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具有磁铅石结构的Al、Cr、Ga和In阳离子多取代铁氧体的制备及磁性研究

Creation and Magnetic Study of Ferrites with Magnetoplumbite Structure Multisubstituted by Al, Cr, Ga, and In Cations.

作者信息

Zhivulin Vladimir E, Sherstyuk Daria P, Zaitseva Olga V, Cherkasova Natalia A, Vinnik Denis A, Taskaev Sergey V, Trofimov Evgeny A, Trukhanov Sergei V, Latushka Siarhei I, Tishkevich Daria I, Zubar Tatiana I, Trukhanov Alex V

机构信息

Laboratory of Single Crystal Growth, South Ural State University, 76, Lenin Av., 454080 Chelyabinsk, Russia.

Faculty of Physics, Chelyabinsk State University, 129, Bratiev Kashirinykh St., 454001 Chelyabinsk, Russia.

出版信息

Nanomaterials (Basel). 2022 Apr 11;12(8):1306. doi: 10.3390/nano12081306.

Abstract

Multisubstituted barium ferrites with a magnetoplumbite structure were obtained by the method of solid-phase reactions with ferritization and pre-firing. Three-charged, mainly diamagnetic cations Al, Cr, Ga, and In were chosen as substituents for the Fe iron cations, the proportion of which in solid solutions did not exceed 50%. The values of the configurational mixing entropy were calculated for all the compositions. A slight deviation of the chemical composition of the obtained solid solutions from the nominal value was established by the energy-dispersive X-ray spectroscopy method. The phase purity and values of the unit cell parameters were refined from X-ray scattering data using full-profile analysis in the Rietveld method. A non-monotonic behavior of the unit cell parameters as a function of the B-sub-lattice average ionic radius of the magnetoplumbite structure was found. A minimum unit cell volume of ~667.15 Å was found for the composition BaFeAlCrGaO with a B-sub-lattice average ionic radius of ~7.449 Å. The average crystallite size varied within 5.5-6.5 μm. The temperature and field dependencies of the magnetization have been measured. The values of the saturation magnetization, residual magnetization, hysteresis loop squareness, and coercivity at 50 K and 300 K were extracted from the experimental data. Using the Law of Approach to Saturation, the magnetic crystallographic anisotropy coefficient and anisotropy field were calculated. Multisubstitution leads to a significant decrease in such magnetic parameters as the magnetic ordering temperature and spontaneous magnetization at both temperatures. The maximum magnetic ordering temperature of ~297.7 K was found for the composition BaFeGaO with a B-sub-lattice average ionic radius of ~7.586 Å in a field of 500 Oe. A maximum saturation magnetization of ~24.7 emu/g was found for the composition BaFeGaO with a B-sub-lattice average ionic radius of ~7.586 Å at 50 K. A maximum hysteresis loop squareness of ~0.72 was found for the composition BaFeAlCrGaO with an average ionic radius of ~7.449 Å at 50 K. A maximum magnetic crystallographic anisotropy coefficient of ~2.09 × 10 Erg/g was found for the composition BaFeAlCrGaInO with a B-sub-lattice average ionic radius of ~7.706 Å at 50 K. The frustrated magnetic state including the nano-sized clusters with an average diameter in the range of 50-200 nm was established from the results of measuring the ZFC and FC temperature magnetizations. The interpretation of the obtained experimental data is carried out taking into account the increased stability of high-entropy phases and regular changes in the intensity of the Fe(Al, Cr, Ga, In)-O-Fe(Al, Cr, Ga, In) indirect superexchange interactions as a result of magnetic dilution of the iron sub-lattice in the magnetoplumbite structure.

摘要

通过具有铁素体化和预烧制的固相反应方法制备了具有磁铅石结构的多取代钡铁氧体。选择三价的、主要为抗磁性的阳离子Al、Cr、Ga和In作为Fe铁阳离子的取代基,其在固溶体中的比例不超过50%。计算了所有组成的构型混合熵值。通过能量色散X射线光谱法确定了所获得的固溶体的化学成分与标称值的轻微偏差。使用Rietveld方法中的全谱分析从X射线散射数据中细化了相纯度和晶胞参数值。发现晶胞参数随磁铅石结构的B亚晶格平均离子半径呈非单调变化。对于B亚晶格平均离子半径约为7.449 Å的BaFeAlCrGaO组成,发现最小晶胞体积约为667.15 ų。平均微晶尺寸在5.5 - 6.5 μm范围内变化。测量了磁化强度的温度和磁场依赖性。从实验数据中提取了50 K和300 K时的饱和磁化强度、剩余磁化强度、磁滞回线矩形度和矫顽力值。利用趋近饱和定律计算了磁晶各向异性系数和各向异性场。多取代导致两个温度下的磁有序温度和自发磁化强度等磁参数显著降低。在500 Oe磁场中,对于B亚晶格平均离子半径约为7.586 Å的BaFeGaO组成,发现最大磁有序温度约为297.7 K。在50 K时,对于B亚晶格平均离子半径约为7.586 Å的BaFeGaO组成,发现最大饱和磁化强度约为24.7 emu/g。在50 K时,对于平均离子半径约为7.449 Å的BaFeAlCrGaO组成,发现最大磁滞回线矩形度约为0.72。在50 K时,对于B亚晶格平均离子半径约为7.706 Å的BaFeAlCrGaInO组成,发现最大磁晶各向异性系数约为2.09×10⁷ Erg/g。根据零场冷却(ZFC)和场冷却(FC)温度磁化强度测量结果确定了包括平均直径在50 - 200 nm范围内的纳米级团簇的受挫磁状态。考虑到高熵相稳定性的增加以及由于磁铅石结构中铁亚晶格的磁稀释导致的Fe(Al, Cr, Ga, In)-O-Fe(Al, Cr, Ga, In)间接超交换相互作用强度的规则变化,对所获得的实验数据进行了解释。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/af99/9029440/1b6d210c13da/nanomaterials-12-01306-g001.jpg

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