1. Introduction
Investigations of innovative materials, particularly half-metals displaying ferromagnetism at a wide range of temperatures, have intensified due to the development of a new generation of spintronic devices [
1]. Among the most extensively studied materials are the Heusler alloys, defined as magnetic intermetallic. The Heusler alloys present a vast family of ternary intermetallic compounds with a variety of magnetic phenomena. Several of such compounds are well known for their unique properties, such as high Curie temperature, half metallicity, and excellent tenability for metallic Heusler alloys, in particular, are of great interest due to the high spin-polarized current close to the Fermi level, which is predicted to increase the efficiency of spintronic devices. This can be exploited to enhance the efficiency of spin-injecting and information storage devices [
2,
3]. Depending on the nature of magnetic sub-lattices, a Heusler alloy is called either half Heusler compounds or full Heusler compounds [
4,
5].
Their generic formula is X
2YZ. In general, X and Y are d-group transition metal elements. X is usually a transition metal 3d (Fe, Co, Ni, Cu, Zn), 4d (Ru, Rh, Pd, Ag, Cd), or 5d (Ir, Pt, Au). The position of Y is usually occupied by 3d (Ti, V, Cr, Mn), 4d (Y, Zr, Nb), 5d (Hf, Ta), or by lanthanides (Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) or actinides (U). While, Z is the p-group main elements III-B (Al, Ga, In, Tl), IV-B (Si, Ge, Sn, Pb), or V-B (As, Sb, Bi) [
6,
7]. The parent phase may be stabilized by the covalent link created by the p-d orbital hybridization between p and d-group atoms. One of the most attractive materials for multiple-function applications are Co
2-based full/half-Heusler alloys with high Curie temperatures (Tc > 1100 K), high magnetic moments, distinct electronic structures, and low Gilbert damping constants (= 0.004) [
4,
8]. Because of their distinctive electronic band structures, some Co
2-based full Heusler alloys also exhibit a significant anomalous Hall effect, in addition to half-metallic ferromagnetism [
9]. Accordingly, Co
2-based Heusler alloys have attracted the scientific community's attention and, therefore, have been widely explored experimentally. Over the past ten years, a theoretical and experimental study has been conducted to fully understand the crystalline structure [
10,
11]. Thus, two crystalline phases of Heusler alloys can be found: the high-symmetry austenite phase, which has the simplest structure as a cubic L2
1 (high-ordered phase) or B2 structure (disorder phase), and the less-symmetrical martensitic phase [
6].
Using the appropriate manufacturing and synthesis procedures, alloys can acquire the ordered austenitic structure. In some cases, the L2
1 phase can be obtained by annealing the alloys at high temperatures for several hours, followed by a long cooling procedure to create a solid-state reaction [
12]. In this instance, the formation of this phase is promoted by the homogenization of the chemical composition and the removal of the impurities in produced alloys [
13,
14]. Other synthesized techniques, like melt spinning or atomization can also be used to obtain the L2
1 phase in Heusler alloys by rapid solidification. These procedures consist of quenching the molten alloy at a high cooling rate to eliminate the formation of other phases and promote the formation of the ordered one [
14,
15,
16,
17]. Otherwise, the formation of nanocrystalline powder alloys can lead to reach the fully ordered L2
1 structure. Alternatively, mechanical alloying consisting of milling of a mixture of the constituent elements of the desired alloy in a ball milling for several hours or even days can be used. Hereafter, the obtained powders can be consolidated into bulk materials by hot pressing or sintering [
18]. It should be noted that the composition of the alloy and the processing techniques employed have a significant impact on the attainment of the L2
1 structure [
15]. Depending on the material's desired qualities and intended applications, different processing conditions may be suitable.
Co
2Mn-based alloys with an L2
1 structure exhibit a ferromagnetic ordering, which makes them attractive for various magnetic applications [
5,
19]. In addition, this ordered structure exhibits, making it suitable for high-temperature applications [
20]. Moreover, to describe the mechanical stability of alloys exhibiting an L2
1-ordered structure, the stability of some elastic constants against external forces was examined. When analyzing the elastic constants and other related mechanical excellent mechanical properties, such as high strength, good ductility, and high fracture toughness, were observed [
21]. Such properties are suitable for thermoelectric applications and development of devices based on spintronic.
Recently, Taylor-Ulitovsky technique involving rapid melt quenching has been successfully used for the fabrication of thin glass-coated magnetic microwires from Heusler alloys [
22,
23]. The Taylor-Ulitovsky process allows preparing of a substantial amount (up to several km) of metallic microwires covered by glass coating from a few grams of master alloy within a few minutes [
22,
24,
25]. As discussed elsewhere, such fabrication technique provides a favorable surface-to-volume ratio, tunable diameter, d, of the metallic nucleus, and glass-coating thickness. Additionally, the internal stress magnitude is tunable by the ratio,
ρ, between the metallic nucleus diameter, d, and total diameter, D [
22]. The preferably axial origin of such internal stresses substantially affects the magnetic anisotropy and particularly the easy magnetization axis of glass-coated microwires [
24,
26]. Besides, the ability to fabricate glass-coated microwires with various structures (such as amorphous, nanocrystalline, and granular) offers a special advantage for researching the impact of various microstructures on the physical properties of the same material [
25,
26].
