钐取代对mnni -纳米尖晶石铁氧体结构、传导机制和介电弛豫的影响

IF 3 3区 化学 Q3 CHEMISTRY, PHYSICAL Physical Chemistry Chemical Physics Pub Date : 2026-10-14 DOI:10.1039/d6cp03090d
B. Ünal,A. Baykal,M. A. Almessiere,E. Mojtahedi
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引用次数: 0

摘要

通过溶胶-凝胶法制备Sm与Mn-Ni尖晶石铁氧体结合形成Mn0.5Ni0.5SmxFe2−xO4 (x≤0.10)纳米尖晶石铁氧体(Sm→MnNi (x≤0.10)NSFs)。对产物进行了不同的表征技术来研究其结构和形态。通过x射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)分别证实其为立方晶体结构和球体形貌。采用介电光谱、电导率和复阻抗分析对Sm→MnNi (x≤0.10)NSFs的电学和介电谱进行了系统的检测。交流电导率谱显示了频率和温度相关的色散,这与Jonscher幂定律(JPL)一致,而直流电导率的Arrhenius分析则揭示了两个由局部和远程小极化子跳变过程主导的热激活机制。在低温区计算得到的活化能为10 ~ 190 meV,高温区计算得到的活化能为420 ~ 530 meV,证实了双导机制。此外,介电常数和损耗谱显示了麦克斯韦-瓦格纳界面极化和Koop现象行为,其中Sm3+离子取代比对晶界电阻和极化动力学的影响最大。此外,复合电模量和Nyquist图显示单个半圆弧,表明晶界主导的传导和非debye弛豫。有趣的是,适度的Sm3+离子取代比(0.050 ~ 0.075)改善了晶格畸变,降低了活化能(EA),增强了跳变传导;相反,过高的替代比率,如0.10,会导致缺陷聚集,显著降低电气性能。所有这些发现都强烈地强调了稀土元素取代在Mn-Ni NSFs中形成传导和介电弛豫的关键作用。
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The effect of samarium substitution on the structure, conduction mechanism, and dielectric relaxation of MnNi-nanospinel ferrites
The incorporation of Sm into Mn–Ni spinel ferrites to form Mn0.5Ni0.5SmxFe2−xO4 (x ≤ 0.10) nanospinel ferrites (Sm → MnNi (x ≤ 0.10) NSFs) was achieved via the sol–gel method. The product was subjected to different characterization techniques to investigate its structure and morphology. A cubic crystal structure and a sphere morphology were confirmed by X-ray Powder Diffractometry (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. The electrical and dielectric spectra of the Sm → MnNi (x ≤ 0.10) NSFs were systematically examined using dielectric spectroscopy, electrical conductivity, and complex impedance analyses. The AC conductivity spectra reveal both frequency- and temperature-dependent dispersions, which are consistent with Jonscher's power law (JPL), whereas the Arrhenius analysis of the DC conductivity discloses two thermally activated regimes dominated by localized and long-range small polaron-hopping processes. The calculated activation energies ranged from 10 to 190 meV in the LT region and 420 to 530 meV in the HT region, confirming the dual conduction mechanism. Furthermore, dielectric constant and loss spectra demonstrated Maxwell–Wagner interfacial polarization and Koop's phenomenological behavior, with Sm3+ ion-substitution ratios most strongly influencing the grain boundary resistance and polarization dynamics. In addition, the complex electrical modulus and Nyquist plots reveal single semicircular arcs, indicating grain-boundary-dominant conduction and non-Debye relaxation. Interestingly, moderate Sm3+ ion-substitution ratios, ranging from 0.050 to 0.075, improve lattice distortion, lower the activation energy (EA), and enhance hopping conduction; conversely, excessive substitution ratios, such as 0.10, lead to defect clustering, significantly reducing electrical performance. All these findings strongly highlight the critical role of rare earth (RE) element substitution in shaping conduction and dielectric relaxation in Mn–Ni NSFs.
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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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