Enhanced electromagnetic microwave absorption of Fe/C/SiCN composite ceramics targeting in integrated structure and function

The Fe/C/SiCN composite ceramics were synthesized by polymer-derived method to obtain the integration of structure and functions. The electromagnetic waves (EMW) absorption properties at X and Ku bands were investigated. The addition of nano-sized Fe particles improved the magnetic loss and impedance matching, and the carbon nanotubes generated by the iron in-situ catalysis increased the internal relaxation polarization and interfacial polarization, which together improved the EMW absorption properties significantly. In particular, the Fe/C/SiCN-9 showed the optimum reflection loss (RL) of ?31.06 dB at 10.03 GHz with an effective absorption bandwidth (EAB, RL < ?10 dB) of 3.03 GHz at 2.51 mm, indicating the excellent EMW absorption properties of Fe/C/SiCN composite ceramics.     

Temperature dependent negative permittivity in solid solutions Sr2Mn1-xSnxO4 (x = 0, 0.3, 0.5)

A few compositions of the system Sr₂Mn_1-xSn_xO₄ (x = 0.0, 0.3, 0.5) were synthesized in the air by the solid-state ceramic route. A change in the sign (positive to negative) of the permittivity above a particular temperature (T_C) is observed at all the measured frequencies. The negative permittivity was analyzed by the Drude-Lorentz model. It was found that negative permittivity is caused by the plasma oscillations of thermally excited free charge carriers. Analysis of XPS spectra confirmed the presence of mixed-valence states of both Mn (Mn⁴⁺ and Mn³⁺) and Sn (Sn⁴⁺ and Sn²⁺) ions. The UV–vis.-IR spectroscopy results indicated generation of a large number of defect states in the forbidden bandgap region of Sr₂MnO₄ on the substitution of Sn at Mn site. Synthesized samples are promising metamaterials for radio frequency (10 Hz -2 MHz) region applications due to the high-temperature plasmonic behavior.     

A-site Ca2+ substitution induced polyvalent Cu cations and correlated polaron relaxations in colossal permittivity Li1-xCaxCuNb3O9

LiCuNb₃O₉ has been reported newly a colossal permittivity (CP) perovskite, in which the B-site NbO₆ octahedra play a bridging role in the polaron hopping. However, how the A-site modification affects the origin of the polarons and further the CP behaviours remains unexplored. To this end, A-site Ca²⁺ was incorporated to form Li_1-xCa_xCuNb₃O₉, and the local states, dielectric relaxations and conduction behaviours were comprehensively studied. The substitution induces the polyvalent Cu cations, i.e. Cu⁺/Cu²⁺/Cu³⁺. Bond valence sum calculations imply that Cu²⁺ and Cu³⁺ are underbonded, and Cu⁺ is overbonded, while B-site Nb⁵⁺ shows slightly different with theoretical pentavalence. All the compositions exhibit a similarly room-temperature CP response, but present two dielectric relaxations, i.e. T_R1:170–300 K and T_R2:260–400 K. Comprehensive investigations on universal dielectric response and bulk dc conductivity indicate that the T_R1 follows the variable-range-hopping where the electron hopping between the mixed Cu⁺/Cu²⁺, while T_R2 contributes from the Cu³⁺ nearest neighbor hopping.     

Synthesis of cubic and monoclinic hafnia nanoparticles by pulsed plasma in liquid method

Hafnia (HfO₂, hafnium dioxide) is a wide band gap and high-κ material, and the metastable cubic hafnia has a much higher permittivity compared with the normal monoclinic hafnia. Here, we employ a one-step process, the pulsed plasma in liquid (PPL) method to synthesize two types of hafnia nanoparticles (NPs): one which is mainly in cubic phase (cubic: 81.7 at%, monoclinic: 18.3 at%) and the other which is in monoclinic phase. High-resolution transmission electron microscopy images showed that the particles were small (particle size ~3 nm). X-ray absorption fine structure analysis showed no chemical shifts, indicating that the synthetic hafnia NPs contained no oxygen vacancy. The synthetic hafnia NPs mainly in cubic phase showed a much higher relative permittivity than that of the commercial hafnia (monoclinic), and have a larger band gap than the synthetic monoclinic hafnia NPs.     

Comment on“Hole-pinned defect-dipoles induced colossal permittivity in Bi doped SrTiO3ceramics with Sr deficiency”

With this contribution,as a comment to the publication in Journal of Mate rials Science&Technology 44(2020)54,reporting giant dielectric response,structural characterization and numerical simulations in Sr_(1-1.5 x)Bi_xTiO₃ceramics,we show that the re ported results are rather contradicting and not well analysed,while the suggested mechanism for the giant permittivity response is not valid or doubtful and has to be reconsidered.Moreover,many details and data are missing making impossible not only to call the obtained results very suitable for practical application but even to reproduce them.     

Disappearance and recovery of colossal permittivity in (Nb+Mn) co-doped TiO2

We investigate the effects of doping and annealing on the dielectric properties of metal ions doped TiO₂ ceramics. Colossal permittivity (CP) above 10⁴ was observed in single Nb ion doped TiO₂, which was dominated by electron transport related interfacial polarization. Moreover, the CP can be dropped to 120 when simultaneously introducing Mn ion into the sample. The disappearance of CP behaviors maybe due to the multivalence of Mn which would inhibit the reduction of Ti⁴⁺ to Ti³⁺, and thus reduce delocalized electrons. Interestingly, the CP was recovered for the (Nb+Mn) co-doped TiO₂ after post-sintering heat treatment in N₂ atmosphere. The recovery of CP in the sample after annealing can be ascribed to the semiconducting grain and the insulating grain boundary, according to impedance spectroscopy. We therefore believe that this work can help us understand the mechanism of CP from a new perspective.     

