizon Europe) project and by the Government of the Basque Country, under PUE_2021_1_0009 and Elkartek (MINERVA, ZE-KONP and MAGAF) projects and by under the scheme of “Ayuda a Grupos Consolidados” (Ref.: IT1670-22). MS wish to acknowledge the funding within the Maria Zambrano contract by the Spanish Ministerio de Universidades and European Union –Next Generation EU (“Financiado por la Unión Europea-Next Generation EU”). We also wish to thank the administration of the University of the Basque Country, which not only provides very limited funding, but even expropriates the resources received by the research group from private companies for the research activities of the group. Such interference helps keep us on our toes.

Data Availability Statement

Not applicable.

Acknowledgments

The authors thank for technical and human support provided by SGIker Magnetic Measurements Gipuzkoa (UPV/EHU/ ERDF, EU).

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. F. Heusler Verhandlungen Dtsch. Phys. Ges., 1903, 5, p. 219.
  2. Elphick, K.; Frost, W.; Samiepour, M.; Kubota, T.; Takanashi, K.; Sukegawa, H.; Mitani, S.; Hirohata, A. Heusler Alloys for Spintronic Devices: Review on Recent Development and Future Perspectives. Sci. Technol. Adv. Mate. 2021, 22, 235–271. [Google Scholar] [CrossRef] [PubMed]
  3. Bai, Z.; Shen, L.E.I.; Han, G.; Feng, Y.P. Data Storage: Review of Heusler Compounds. Spin 2012, 2, 1230006. [Google Scholar] [CrossRef]
  4. Chumak, O.M.; Pacewicz, A.; Lynnyk, A.; Salski, B.; Yamamoto, T.; Seki, T.; Domagala, J.Z.; Głowiński, H.; Takanashi, K.; 423 Baczewski, L.T.; et al. Magnetoelastic Interactions and Magnetic Damping in Co2Fe0.4Mn0.6Si and Co2FeGa0.5Ge0.5 Heusler Alloys Thin Films for Spintronic Applications. Sci. Rep. 2021, 11, 7608. [Google Scholar] [CrossRef] [PubMed]
  5. Li, P.; Koo, J.; Ning, W.; Li, J.; Miao, L.; Min, L.; Zhu, Y.; Wang, Y.; Alem, N.; Liu, C.X.; et al. Giant Room Temperature Anomalous Hall Effect and Tunable Topology in a Ferromagnetic Topological Semimetal Co2MnAl. Nat. Commun. 2020, 421 11, 1–8. [Google Scholar] [CrossRef]
  6. Gutfleisch, O.; Willard, M.A.; Bruck, E.; Chen, C.H.; Sankar, S.G.; Liu, J.P. Magnetic Materials and Devices for the 21st Century: Stronger, Lighter, and More Energy Efficient. Adv. Mater. 2011, 23, 821–842. [Google Scholar] [CrossRef]
  7. Franco, V.; Blázquez, J.S.; Ipus, J.J.; Law, J.Y.; Moreno-Ramírez, L.M.; Conde, A. Magnetocaloric effect: From materials research to refrigeration devices. Prog. Mater. Sci. 2018, 93, 112–232. [Google Scholar] [CrossRef]
  8. Chatterjee, S.; Chatterjee, S.; Giri, S.; Majumdar, S. Transport properties of Heusler compounds and alloys. J. Phys. Condens. Matter 2022, 34, 013001. [Google Scholar] [CrossRef]
  9. Silber, R.; Kral, D.; Stejskal, O.; Kubota, T.; Ando, Y.; Pistora, J.; Veis, M.; Hamrle, J.; Kuschel, T. Scaling of quadratic and linear magneto-optic Kerr effect spectra with L2(1) ordering of Co2MnSi Heusler compound. Appl. Phys. Lett. 2020, 116, 262401. [Google Scholar] [CrossRef]