In our previous investigations, we attempted to obtain a high degree of ordered Co
2Mn-based glass-coated microwires prepared by the Taylor-Ulitovsky technique [
27,
28,
29]. We evaluated various parameters, such as excreting annealing treatments [
30] and varying chemical composition, to improve the structured ordered degree [
31]. High-ordered L2
1 structure is attained at Co
2MnGe as described elsewhere [
19]. Recently, a strong dependence of the geometrical aspect ratio on magneto-structural properties of Heusler glass-coated microwires was discussed [
31]. Therefore, the main objective of the present study is to illustrate the influence of the aspect ratio change on the magneto-structural behavior of the well know Co
2MnSi alloys for multifunctional applications.
2. Materials and Methods
Two significant steps are involved in the production of Co
2MnSi glass-coated microwires. First of all, the melting process begins by melting the nominal high purity (Co (99.99%), Mn (99.9%), and Si (99.9%)) elements in an arc melting furnace. The alloy components were weighed according to the desired composition and placed in a water-cooled copper mold. Manganese was supplemented with an extra two weight percent to compensate for the losses that can be caused by
its evaporation during the production process. The melting procedure was repeated five times to attain an alloy with higher homogeneity and a uniform microstructure [
16,
27,
28]. At this stage, the Co
2MnSi alloy has solidified into an ingot, permitting us to proceed to the manufacturing of Co
2MnSi glass-coated microwires through the Taylor-Ulitovsky technique [
26,
27,
28] Afterwards, the obtained metal ingot (normally a few grams) is again subjected to melting inside a Pyrex glass tube by a high-frequency inductor (normally 350-500 kHz). The glass capillary softened glass is then formed from the softened glass, which is picked up by a spinning pick-up spool [
32]. Hereafter, a microwire with a metallic core completely coated in a continuous, thin, and flexible glass covering is fashioned as the molten metallic alloy fills the glass capillary. In this fabrication process, a combined microwire having a glass capillary over a metallic nucleus inside of it is susceptible to rapid solidification, as it passes through a stream of coolant water [
33]. Although the diameter of the metallic nucleus is constrained by the starting amount of the master alloy droplet, the amount of glass employed in the process is balanced by the continual passing of the glass tube through the inductor zone. One
of the advantage
s of the Taylor-Ulitovsky procedure is that it allows for the preparation of microwires with a very thin glass coating, normally a few micrometers in thickness. The metallic nucleus diameter, d, and glass-coating thickness can be adjusted by the speed at which the wire is drawn and by the glass, tube feed rate. For this, we are producing two types of Co
2MnSi glass-coated microwires with different geometrical parameters (varying the diameters of nucleus and core-shell), where the diameter of the metallic nuclei, d, and the total wire D is tuned by adjusting the speed of wire drowning and pick-up bobbin rotation [
30]. This manufacturing process is particularly advantageous for alloys containing manganese
as it protects against oxidation by the surrounding glass layer due to the rapid solidification [
27]. Therefore, this procedure proves suitable for the production of such materials, while achieving desired results in terms of quality control. The origins of mechanical internal stresses in glass-coated ferromagnetic microwire are attributed to several factors, such as the difference in the thermal expansion coefficients of metallic alloy solidifying inside the glass coating, the quenching stresses related to the rapid quenching of the metallic alloy and the drawing stresses [
22,
24,
34]. The stresses induced by the difference in the thermal expansion coefficients of metallic alloy and the glass coating are the largest one, being an order of magnitude higher than the other stresses [
22,
34]. The ratio of the metallic nucleus to the entire diameter (d/D) can be used to estimate the first type of stress; glass shell-induced stress. It implies that raising the d/D lowers the stresses caused by the shell [
22,
24,
31,
34].
Henceforward, from the optical microscope, we can extract the diameters of microwires after their production; one with aspect ratio ρ = d/D total = 0.46 and the other with ρ = d/D total = 0.31. Therefore, in this work, two groups of Co2MnSi glass-coated microwires with different d/D; (10.2 µm/ 22.2 µm) and (7.4 µm/ 23.2 µm) were produced and investigated.
For investigating the microstructure, morphology and composition of the obtained glass-coated microwires, we used a scanning electron microscope, attached with an energy-dispersive spectrometry (EDX) device. In addition, their structural analysis has been scrutinized by using a BRUKER X-ray diffractometer (D8 Advance, Bruker AXS GmbH, Karlsruhe, Germany), executed with Cu Kα (λ = 1.54 Å) radiation. The magnetic studies of the Co2MnSi glass-coated microwires are performed by means a Physical Property Measurement System (PPMS) (Quantum Design Inc., San Diego, CA). The measurements of the magnetization curves were executed parallel to the wire axis, where the easy magnetization axis is expected due to the shape magnetic anisotropy, and performed at a varied range of temperature (5- 300 K) and magnetic fields (50 Oe - 1kOe). In order to examine the potential magnetic phase transition or irreversibility, zero-field cooling (ZFC), field cooling (FC), and field heating (FH) protocols were used. The findings are expressed as the normalized magnetization, M/M5K, where M5K is the magnetic moment obtained at 5 K.