Enhanced relative permittivity in niobium and europium co-doped TiO2 ceramics

The appearance of colossal permittivity materials broadened the choice of materials for energy-storage applications. In this work, colossal permittivity in ceramics of TiO₂ co-doped with niobium and europium ions ((Eu_0.5Nb_0.5)_xTi_1-xO₂ ceramics) was reported. A large permittivity (ε_r ～ 2.01?×?10⁵) and a low dielectric loss (tanδ ～ 0.095) were observed for (Eu_0.5Nb_0.5)_xTi_1-xO₂ (x?=?1%) ceramics at 1?kHz. Moreover, two significant relaxations were observed in the temperature dependence of dielectric properties for (Eu, Nb) co-doped TiO₂ ceramics, which originated from defect dipoles and electron hopping, respectively. The low dielectric loss and high relative permittivity were ascribed to the electron-pinned defect-dipoles and electrons hopping. The (Eu_0.5Nb_0.5)_xTi_1-xO₂ ceramic with great colossal permittivity is one of the most promising candidates for high-energy density storage applications.     

Giant permittivity and low dielectric loss of Fe doped BaTiO3 ceramics: Experimental and first-principles calculations

Fe doped BaTiO₃ ceramics with giant permittivity and low dielectric loss were synthesized in N₂/H₂ atmosphere started with BaTiO₃ powders and iron powders. XRD analysis exhibited the tetragonal-pseudocubic phase transition when the Fe content is 3 mol%. XPS spectra confirmed the iron oxides with mixed-valence structure of Fe²⁺/Fe³⁺, while Ti-ions maintain Ti⁴⁺3d⁰ states without any oxidization-reduction. For the case of ceramics with 5 mol% Fe, the dielectric constant was 66,650 at 1000 Hz at room temperature, 19 times higher than that of pure BaTiO₃ ceramics, while the dielectric loss tangent was 0.13. Comparison with other giant-permittivity materials demonstrated the superior potential of present ceramics. First-principles calculations investigated the interfacial interaction of Fe-[TiO₂] interface and Fe-[BaO] interface. Giant dielectric constant was induced by the interfacial polarization between insulating ferroelectrics and semiconducting iron oxides with mixed-valence states, as well as the contribution from the generated electron hopping conduction.     

Li2AGeO4 (A = Zn,Mg): Two novel low-permittivity microwave dielectric ceramics with olivine structure

Two low-permittivity dielectric materials Li₂AGeO₄ (A?=?Zn, Mg) were prepared via the solid-state reaction method. X-ray diffraction analysis and Rietveld refinement indicated that both ceramics crystallize in an orthorhombic olivine structure with a space group Pmn2₁. Dense ceramics with high relative density and homogeneous microstructure were obtained. Li₂ZnGeO₄ densified at 1200?°C possessed a relative permittivity ε_r?=?6.5, a quality factor Q?×?f?=?35,400?GHz, and a temperature coefficient of resonant frequency. Li₂MgGeO₄ exhibited ε_r?=?6.1, Q?×?f?=?28,500?GHz, and τ_f?=?–74.7?ppm/°C when sintered at 1220?°C. Additionally, the large negative τ_f values of Li₂AGeO₄ (A?=?Zn, Mg) ceramics were successfully adjusted compensated by forming composite ceramics with CaTiO₃ and near-zero τ_f values of +2.9?ppm/°C and +5.8?ppm/°C were achieved in 0.92Li₂ZnGeO₄-0.08CaTiO₃ and 0.90Li₂MgGeO₄-0.10CaTiO₃, respectively.     

Effect of ionic radius on colossal permittivity properties of (A,Ta) co-doped TiO2 (A= alkaline-earth ions) ceramics

(A, B) co-doped TiO₂ ceramics attract great interests due to the excellent dielectric properties. In this work, the (A, Ta) co-doped TiO₂ ceramics were prepared by a solid state reaction process. The effect of the acceptors ionic radius on the structure and properties of TiO₂ ceramics was investigated. According to XRD analysis, the main phase is rutile TiO₂ for all samples. Due to the larger ionic radius, it is hard to replace Ti site in TiO₆ octahedron. As a result, the content of the secondary phase increased with increasing ionic radius. The dielectric properties were significantly enhanced by co-doping of alkaline-earth ions and tantalum ions, and the best dielectric constant obtained at 3% (Sr, Ta) co-doped compositions, where ε’ = 2.1 × 10⁵, tanδ = 0.21. Meanwhile, the XPS analysis suggested that the concentration of the defect dipoles exhibit a maximum in Sr-doped TiO₂ ceramics. The larger ionic radius of the acceptors leads to the more stability of the defect structure. However, for Ba ions, the replacement concentration decreased due to the excessive ionic radius, which in turn reduces the defect concentration. This work is meaningful for the further investigations on TiO₂-based colossal permittivity materials.