K. GRUSZKA: ANALYSIS OF THE STRUCTURAL-DEFECT INFLUENCE ON THE MAGNETIZATION PROCESS ... 707–718 ANALYSIS OF THE STRUCTURAL-DEFECT INFLUENCE ON THE MAGNETIZATION PROCESS IN AND ABOVE THE RAYLEIGH REGION ANALIZA VPLIVA STRUKTURNIH DEFEKTOV NA PROCES MAGNETIZACIJE V IN NAD RAYLEIGH PODRO^JEM Konrad Gruszka Czestochowa University of Technology, Faculty of Production Engineering and Materials Technology, Institute of Physics, Armii Krajowej Av. 19, 42-200 Czestochowa, Poland kgruszka@wip.pcz.pl Prejem rokopisa – received: 2015-06-30; sprejem za objavo – accepted for publication: 2015-09-16 doi:10.17222/mit.2015.154 The paper presents studies of the structural-defect influence on the magnetization process in low magnetic fields (H < 0.4 Hc) and above the Rayleigh range. The investigated Fe62Co10Y8B20 alloy samples were obtained with the injection casting method resulting in the amorphous-structure state, which was confirmed with XRD. The studies were conducted by analyzing the disaccommodation of the magnetic-susceptibility process and using Kronmüller’s theory in the approach to the ferromagnetic saturation area. On the basis of the obtained results, it was found that the main factor responsible for the processes of magnetization in low magnetic fields are point defects, whereas in the case of high magnetic fields, the magnetization process depends mainly on second-type pseudo-dislocation dipoles. Keywords: metallic glasses, defects, disaccommodation, Kronmüller’s theory ^lanek predstavlja {tudij vpliva strukturnih defektov na proces magnetizacije v {ibkem magnetnem polju (H < 0,4 Hc) in nad Rayleigh podro~jem. Vzorci preiskovane zlitine Fe62Co10Y8B20 so bili izdelani z metodo injekcijskega brizganja, kar je povzro~ilo amorfno strukturo, ki je bila potrjena z rentgensko analizo (XRD). [tudije so bile izvedene z analizo procesa neustreznosti magnetne ob~utljivosti in z uporabo Kronmülerjeve teorije pri pribli`evanju feromagnetno nasi~enemu podro~ju. Na osnovi dobljenih rezultatov je bilo ugotovljeno, da so pri procesu magnetizacije glavni faktor to~kaste napake, medtem ko je v primeru magnetizacije v mo~nem magnetnem polju proces odvisen predvsem od druge vrste psevdodislociranih dipolov. Klju~ne besede: kovinska stekla, napake, neustreznost, Kronmüllerjeva teorija 1 INTRODUCTION Iron-based amorphous materials are extensively stu- died because of their excellent soft-magnetic proper- ties.1–3 For this reason, they have been widely used in the electrical industry, primarily as high-efficiency cores for power transformers and chokes and also as coatings due to their high corrosion resistance.4,5 In terms of topological structure, amorphous mate- rials have properties similar to those of liquids. The atoms forming the material are scattered in a chaotic manner so that the observation of the long-range order is not possible. When the cooling rate of a liquefied alloy is sufficiently large, the kinetic energy of the atoms is taken so fast that they are trapped at higher energy positions. This results in the density and local chemical-compo- sition fluctuations, and is the major cause of the areas with a deficiency of atoms. This type of local voids are called point defects (by analogy with the vacancies occurring in a crystal structure). In the cases where several point defects are located in a small local envi- ronment, a concentration to two-dimensional defects occurs and it is referred to as pseudo-dislocation dipoles. Point defects and their conglomerates have a signifi- cant impact on the process of magnetization in high magnetic fields.6,7 The presence of structural defects, which are the centers of internal stresses, causes a defor- mation of local magnetization vectors. The presence of structural defects in amorphous materials affects the magnetization process in the area called the approach to ferromagnetic saturation.8 In close proximity to a point defect, the magnetization vectors are arranged in a "streamline" way9,10 which is a potential cause of do- main-wall anchors. A more complicated situation occurs in the presence of a pseudo-dislocation dipole, where the arrangement