  10. Tavares, S.; Yang, K.; Meyers, M.A. Heusler alloys: Past, properties, new alloys, and prospects. Prog. Mater. Sci. 2023, 132, 101017. [Google Scholar] [CrossRef]
  11. Balke, B.; Wurmehl, S.; Fecher, G.H.; Felser, C.; Kübler, J. Rational Design of New Materials for Spintronics: Co2FeZ (Z=Al, Ga, Si, Ge). Sci. Technol. Adv. Mater. 2008, 9, 014102. [Google Scholar] [CrossRef]
  12. Jourdan, M.; Minár, J.; Braun, J.; Kronenberg, A.; Chadov, S.; Balke, B.; Gloskovskii, A.; Kolbe, M.; Elmers, H.J.; Schönhense, G.; et al. Direct Observation of Half-Metallicity in the Heusler Compound Co2MnSi. Nat. Commun. 2014, 5, 3974. [Google Scholar] [CrossRef] [PubMed]
  13. Životský, O.; Skotnicová, K.; Čegan, T.; Juřica, J.; Gembalová, L.; Zažímal, F.; Szurman, I. Structural and Magnetic Properties of Inverse-Heusler Mn2FeSi Alloy Powder Prepared by Ball Milling. Materials 2022, 15, 697. [Google Scholar] [CrossRef] [PubMed]
  14. Salaheldeen, M.; Garcia, A.; Corte-Leon, P.; Ipatov, M.; Zhukova, V.; Zhukov, A. Unveiling the Effect of Annealing on Magnetic Properties of Nanocrystalline Half-Metallic Heusler Co2FeSi Alloy Glass-Coated Microwires. J. Mater. Res. Technol. 2022, 20, 4161–4172. [Google Scholar] [CrossRef]
  15. Khovaylo, V.V.; Rodionova, V.V.; Shevyrtalov, S.N.; Novosad, V. Magnetocaloric Effect in “Reduced” Dimensions: Thin Films, Ribbons, and Microwires of Heusler Alloys and Related Compounds. Phys. Status Solidi 2014, 251, 2104–2113. [Google Scholar] [CrossRef]
  16. Herzer, G. Amorphous and Nanocrystalline Materials. In Encyclopedia of Materials: Science and Technology; Elsevier: Amsterdam, The Netherlands, 2001; pp. 149–156. [Google Scholar]
  17. Salaheldeen, M.; Garcia-Gomez, A.; Corte-León, P.; Gonzalez, A.; Ipatov, M.; Zhukova, V.; Gonzalez, J.M.; López Antón, R.; Zhukov, A. Manipulation of Magnetic and Structure Properties of Ni2FeSi Glass-Coated Microwires by Annealing. J. Alloys Compd. 2023, 942, 169026. [Google Scholar] [CrossRef]
  18. Antonov, A.S.; Borisov, V.T.; Borisov, O.V.; Prokoshin, A.F.; Usov, N.A. Residual quenching stresses in glass-coated amorphous ferromagnetic microwires. J. Phys. D: Appl. Phys. 2000, 33, 1161–1168. [Google Scholar] [CrossRef]
  19. Zhukova, V.; Cobeño, A.F.; Zhukov, A.; de Arellano Lopez, A.R.; López-Pombero, S.; Blanco, J.M.; Larin, V.; Gonzalez, J. Correlation between magnetic and mechanical properties of devitrified glass-coated Fe71.8Cu1Nb3.1Si15B9.1 microwires. J. Magn. Magn. Mater., 2002, 249, 79–84. [Google Scholar] [CrossRef]
  20. Wang, C.; Cao, G.; Liu, J.; Zhang, Y.; Liu, R.; Wang, F.; Zhang, M.; Wang, L.; Zhang, B. Direct Current Annealing Modulated Ordered Structure to Optimize Tensile Mechanical Properties of Co-Based Amorphous Metallic Microwires. Metals 2022, 12, 1427. [Google Scholar] [CrossRef]
  21. Chiriac, H.; Óvári, T.A.; Pop, G. Internal stress distribution in glass-covered amorphous magnetic wires. Phys. Rev. B 1995, 52, 10104–10113. [Google Scholar] [CrossRef]
  22. Ulitovsky, A.V.; Maianski, I.M.; Avramenco, A.I. 1960 Method of Continuous Casting of Glass Coated Microwire. USSR Patent 128427, 6 May 2015. Bulletin, No 10, p. 14. 128427, 6 May 2015. Bulletin, No 10, p.
