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Thermal effect on structural and magnetic properties of Fe78B13Si9 annealed amorphous ribbons

In the present work, we study the influence of thermal treatments on the magnetic properties of as-quenched and pre-crystallized Fe78Si9B13 after stress relaxation. The crystallization behavior of amorphous and treated Fe78Si9B13 ribbons was revisited. The measurements were carried out by means of Differential Scanning Calorimetry, by X-ray diffraction and by Vibrating Sample Magnetometer, Susceptometer and fluxmeter. Relaxed samples were heated in the resistivity device up to 700°C and annealed near the onset temperature about 420°C for respectively 1, 3, 5, 8 hours. In asquenched samples, two transition points occur at about 505°C and 564°C but in relaxed sample, the transition points have been found about 552°C and 568°C. Kinetics of crystallization was deduced for all studied samples. Annealing of the as-purchased ribbon shows the occurrence of -Fe and tetragonal Fe3B resulting from the crystallization of the remaining amorphous phase. The effects on magnetic properties were pointed out by relating the structural evolution of the samples. The magnetic measurements show that annealing change the saturation magnetization and the coercive magnetic field values, hence destroying the good magnetic properties of the material. The heat treatment shows that the crystallization has greatly altered the shape of the cycles and moved the magnetic saturation point of the samples. The effect of treatment on the magneto-crystalline anisotropy is also demonstrated.


Introduction
To obtain nanocrystalline structure, different techniques are available; the crystallization method is an effective one. The basic idea is to control the crystal nucleation and growth during the crystallization process by empirical adjusting of the heat treatment conditions. As an example, the isothermal heat treatment at 450°C leads to complete crystallization of the amorphous Fe-B-Si in about 72 hours. By extrapolation, one can estimate that about 277 hours are required for the formation of nanograins of 400 nm size, as reported by [1] The amorphous alloys based on Fe-B-Si are successfully applied as the core materials in distribution transformers due to their low core losses and relatively high saturation magnetization and low exciting current [2]. Therefore, it is necessary to determine both the conditions in which the properties of the as-received state of the metallic glass are conserved and the parameters of the kinetics of change. Knowledge of the crystallization kinetics of amorphous alloys offers the possibility for specific crystalline structures and hence for optimizing their properties. The elimination of both internal and external stresses improves the mobility of the Bloch walls of magnetic domains and facilitates reorientation of spins and magnetic saturation under an applied field H. Stress relaxation is observed by annealing the amorphous alloy at temperatures allowing sufficient atomic diffusion for structural relaxation but not enough to initiate crystallization [3]. The optimization of softmagnetic properties of metallic glasses can be made by dynamical current annealing, One can obtain the structure relaxation, where the atoms rearrange to become more ordered with increasing annealing temperature, without bulk crystallization occurring. Authors reported that whereas there is no trace of crystalline phase for the samples annealed at 420°C, the asquenched sample exhibits a broad peak from amorphous phase which is slightly larger than the corresponding peak of the relaxed sample, implying the occurrence of atomic rearrangement during annealing [4] Moreover, in the relaxed sample, the crystalline phase is still dispersed in the amorphous matrix and the small peak centered in the broad amorphous peak corresponds to Į-Fe phase. The annealing effects on the thermomagnetic structural evolution of the Fe 78 B 13 Si 9 amorphous alloy have an effective disadvantage: the amorphous alloys such as Fe-B-Si are ductile in the as-cast state, but become brittle during conventional annealing [5]. After crystallization, the most attractive properties of an amorphous alloy, such as soft magnetic behavior, high strength, and ductility are usually lost. Thus, the limiting factor of many technological applications of nanocrystalline materials is their brittleness [6].
The magnetic saturation would depend on the internal stress states resulting from the ascast conditions and further treatments of the alloy. Escobar et al. [3] have reported, also like Kronmüller quoted by Luborsky [7], the coercive field dependence on temperature [8]. H. Kronmüller, in [9], again pointed out that the defect concentration and fluctuations affect the magnetic properties of amorphous alloys. This behavior may be compared with the results of Escobar et a1. [3] who optimized the magnetic properties of Fe-Si-B alloys by a very short annealing at 430°C. But it seems that the absolute magnetic saturation of this alloy occurs at higher field in accordance with the work of Pankhurst et a1 [10], who using Mossbauer studies did not reach the saturation state for the same composition with applied field of up to 5T.
The aim of this study is to analyze the thermal, microstructural and magnetic properties of Fe-B-Si metallic glass. As-quenched alloys exhibit the typical macroscopic behavior of fully amorphous structures, while annealing induces, besides strain relaxation, moderate growth of the nanocrystals.
Quenched state (as-cast) and relaxed ribbons which exhibit in a dispersed Į-Fe crystallites, have been investigated, particularly, in point of view of kinetics of crystallization of Fe-B-Si. The non-isothermal Differential Scanning Calorimetry (DSC) was used with the effect of annealing procedure on the structural and magnetic properties.