of individual vectors is not collinear and the centers of the deformation of these vectors are hooked at the dipole ends.11–13 Ferromagnetic materials, especially the ones based on the Fe-Co-B composition are well known for their great soft-magnetic properties, in particular a low coer- cive field and magnetostriction while they are not expen- sive and have a high sensitivity to alloying additives. In the compounds of this type, iron is typically the major part (more than a 50 % amount fraction) while Co, which has similar properties, allows an increase in the magnetization. Boron, due to a significant difference in the atomic radius, improves the glass-forming ability (GFA). In order to further increase the GFA, a small Materiali in tehnologije / Materials and technology 50 (2016) 5, 707–718 707 UDK 620.1:67.017:621.318 ISSN 1580-2949 Original scientific article/Izvirni znanstveni ~lanek MTAEC9, 50(5)707(2016) amount of yttrium atoms are introduced. According to the literature, a concentration of up to a 4 % amount fraction has a positive effect on the GFA but exceeding this value brakes down good soft-magnetic properties. Using the studies on susceptibility-disaccommodation phenomena and approach to the ferromagnetic saturation area, it is possible to indirectly describe the structural defects existing in a material. This paper focuses on defects – the relations within a magnetization process and shows that despite an yttrium addition of up to 8 %, one can obtain reasonable results in terms of soft-mag- netic parameters. 2 STUDIED MATERIAL AND METHODOLOGY The investigated material comprises chemical ele- ments of high purity (Fe – a 99.95 % amount fraction, the remaining component elements – 99.99 % amount fractions). A two-step preparation procedure was used. Initially, the ingredients were melted using a plasma arc (a working current of ~300 A) under a reduced pressure in a protective atmosphere of argon. The samples were melted several times to ensure a good homogeneity of the constituent distribution. Then the resulting ingot was melted, using an induction furnace, in a quartz tube and injected into a copper water-cooled mold, which was also under an argon atmosphere (at a pressure of 700 hPa). In the radial cooling process, good-quality amorphous solid samples with dimensions of 15 mm × 10 mm × 0.5 mm were obtained. The structure of the obtained samples was examined using an X-ray diffractometer (Bruker D8 Advance, Cu-K). The magnetic properties were deter- mined with an analysis of the static hysteresis loop and the initial magnetization curve, which were obtained from the measurements of the magnetization as a func- tion of the magnetic-field strength using a vibrating sample magnetometer (model Lakeschore 7301). Measu- rements of the initial permeability of the samples were taken over a wide temperature range of 300–650 K. The samples were suspended in a permalloy frame and placed in a quartz vacuum tube with a thermocouple, and the whole system was placed in an accumulative furnace. The disaccommodation-aftereffect intensity defined as Δ 1 1 1 1 0x t t ⎛ ⎝ ⎜ ⎞ ⎠ ⎟ = −  ( ) ( ) was measured in time (t1 – t0) = 118 s with the transformer method. The frequency of the ac field was set to 50 Hz. The samples were demagnetized by applying a sinusoidal decreasing magnetic field of 120 kHz. 3 RESULTS Figure 1 shows the XRD of a sample after the solidi- fication, measured for the 2 angle in a range from 30° to 100°. The diffraction pattern shows only the broad fuzzy maximum, located in a 2 angle range from approxima- tely 35° to 50°. This means that in a sample in the as-quenched state, there is no long-range order and the interactions between the atoms have a close- or me- dium-range character. Such a shape of a diffraction pattern is typical for the materials with an amorphous structure. Then measurements of the static magnetic hysteresis loop were carried out and the result is shown in Figure 2. The observed shape of the curve is characteristic for a magnetic material with soft magnetic properties. Based on the analysis of the static magnetic hysteresis loop, the basic