  23. Salaheldeen, M.; Wederni, A.; Ipatov, M.; Zhukova, V.; Zhukov, A. Carbon-Doped Co2MnSi Heusler Alloy Microwires with Improved Thermal Characteristics of Magnetization for Multifunctional Applications. Materials 2023, 16, 5333. [Google Scholar] [CrossRef]
  24. Zhukov, A.; Corte-Leon, P.; Gonzalez-Legarreta, L.; Ipatov, M.; Blanco, J.M.; Gonzalez, A.; Zhukova, V. Advanced Functional Magnetic Microwires for Technological Applications. J. Phys. D. Appl. Phys. 2022, 55, 253003. [Google Scholar] [CrossRef]
  25. Nematov, M.G.; Baraban, I.; Yudanov, N.A.; Rodionova, V.; Qin, F.X.; Peng, H.X.; Panina, L.V. Evolution of the magnetic anisotropy and magnetostriction in Co-based amorphous alloys microwires due to current annealing and stress-sensory applications. J. Alloys Compd. 2020, 837, 155584. [Google Scholar] [CrossRef]
  26. Salaheldeen, M.; Wederni, A.; Ipatov, M.; Zhukova, V.; Lopez Anton, R.; Zhukov, A. Enhancing the Squareness and Bi- Phase Magnetic Switching of Co2FeSi Microwires for Sensing Application. Sensors 2023, 23, 5109. [Google Scholar] [CrossRef] [PubMed]
  27. Chiriac, H.; Lupu, N.; Stoian, G.; Ababei, G.; Corodeanu, S.; Óvári, T.A. Ultrathin Nanocrystalline Magnetic Wires. Crystals 2017, 7, 48. [Google Scholar] [CrossRef]
  28. Salaheldeen, M.; Wederni, A.; Ipatov, M.; Zhukova, V.; Zhukov, A. Novel Co2Mn-Based Heusler Alloy Microwires with Promising Magnetization Thermal Stability for Multifunctional Applications. Preprints.org 2023, 2023061088. [Google Scholar] [CrossRef]
  29. Cobeño, A.F.; Zhukov, A.; de Arellano - Lopez, A.R.; Elías, F.; Blanco, J.M.; Larin, V.; González, J. Physical properties of nearly zero magnetostriction Co-rich glass-coated amorphous microwires. J. Mater. Res 1999, 14, 3775–3783. [Google Scholar] [CrossRef]
  30. Torcunov, A.V.; Baranov, S.A.; Larin, V.S. The internal stresses dependence of the magnetic properties of cast amorphous microwires covered with glass insulation. J. Magn. Magn. Mater. 1999, 196–197, 835–836. [Google Scholar] [CrossRef]
  31. Kozejova, D.; Fecova, L.; Klein, P.; Sabol, R.; Hudak, R.; Sulla, I.; Mudronova, D.; Galik, J.; Varga, R. Biomedical Applications of Glass-Coated Microwires. J. Magn. Magn. Mater. 2019, 470, 2–5. [Google Scholar] [CrossRef]
  32. Grabco, D.; Dyntu, M.; Meglei, D.; Shikimaka, O. Microstructure and Strength Properties of Germanium Microwires for Biomedical Devices. In: Gogotsi, Y.G., Uvarova, I.V. (eds) Nanostructured Materials and Coatings for Biomedical and Sensor Applications. NATO Science Series, 2003, vol 102. Springer, Dordrecht. [CrossRef]
  33. Mitxelena-Iribarren, O.; Campisi, J.; de Apellániz, I.M.; Lizarbe-Sancha, S.; Arana, S.; Zhukova, V.; Mujika, M.; Zhukov, A. Glass-coated ferromagnetic microwire-induced magnetic hyperthermia for in vitro cancer cell treatment. Mater. Sci. Eng. C 2020, 106, 110261. [Google Scholar] [CrossRef]
  34. Salaheldeen, M.; Wederni, A.; Ipatov, M.; Gonzalez, J.; Zhukova, V.; Zhukov, A. Elucidation of the Strong Effect of the Annealing and the Magnetic Field on the Magnetic Properties of Ni2-Based Heusler Microwires. Crystals 2022, 12, 1755. [Google Scholar] [CrossRef]
  35. Salaheldeen, M.; Wederni, A.; Ipatov, M.; Zhukova, V.; Zhukov, A. Preparation and Magneto-Structural Investigation of High-Ordered (L21 Structure) Co2MnGe Microwires. Processes 2023, 11, 1138. [Google Scholar] [CrossRef]