Experimental
Specimen used in this work are cut from ribbons approximately 25-ȝP WKLFN DQG -mm wide wired, purchased from Allied Chemical Ltd (2605-S2). The amorphous ribbon, which has undergone structural relaxation by heat treatment at about 250° C, for a period of 2 hours, is referred to as a relaxed amorphous alloy.
This treatment is carried out immediately after rapid quenching by Allied Corp either without the application of a magnetic field or under magnetic field according to the requirement. In the case of this study, the magnetic field which allows uniaxial magnetic anisotropy is not applied. This structural relaxation makes it possible to reorganize the amorphous structure by relaxing the constraints due to rapid solidification.
Differential Scanning Calorimetry (DSC) measurements are used to study the thermal behavior. The METLER TOLEDO DSC 822 e apparatus is used. Amorphous and relaxed samples were continuously heated in the device to temperatures at which different crystallization stages could be obtained.
The measurements were carried out at continuous heating rates between 5 and 80 K/minute up to 700°C with accuracy of ±1°C, for as-quenched, relaxed, fully crystallized and isothermally annealed samples at different times. Heat treatment conditions were selected according to the beginning of the pre-crystallization process resulting from the first heating and cooling. At 420 °C, measurements are performed as function of time. This temperature is known to bring the optimum of magnetic quality (near Curie Temperature Tc § & Crystalline phase's characterization was obtained by means of a Siemens D5000 diffractometer using Cu-KĮ radiation. Susceptometer-3Tesla and VSM-9Tesla Quantum Design-PPMS (Physical Property Measurement System) were used for magnetic saturation measurements with high applied magnetic field up to 2 Tesla in order to saturate the asreceived and 420°C-annealed samples.
To observe, in experiments, the dynamics of the walls in ferromagnetic one choose a Fluxmeter [11] for hysteresis loop measurements at variable amplitude. One connected a magnetic circuit like a transformer, by taking the values of magnetic applied field H (T) from primary circuit and magnetic induction B (T) from secondary circuit simultaneously.

DSC results
The Differential Scanning Calorimetry DSC was used to study the crystallization kinetics of Fe 78 Si 9 B 13 glasses at the heating rates of 5, 20, 40 and 80K/m. Differential scanning calorimetry (DSC) measurements of the as-cast Fe 78 Si 9 B 13 metallic glass are presented in Figure 1. In each DSC curve, two clearly separated exothermic peaks are observed; this indicates that during the transformation two principal crystalline phases appear. One can see that the peaks temperatures are higher at higher heating rates.  Differential scanning calorimetry (DSC) measurements of thermally treated and annealed samples at 420°C are presented in figure 2. One can observe from the DSC curve of the sample annealed at 420°C for 8h that only the second crystallization appears. Thus it explains that at this annealing time, the first stage of crystallization have been achieved completely. Figure 2 presents the continuous crystallization process and shows the fully crystallized structure without any transition observed in DSC measurement. However, the DSC curve in fully sample presents a solid-state phase transformation that is not reversible (not reported here).The kinetics indicates that during transformations two crystallization steps appear in table 1. The first crystallization temperatures observed in the thermograms are moved towards higher values with the increasing annealing time.

Analysis of kinetics
These phase transformations may be assumed to be thermally activated processes. For thermally activated processes the heating rate E and the peak temperatures T p are linked by the following equation: E is the pre-exponential factor, R: the gas constant and E a : the apparent activation energy.
The results for activation energies and pre-exponential factors of the two crystallization events observed in the DSC plots are summarized in table 1.  Figure 3 shows the plots of ln(E7 P 2 ) against 1000/T p . We can use the slope of the fitted data to calculate the activation energy E c . Then the Kissinger analysis of the DSC scans gives the parameters compiled in table 2.  Activation energy E c1 for the first crystallization stage (kJmol -1 )

301.679
By comparison, the Auguis-Bennet's model describes the kinetics by using Equation 3 to calculate the activation energy E c of the crystallization as well as the frequency factor K 0 .
The figure 4 and the table 3 describe the deduction of E c and K 0 with the same procedure previously used. Since the Fe-Si grains determine the magnetic properties of the material, the study of the first peak is interesting. So, the apparent activation energy according to thermally activated process was deducted (E c1 = 384 KJ mol -1 ) and agrees with a kinetic evaluation of the peak temperature according to Kissinger's and Auguis-Bennet's models [13][14]. More kinetic analysis can be described using different models like The Advance Model Free Kinetics (AMFK) model developed by Vyazovkin [15][16]. Results of kinetics for relaxed and annealed samples give further information concerning the crystallization process. It should be noted that the activation energy changes fundamentally during crystallization.  Activation energy E c1 for the first crystallization stage (kJmol -1 )