4. Discussion
There are several parameters of the Taylor-Ulitovsky fabrication method that affect the metallic nucleus diameter, d, and glass coating thickness of the produced glass-coated microwires. Among these factors are the speed at which the wire is drawn and the glass tube feed or the ingot temperature [
22,
34]. There are several sources o the internal stresses, such as the difference in the thermal expansion coefficients of metallic alloy solidifying inside the glass coating, the quenching stresses related to the rapid quenching of the metallic alloy and the drawing stresses [
22,
24,
34]. The stresses induced by the difference in the thermal expansion coefficients of metallic alloy and the glass coating are the largest one, being an order of magnitude higher than the othe stresses [
22,
34]. As thicker is glass-coating as stronger are internal stresses. Accrodingly, the internal stresses can be modified by the ratio of the metallic nucleus to the entire diameter /D. Thus, raising the d/D ratio diminishes the stresses caused by the shell [
22,
24,
34]. However, it must be taken into account that the quenching rate of the metallic alloy is affected by the thickness of the insulating glass-coating [
22]. Therefore, the crystalline structure can be also affected by the glass-coating thickness [
22,
42,
43,
44]. Additionally, the influence of the internal stresses on crystallization process must be related to the non-equilibrium thermodynamics: the crystals nucleation and growth are affected by the atomic diffusion in the presence of the stress [
45]. From studies of Co
2MnSi microwires, we can deduce that decreasing the d/D ratio from 0.46 (GCMW-B) to 0.31 (GCMW-A) can lead to enhancing the crystallinity and the degree of structural order from a disordered A2 type to an ordered L2
1 cubic structure. Furthermore, changing the geometrical parameters has a huge effect on the magnetic behavior. When compared to GCMW-B, the magnetic behavior of GCMW-A can be significantly modified by applying a moderate magnetic field of 200 Oe instead of 50 Oe. This can be explained by the sensitivity of GCMW-A to small magnetic field changes. However, substantial variations in the magnetic behavior of GCMW-B by applying 1 kOe are detected. Thus, such modification in GCMW-B magnetic behavior is correlated with the X-ray diffraction results, owing to the disordered A2 cubic structure. Moreover, the magnetization curves in GCMW-A tend to overlap gradually by increasing the magnetic field application from 50 Oe to 1 kOe. Therefore, glass-coated Co
2MnSi microwires are sensitive to changing temperature and applied magnetic field, as demonstrated by the magnetic behavior of the GCMW-A sample, making them an appropriate candidate for use as sensing materials.
The current results illustrate the strong dependence of the microstructure and thermomagnetic properties of rather well-known Heusler alloys, i.e., Co2MnSi-based glass coating microwires on its geometric parameters. The ability to tailor the magnetic & structure properties of Heusler –based glass-coated microwires makes these smart systems promising for different applications.
5. Conclusions
In summary, in the current study, we illustrate the effect of changing geometrical parameters during the manufacturing process of Co2MnSi glass-coated microwires on the structure and magnetic properties. Two Co2MnSi microwires coated with glass are produced employing the Taylor Utilovsky method by changing the diameters of the core and total microwire. First microwire GCMW-A shows the average metal core (d) and total (D) diameters of 10.2 and 22.2 μm, respectively. However, the second one present the average metal core (d) and total (D) diameters of 7.4 and 23.8 μm, respectively. From X-ray analysis, we remark that GCMW-A exhibits an L21 cubic ordered structure with Fm3¯m space group, whereas, GCMW-B demonstrates an A2 cubic disordered structure with Im3¯m space group. By comparing both of the XRD diffractograms, the well-defined diffraction patterns presented in GCMW-A express a high crystallinity. Thus, the intensity of the diffraction peak declines with increasing the aspect ratio. This proves that, with relatively low crystallinity, the crystalline size diminishes relating to GCMW-B from 36.62 to 28.02 nm. Regarding the magnetic properties, both samples display dissimilar magnetic responses with the temperature and applied magnetic field. Firstly, by applying 50 Oe the ZFC-FC-FH magnetization curves express an irreversible magnetic behavior, accompanied by a mismatching between the ZFC and FH curves. Furthermore, when applying an extra magnetic field of 200 Oe, no change was perceived, for the (M, T) curves of GCMW-B. However, applying an additional magnetic field in GCMW-A, reduces the gap occurring between ZFC and FH magnetization curves. While applying a stronger magnetic field of 1kOe, ZFC and FH magnetization curves in GCMW-A coincide and express a strong change and mismatching in GCMW-B, relating to the disordered crystalline structure that occurred. Because of the extraordinary thermal stability of the coercivity values of GCMW-A and GCMW-B, Co2MnSi microwires, can be combined in generators, sensors, transformers, and actuators for application potentials.