parameters for the magnetic sample were deter- mined: magnetization saturation Ms = 1.27 (T), coercive field Hc = 289 (A/m). Next, an analysis of the primary magnetization curve in the approach to the ferromagnetic saturation area was carried out. Figures 3 and 4 show magnetization curves as a function of (μ0H)–2 and (μ0H)1/2. With respect to Kronmüller’s theory, as a result of the analysis of the primary magnetization curve, it was found that in a Fe62Co10Y8B20 alloy sample the magne- tization process in the area called "Ewing’s knee" relates to the change in magnetization vector directions caused by the presence of free-volume conglomerates. The linear-defect size (Ddip) must therefore be larger than the exchange distance. Assuming that Ddip > lH, the a2/(μ0H)2 law of approach to the ferromagnetic saturation area is K. GRUSZKA: ANALYSIS OF THE STRUCTURAL-DEFECT INFLUENCE ON THE MAGNETIZATION PROCESS ... 708 Materiali in tehnologije / Materials and technology 50 (2016) 5, 707–718 Figure 2: Static magnetic hysteresis loop for the Fe62Co10Y8B20 alloy Slika 2: Stati~na magnetna histerezna zanka zlitine Fe62Co10Y8B20 Figure 1: X-ray diffraction pattern of Fe62Co10Y8B20 in the as-quenched state Slika 1: Rentgenska difrakcija Fe62Co10Y8B20 v kaljenem stanju fulfilled. Thus, these defects are the main source of stress in the magnetic-field strength from 0.084 (T) to 0.25 (T). Above the (μ0H)–2 dependence, Holstein-Primakoff’s process intensifies, indicating that the further process of magnetization is associated with the damping of ther- mally excited spin waves with an external magnetic field (the b coefficient). The parameters obtained from the analysis of the primary magnetization curve are summar- ized in Table 1. Table 1: Parameters obtained with the analysis of the primary mag- netization curve Tabela 1: Parametri, dobljeni z analizo primarne krivulje magnetiza- cije a2 (10–2 T2) b (10–2 T1/2) Dsp (10–2 meV nm2) Aex (10–12 J m–1) lh (nm) 0.056 6.59 40.70 1.64 3.59 The absence of the a1/2 and a1 factors indicate that the point defects and linear defects of a smaller size had no effect on the magnetization process in magnetic fields greater than 0.4 Hc (above the Rayleigh region). This does not mean, however, that those defects are not pre- sent in the sample’s structure but only that they are insig- nificant for the magnetization process. To investigate their potential impact on the magnetization at low fields, the susceptibility disaccommodation studies were con- ducted. According to Kronmüller’s theory, it is possible to calculate the exchange distance of pseudo-dislocation dipoles (the lh parameter) and the exchange-constant (Aex) parameter. The latter is responsible for transferring magnetic interactions between the nearest neighbors (the energy of aligned spins) and the former describes the size of a defect’s influence zone. The Dsp parameter, which describes the spin-wave stiffness (and, therefore, the ability to transfer the spin torque) is more than twelve times higher (Dsp/DFe = 12.96) than with pure Fe (the largest percentage share in the alloy), which is found to be between DFe = 2.8 meV nm2 at 4.2 K14 and DFe = 3.14 meV nm2 at room temperature.15 This parameter is connected with the atomic packing density (a higher Dsp means a higher surface density16) and it may indicate that linear defects should rather be considered as swellings of voids resulting in an increase in the local density around the defects, while keeping the overall material density low. The thermal stability of the initial magnetic suscep- tibility was also investigated. This parameter is very important and often determines possible applications. For the studied sample, the shape of the dependency is shown in Figure 5. Quite minor temperature-related changes in the value of the initial magnetic susceptibility were observed. A good stability and an almost linear growth may indicate that, in magnetic terms, the material is homogeneous and no other magnetic phases were formed (in accordance to K. GRUSZKA: ANALYSIS OF THE STRUCTURAL-DEFECT INFLUENCE ON THE MAGNETIZATION PROCESS ... Materiali in tehnologije / Materials and technology 50 (2016) 5, 707–718 709 Figure 5: Dependence of the low-field magnetic susceptibility as a function of temperature for the Fe62Co10Y8B20 sample Slika 5: Odvisnost magnetne ob~utljivosti v {ibkem polju od tempera- ture vzorca Fe62Co10Y8B20 Figure 3: Magnetization as a function of (μ0H)–2 for the Fe62Co10Y8B20 alloy Slika 3: Magnetizacija kot funkcija (μ0H)–2 zlitine Fe62Co10Y8B20 Figure 4: Magnetization as a function of (μ0H)1/2 for the Fe62Co10Y8B20 alloy. Holstein-Primakoff process Slika 4: Magnetizacija kot funkcija (μ0H)1/2 zlitine Fe62Co10Y8B20. Proces Holstein-Primakoff the XRD). Considering the rather low temperatures region, the conspicuous increase between 325 K and 400 K can be elucidated mainly with the sample’s internal- tension relaxation processes, together with a minor con- tribution of the magnetic-anisotropy reduction. The sharp decline observed near 600 K is associated with the paramagnetic transition when the ferromagnetic order is destroyed. The time dependence of the initial susceptibility after the demagnetization at various temperatures, or the magnetic-susceptibility disaccommodation curve for the investigated alloy, is presented in Figure 6. As can be seen in Figure 6, the disaccommodation intensity linearly rises up to the broad maximum located at about 542 K. Above 542 K, the intensity decreases, which is directly connected with the decrease in the amount of the atom pairs reorienting in the point-defect vicinity. A pair reorientation can occur in two cases: the first one is associated with a reversible process, in which, through energy delivery, atom pairs near the point defects can swap their positions and return to the initial state after the energy reduction, and in the second one, this displacement is permanent due to the major changes in the local space involving a minimum of three atoms. Both processes can occur in the same time and the curve observed in Figure 6 indicates the effect of the impo- sition of these two phenomena. The visible kink in the same temperature region as in the case of the stability of the initial-susceptibility curve (Figure 5) is presumably also caused by the relaxation processes. This phenome- non must therefore at least partially occur through the irreversible atomic-pair reorientation, clearly manifested between 325 K and 400 K (Figure 6). As the relaxation process of the material has to occur through the displace- ment of atoms into positions that lead to a lower total energy of the system, a part of these movements must therefore lead to the reorientation of atomic pairs visible as disaccommodation phenomena. Next, a numerical analysis of the disaccommodation curve was done (Fig- ure 7). The isochronal magnetic-susceptibility disaccommo- dation curve was numerically analyzed using the depen- dence given with Equation (1): Δ 1 3 3 1 1 x I T T e i i mi i l pi pi t ⎛ ⎝ ⎜ ⎞ ⎠ ⎟ = ⋅ ⋅ −= − ∫∑          e t e z z mi z ie e z− ⎛ ⎝ ⎜ ⎞ ⎠ ⎟ − − ⎛ ⎝ ⎜⎜ ⎞ ⎠ ⎟⎟ 2 2    d (1) where the mean relaxation time mi is given:  mi mi pi Q k T T = − − ⎛ ⎝ ⎜ ⎞ ⎠ ⎟ ⎛ ⎝ ⎜⎜ ⎞ ⎠ ⎟⎟exp 1 1  – the pre-exponential factor in the Arrhenius law, Ipi – the intensity of the ith process at temperature Tpi, Qmi – the mean activation energy,  – the distribution width and z mi= ln /  . The results of the analysis of the disaccommodation curve in function of temperature, based on the above formula done using the least squares method is presented in Table 2. Table 2: Results obtained from the numerical analysis of dis- accommodation curve Tabela 2: Rezultati, dobljeni iz numeri~ne analize neustrezne krivulje a 1.095*10–7  (s) b –2.230*10–5 Tp (K) 433.20 2.62×10-15 Ip 5.223*10–6 Q (eV) 1.378  6.9368 Tp (K) 479.17 2.98×10-15 Ip 3.215*10–5 Q (eV) 1.5189  5.0638 Tp (K) 542.87 5.26×10-15 Ip 2.52*10–5 Q (eV) 1.6942  3.7668 The isochronal magnetic-susceptibility disaccommo- dation curve was decomposed into three elementary K. GRUSZKA: ANALYSIS OF THE STRUCTURAL-DEFECT INFLUENCE ON THE MAGNETIZATION PROCESS ... 