  36. Salaheldeen, M.; Talaat, A.; Ipatov, M.; Zhukova, V.; Zhukov, A. Preparation and Magneto-Structural Investigation of Nanocrystalline CoMn-Based Heusler Alloy Glass-Coated Microwires. Processes 2022, 10, 2248. [Google Scholar] [CrossRef]
  37. Hennel, M.; Varga, M.; Frolova, L.; Nalevanko, S.; Ibarra-Gaytán, P.; Vidyasagar, R.; Sarkar, P.; Dzubinska, A.; Galdun, L.; Ryba, T.; et al. Heusler-Based Cylindrical Micro- and Nanowires. Phys. Status Solidi A 2022, 219, 2100657. [Google Scholar] [CrossRef]
  38. Zhukov, A.; Ipatov, M.; del Val, J.J.; Zhukova, V. and Chernenko, V.A. Magnetic and structural properties of glass-coated Heusler-type microwires exhibiting martensitic transformation, Sci. Rep., 2018, 8, 621. [CrossRef]
  39. Salaheldeen, M.; Ipatov, M.; Corte-Leon, P.; Zhukova, V.; Zhukov, A. Effect of Annealing on the Magnetic Properties of Co2MnSi-Based Heusler Alloy Glass-Coated Microwires. Metals 2023, 13, 412. [Google Scholar] [CrossRef]
  40. Hennel, M.; Galdun, L.; Džubinská, A.; Reiffers, M.; Varga, R. High efficiency direct magnetocaloric effect in Heusler Ni2MnGa microwire at low magnetic fields. J. Alloys Compd. 2023, 960, 170621. [Google Scholar] [CrossRef]
  41. Rodionova,V. ; Ilyn, M. ; Granovsky, A. ; Perov, N. ; Zhukova, V. ; Abrosimova, G. ; Aronin, A. ; Kiselev, A. ; Zhukov, A. Internal stress induced texture in Ni-Mn-Ga based glass-covered microwires. J. Appl. Phys. 2013, 114,123914.
  42. Zhukov, A.; Rodionova, V.; Ilyn, M.; Aliev, A. M.; Varga, R.; Michalik, S.; Aronin, A.; Abrosimova, G.; Kiselev, A.; Ipatov, M.; Zhukova, V. Magnetic properties and magnetocaloric effect in Heusler-type glass-coated NiMnGa microwires. J. Alloys. Compd. 2013, 575, 73–79. [Google Scholar] [CrossRef]
  43. Baranov, S.A.; Larin, V.S.; Torcunov, A.V. Technology, Preparation and Properties of the Cast Glass-Coated Magnetic Microwires. Crystals 2017, 7, 136. [Google Scholar] [CrossRef]
  44. Chiriac, H.; Ovari, T.-A. Amorphous glass-covered magnetic wires: Preparation, properties, applications. Prog. Mater. Sci. 1996, 40, 333–407. [Google Scholar] [CrossRef]
  45. Zhukova, V.; Blanco, J.M.; Ipatov, M.; Zhukov, A. Magnetoelastic contribution in domain wall dynamics of amorphous microwires. Physica B 2012, 407, 1450–1454. [Google Scholar] [CrossRef]
  46. Klein, P.; Varga, R.; Badini-Confalonieri, G.A.; Vazquez, M. Domain Wall Dynamics in Amorphous and Nanocrystalline 492 FeCoMoB Microwires. J. Nanosci. Nanotechnol. 2012, 12, 7464–7467. [Google Scholar] [CrossRef]
  47. Corodeanu, S.; Hlenschi, C.; Chiriac, H.; Óvári, T.-A.; Lupu, N. Comparative Study of the Magnetic Behavior of FINEMET Thin Magnetic Wires: Glass-Coated, Glass-Removed, and Cold-Drawn. Materials 2023, 16, 1340. [Google Scholar] [CrossRef] [PubMed]
  48. Salaheldeen, M.; Ipatov, M.; Zhukova, V.; García-Gomez, A.; Gonzalez, J.; Zhukov, A. Preparation and magnetic properties of Co2-based Heusler alloy glass-coated microwires with high Curie temperature. AIP Adv. 2023, 13, 025325. [Google Scholar] [CrossRef]
  49. Salaheldeen, M.; Zhukova, V.; Wederni, A.; Ipatov, M.; Zhukov, A. Magnetic Properties of Co2MnSi-based Heusler Alloy Glass-coated Microwires. IEEE Trans. Magn 2023. [Google Scholar] [CrossRef]
  50. Ahmad, A.; Mitra, S.; Srivastava, S.K.; Das, A.K. Size-Dependent Structural and Magnetic Properties of Disordered Co2FeAl Heusler Alloy Nanoparticles. J. Magn. Magn. Mater. 2019, 474, 599–604. [Google Scholar] [CrossRef]