X-Ray Diffraction results
Indeed, we are speaking of amorphous ribbons. We then stated that the samples are "partially crystalline". This can be contradictory. In reality, the ribbons exhibit, as we shall see with the X-UD\ GLIIUDFWLRQ D VPDOO RXWJURZWK LQGLFDWLQJ DQ DSSHDUDQFH RI Į-Fe crystallites. The as-purchased material is a relaxed amorphous ribbon that contains some amounts of Į-Fe of bcc structure whose (110) line emerges over the stretched amorphous halo. This demonstrates that the heat treatment slightly modified the structure which is not completely amorphous (see fig.5a). The following annealing treatments on samples from the relaxed ribbon induce an increase of the amount of the Į-Fe of bcc structure from the residual amorphous phase with the formation of borides. The X-rays diffraction patterns (XRD) of the annealed ribbons show, in fig.5b, the main lines belong WR EFF VROLG VROXWLRQ Į-(Fe, Si) and tetragonal Fe 3 B. The proportions of the crystalline phases related to the X-rays intensity indicate a different amount of phases within the different samples. At 420°C-+ D Į-Fe peak corresponding to d hkl at about 2.02 nm on the XRD spectrum can be observed along with a small peak of (301) tetragonal (t) Fe 3 B at d hkl = 2.33 nm. This latter increases following the annealing time. Moreover, the 2.02 nm peak shows a side peak at about 2.01 nm which is likely that of (121) of t-Fe 2 B. However in the XRD spectrum of the sample heated to 700°C, the intensity of the peak at 2.02 nm is greater than that of the peak at 2.33 nm without any additionnal peak of t-Fe 2 % 7KHVH REVHUYDWLRQV LQGLFDWH WKDW WKH SURSRUWLRQ RI WKH Į-Fe is greater in the sample heated than in the annealing samples. Thus long annealing time favours the borides formation.

Magnetic properties
We performed two separate experiments over time with the same samples. The first, to evaluate the saturation magnetization at high magnetic field and to confirm the role of the increase of the DFe-Si) phase in the annealed material. Figure 6 shows the magnetization of annealed samples as a function of the applied magnetic field up 2 tesla (20000 Oersted). Progression to complete saturation seems faster for samples annealed during 5h and 8h with a tendency to unidirectional anisotropy. For the relaxed (amorphous) sample, the saturation is more difficult to achieve and is reached beyond the maximum applied field , this suggests that saturation is facilitated with the increase of volume fraction RI WKH Į-(Fe,Si) phase. For the relaxed sample, the structural relaxation may cause the value of the saturation relatively low compared to the treated samples from 5h to 8h when the soft magnetic phase (Fe, Si) is present in more large quantities.
In order to better define the remarkable properties of this soft magnetic material, we use a lower magnetic field experiment using a fluxmeter. Coercivity and anisotropy could be deduced from the hysteresis cycles for all samples. For a good comparison, as-cast amorphous samples show a low coercivity H c and a fairly high magnetization with a low magnetocrystalline anisotropy indicating a rounded cycle characteristic of the amorphous structure.
An annealing procedure without applied magnetic field makes a somewhat rounded appearance. In this case, two processes are present: domain wall movement and rotation of moments.  Table 4 presents some characteristic values inferred from hysteresis loops for maximum applied magnetic field H max =1 kOe (VSM) giving magnetization M s and hysteresis loops up to 27000 A/m (about 300 Oe) give the coercive field and relative anisotropy.
The amorphous Fe-Si-B alloys which are treated at 420°C for 1 hour remain amorphous. Structural relaxation takes place due to the formation of Fe 3 Si, which is a soft magnetic phase. For the annealed alloys, we observe a strong increase in coercivity for the Fe-Si-B alloy with the annealing time. The growth of dendrites increases the coercivity by providing additional obstacles for the movement of the domain walls. In addition, the formation of hard magnetic phase Fe 3 B results in a deterioration of soft magnetic properties. Indeed, the formation of the Fe 3 B phase leads to an increase in the magnetocrystalline anisotropy, following which the magnetic curing takes place. For longer annealing times up to 8 hours, the saturation magnetization continues to increase due to the formation of the Fe 3 Si phase. The Fe 3 B phase continues to increase in parallel. When the sample is brought to 700 ° C, the magnetization continues to increase for the Fe-Si-B alloy due to the stopping of Fe 3 B evolution as well as the (Fe,Si) phase progression (see section 3.3). Thus, the anisotropy decreases due to the reduction of the influence of the Fe 3 B phase which no longer progresses.

Conclusion
We have studied the thermal behavior of amorphous and thermally treated Fe 78 B 13 Si 9 ribbons that contain a certain amount of bcc-Į)H '6& DQG ;5' ZHUH XVHG Pre-annealed samples were annealed at 420°C during 1, 3, 5 and 8 hours.
The kinetics indicates that during transformations two crystallization steps appear. XRD diffraction confirmed the presence of the latter phase and the stability of the bcc-Į-Fe crystals due to the crystallization of the residual amorphous phase during the increase of the heating time.
Magnetic measurements indicate an evolution by annealing procedure which suggests improvement of saturation magnetization and occurring of directional anisotropy characterized by a growing remnant magnetization, but also destroying of mechanical properties as ductility and leads to magnetic hardening by increasing of coercive field H c .