710 Materiali in tehnologije / Materials and technology 50 (2016) 5, 707–718 Figure 7: Theoretical magnetic-susceptibility disaccommodation curve (solid line) and experimental data for the Fe62Co10Y8B20 alloy after solidification Slika 7: Teoreti~na krivulja neprimerne magnetne ob~utljivosti (polna linija) in eksperimentalni podatki za zlitino Fe62Co10Y8B20 po strje- vanju Figure 6: Magnetic-susceptibility disaccommodation curve for the Fe62Co10Y8B20 alloy after solidification Slika 6: Neprimerna krivulja magnetne ob~utljivosti zlitine Fe62Co10Y8B20 po strjevanju processes (peaks). The first peak with the maximum localized at 433 K has the lowest activation energy (Q), the highest width () and the highest intensity (Ip). Most of the elementary-pair-reconfiguration processes there- fore require a minimum activation energy of 1.38 eV. An analysis of Table 2 reveals that the peak maximum temperature (Tp) increases together with the activation energy and relaxation time . At the same time, the distribution width and process intensity decrease. This phenomena is probably related with the atomic mass (and also the radius) of the ingredients. Thus, atom pairs with a higher mass or a bigger size require more energy and time for the relaxation to occur. On this basis, it can be concluded that the first elementary process is mostly caused by boron (a radius of 82 pm, a weight of 10.8 u), the second process mainly involves Fe (r. 126 pm, w. 55.9 u) and Co (r. 125 pm, w. 58.7 u) and the last pro- cess, which requires the largest activation energy, is caused due to an increasing involvement of yttrium (r. 180 pm, w. 88.9 u) atoms. Obviously, due to the smallest size and weight of B, this element probably has the largest share in each of the elementary processes, but it should be noted that the pair reorientation involving atoms with extreme size differences, tends to be irreversible. 4 CONCLUSIONS In the radial cooling process, a good-quality bulk amorphous sample of the Fe62Co10Y8B20 composition was prepared. Studies of its magnetic properties showed that despite a notably large yttrium share, it is possible to make the material to be rather soft (Hc = 289 A/m). Susceptibility studies showed that in terms of magnetic properties, the material is homogeneous. Simultaneously, magnetic-susceptibility disaccommodation studies clear- ly revealed a presence of point defects, which are res- ponsible for the magnetization process in the Rayleigh area. Therefore, point defects must also be distributed uniformly across the entire volume of the material. The decomposition of the susceptibility disaccommodation curve in three elementary processes was sufficient to completely describe the pair reorientation, showing the dependence of the activation energy, intensity and rela- xation time on the mass (and radius) of the elements involved in the reorientation process. At H > 0.4 Hc, in the approach to the ferromagnetic saturation area, the initial-magnetization-curve analysis, with respect to Kronmüller’s theory, led to the conclusion that in the magnetization process, linear defects of the second type play the main role. A detailed analysis of the parameters obtained on the basis of this theory showed that the defects of this type can be considered as swellings of voids, leading to an increase in the local density around them. On the other hand, as it is known, long-term annealing below the crystallization temperature leads to a decrease in dis- accommodation phenomena17 associated with the stress relaxation (due to the atom expansion) and defect diffu- sion to the sample’s surface. There are no indications that the linear defects are not subjected to the same processes, leading to their decomposition into smaller point defects. At the same time, no increase in the intensity of disaccommodation phenomena is observed (directly related to the amount of point defects). This may suggest that the linear conglomerates of defects disappear because of collapse-like processes and not due to shredding. This is consistent with the conclusion about an increase in the structural stresses around the linear defects, pushing to fill the voids and, therefore, reduce the system energy. 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