Effect of Previous Milling of Precursors on Magnetoelectric Effect in Multiferroic \({\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}}\) Ceramic
Abstract
\(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\) magnetoelectric (ME) ceramics have been synthesized and investigated. The ME effect can be described as an induced electric polarization under an external magnetic field or an induced magnetization under an external electric field. The materials in the ME effect are called ME materials, and they are considered to be a kind of new promising materials for sensors, processors, actuators, and memory systems. Multiferroics, the materials in which both ferromagnetism and ferroelectricity can coexist, are the prospective candidates which can potentially host the gigantic ME effect. \(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\), an Aurivillius compound, was synthesized by sintering a mixture of \(\mathrm{Bi}_{2}\mathrm{O}_{3}, \mathrm{Fe}_{2}\mathrm{O}_{3}\), and \(\mathrm{TiO}_{2}\) oxides. The precursor materials were prepared in a high-energy attritorial mill for (1, 5, and 10) h. The orthorhombic \(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\) ceramics were obtained by a solid-state reaction process at 1313 K. The ME voltage coefficient (\(\alpha _\mathrm{ME}\)) was measured using the dynamic lock-in method. The highest ME voltage coefficient (\(\alpha _\mathrm{ME} = 8.28\,\text{ mV }{\cdot }\text{ cm }^{-1}{\cdot }\text{ Oe }^{-1})\) is obtained for the sample milled for 1 h at \(H_\mathrm{DC }= 4\) Oe (1 Oe = 79.58 \(\text{ A }{\cdot }\text{ m }^{-1})\).
Keywords
\(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\) Dielectric properties Ferroelectric High-energy ball milling Magnetoelectric (ME) effect Sintering1 Introduction
The magnetoelectric (ME) effect, i.e., the induction of ferroelectric polarization by a magnetic field and magnetization by an electric field can be achieved in multiferroic materials that show the coexistence of ferroelectricity and ferromagnetism [1, 2, 3, 4, 5, 6, 7]. The ME effect can be observed in some chemical compounds and solid solutions with different crystal structures including perovskites, \(\mathrm{BiFeO}_{3}\) [8] bismuth oxides with a layered structure, boracites, orthorhombic manganites of the \(\mathrm{RMnO}_{3}\) (R = Eu, Gd, Tb) type [9], hexagonal fluorites of the \(\text{ Ba-MeF }_{4}\) type, and some compounds with the \(\mathrm{BaTiO}_{3}\) and \(\mathrm{GdFe}_{3}(\mathrm{BO}_{3})_{4}\) structure [10]. In most of these materials, the ME effect is observed in an \(H > 10\) Oe (1 Oe = 79.58 A \({\cdot }\text{ m }^{-1})\) magnetic field [11] or at low temperatures. \(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\) ceramics with their bismuth-layered perovskite-like structure are characterized by the ME effect in an \(H = 4\) Oe magnetic field at room temperature.
2 Measurements
2.1 Specimens
2.2 Procedures
The measurements of \(^{57}\)Fe Mössbauer spectra were performed in transmission geometry by means of a constant spectrometer of the standard design. The 14.4 keV gamma rays were provided by a 50 mCi source of \(^{57}\)Co/Rh. The spectra of the samples were measured at room temperature. Hyperfine parameters of the investigated spectra were related to the \(\alpha \)-Fe standard. The experimental spectrum shape was described with a transmission integral calculated according to the numerical Gauss–Legendre procedure.
X-ray analysis was carried out using the X-Pert Philips diffractometer equipped with a curved graphite monochromator on a diffracted beam and a tube provided with a copper anode. It was supplied by a current intensity of 30 mA and voltage of 40 kV. The length of radiation (\(\lambda _{\mathrm{CuK}\!\upalpha }\)) was 1.54178 Å. The diffraction lines were recorded by the “step-scanning” method in the range of 2\(\theta \) from \(15^{\circ }\) to \(140^{\circ }\) with a \(0.05^{\circ }\) step. The Rietveld analysis was performed applying the DBWS-9807 program that is an updated version of the DBWS programs for Rietveld refinement with PC and mainframe computers. The pseudo-Voigt function was used in the description of diffraction line profiles at Rietveld refinement [13, 15, 16, 17, 18]. The phase abundance was determined using the relation proposed by Hill and Howard [16].