  51. Zhang, X.; Han, L.; Dehm, G.; Liebscher, C.H. Microstructure and Physical Properties of Dual-Phase Soft Magnetic Fe-Co-Ti-Ge Alloys. J. Alloys Compd. 2023, 945, 169282. [Google Scholar] [CrossRef]
  52. Zhang, H.G.; Song, B.T.; Chen, J.; Yue, M.; Liu, E.K.; Wang, W.H.; Wu, G.H. Magnetization Variation in Fe–Cr-Ga System. Intermetallics 2019, 113, 106580. [Google Scholar] [CrossRef]
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Figure 1. X-ray diffraction pattern of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires at room temperature.
Figure 1. X-ray diffraction pattern of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires at room temperature.
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Figure 2. (a) Hysteresis loops at room temperature of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio.
Figure 2. (a) Hysteresis loops at room temperature of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio.
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Figure 3. Hysteresis loops at different temperature of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio. All loops have been measured at a temperature range from 300 K to 5 K.
Figure 3. Hysteresis loops at different temperature of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio. All loops have been measured at a temperature range from 300 K to 5 K.
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Figure 4. Temperature dependence of the coercivity (a) and normalized remanence (b) of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio. (Lines for eye guide).
Figure 4. Temperature dependence of the coercivity (a) and normalized remanence (b) of as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio. (Lines for eye guide).
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Figure 5. Temperature dependence of magnetization measured of as prepared (a) Ni2FeSi, (b) Co2FeSi and (c) Co2MnSi glass-coated microwires with fixed aspect ratio with applied external magnetic field 50 Oe.
Figure 5. Temperature dependence of magnetization measured of as prepared (a) Ni2FeSi, (b) Co2FeSi and (c) Co2MnSi glass-coated microwires with fixed aspect ratio with applied external magnetic field 50 Oe.
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Table 1. The geometrical parameters dmetal (µm), Dtotal (µm), aspect ratio, nominal ratio and average (Av.) of atomic percentage of Ni, Co, Fe, Mn and Si elemental composition in as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires.
Table 1. The geometrical parameters dmetal (µm), Dtotal (µm), aspect ratio, nominal ratio and average (Av.) of atomic percentage of Ni, Co, Fe, Mn and Si elemental composition in as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires.
Sample dmetal (µm) Dtotal (µm) Aspect ratio
(ρ = dmetal/ Dtotal)		 Chemical composition Nominal ratio
Ni2FeSi 9.79± 0.1 20.02± 0.1 0.49± 0.02 Ni51Fe23Si26 2:1:1
Co2FeSi 9.65± 0.1 19.88± 0.1 0.49± 0.01 Co48Fe25Si31 2:1:1
Co2MnSi 9.83± 0.1 19.94± 0.1 0.50± 0.01 Co46Mn24Si30 2:1:1
Table 2. Crystallographic information as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio.
Table 2. Crystallographic information as prepared Ni2FeSi, Co2FeSi and Co2MnSi glass-coated microwires with fixed aspect ratio.
Sample Crystallite size (nm) Space group Cell parameters
(a (Å))		 Strukturbericht Designation
Ni2FeSi 21.3± 0.3 Fm3¯m (FCC) 5.78 B2 (disordered)
Co2FeSi 37.3± 0.5 Fm3¯m (FCC) 2.81 A2 (disordered)
Co2MnSi 36.92± 0.5 Fm3¯m (FCC) 5.71 L21 (ordered)
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