3 Results
Hyperfine parameters for the \(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\) ceramics
Sample | Subspectra | QS (\(\text{ mm }{\cdot }\text{ s }^{-1}\)) | SD (\(\text{ mm }{\cdot }\text{ s }^{-1}\)) | IS (\(\text{ mm }{\cdot }\text{ s }^{-1}\)) | SD (\(\text{ mm }{\cdot }\text{ s }^{-1}\)) | \(A\) (%) | SD (%) | \(B_\mathrm{hf}\) (\(10^{4}\) Gs) | SD (\(10^{4}\) Gs) |
---|---|---|---|---|---|---|---|---|---|
1 h BTFO | \(Z_{1}\) | \(-0.02\) | 0.02 | 0.16 | 0.02 | 54.8 | 0.1 | 14.1 | 0.3 |
\(Z_{2}\) | 0.32 | 0.02 | 0.19 | 0.02 | 45.2 | 0.1 | |||
5 h BTFO | \(Z_{1}\) | 0.01 | 0.02 | 0.13 | 0.02 | 36.3 | 0.1 | 18.3 | 0.3 |
\(Z_{2}\) | 0.28 | 0.02 | 0.17 | 0.02 | 63.7 | 0.1 | |||
10 h BTFO | \(Z_{1}\) | \(-0.09\) | 0.02 | 0.18 | 0.02 | 31.3 | 0.1 | 21.9 | 0.3 |
\(Z_{2}\) | 0.30 | 0.02 | 0.16 | 0.02 | 68.7 | 0.1 |
The isometric shift (IS) characteristic of the \(Z_{1}, Z_{2}\) component confirms that this layer contains both the Fe and Ti atoms and that their mutual redistribution is caused by the milling process. Low quadrupole splitting (QS) values—of the parameter which describes the symmetry of the set—calculated for the \(Z_{1}\) component prove that the set of elements is homogeneous (Table 1).
The differences in the values of the IS demonstrate that the local environment of the Mössbauer nuclide changes. High QS values calculated for the \(Z_{2}\) component are a sign of some disturbances in the homogeneous set of elements in both the perovskite and bismuth oxide layers. The values of the isometric shift determined for all components clearly show that Fe atoms in the perovskite layer are surrounded by Ti and Bi atoms [16, 17, 18].
The realization of the ME coupling parameter in the multiferroic material is due to the product’s property, which is the ferroelectric and piezoelectric phase and the ferromagnetic phase. The coupling nature depends on the mechanical coupling between (\(\mathrm{Bi}_{2}\mathrm{O}_{2})^{2+}\) and (\(\mathrm{A}_{\mathrm{m}-1}\mathrm{B}_\mathrm{m}\mathrm{O}_{3\mathrm{m}+1})^{2-}\) phases, where A = Bi, B = Ti, Fe, and m = 4 phases. If the transfer of stress from the (\(\mathrm{A}_{\mathrm{m}-1}\mathrm{B}_\mathrm{m}\mathrm{O}_{3\mathrm{m}+1})^{2-}\) magnetostrictive phase to the (\(\mathrm{Bi}_{2}\mathrm{O}_{2})^{2+ }\) ferroelectric and piezoelectric phase is strong enough, a high value of the ME coupling parameter can be obtained [20].
The ME hysteresis loops are observed for the multiferroic material at room temperature; a strictly induced polarization takes place. The presence of Fe in the lattice can induce bulk magnetization in such perovskites. The observed phenomenon may arise due to the slight canting of the Fe–O–Fe chain of spins in the regular octahedra, which is slightly tilted. The addition of (\(\mathrm{Bi}_{2}\mathrm{O}_{2})^{2+}\) to (\(\mathrm{A}_{\mathrm{m}-1}\mathrm{B}_\mathrm{m}\mathrm{O}_{3\mathrm{m}+1})^{2-}\) reduces the degree of incommensurate structure, but preserves the nonlinearity [21].
4 Conclusions
- 1.
Mössbauer studies performed with the use of conversion electron Mössbauer spectroscopy (CEMS) technique confirmed the magnetic properties of the \(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\) ceramic.
- 2.
The ME effect in the \(\mathrm{Bi}_{5}\mathrm{Ti}_{3}\mathrm{FeO}_{15}\) ceramics is weak, yet measurable at room temperature.
- 3.
The fastest growth of the ME effect is obtained for the 1 h BTFO sample.
- 4.
The highest values of the ME coefficient were obtained for the 1 h BTFO sample.
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