Influence of processing conditions on the ionic conductivity of holmium zirconate (Ho2Zr2O7)

Nanopowders of holmium zirconate (Ho₂Zr₂O₇) synthesised through carbon neutral sol-gel method were pressed into pellets and individually sintered for 2 h in a single step sintering (SSS) process from 1100 °C to 1500 °C at 100 °C interval and in a two step sintering (TSS) process at (I) −1500 °C for 5 min followed by (II) - 1300 °C for 96 h. Relative density of each of the sintered pellet was determined using the Archimedes’ technique and the theoretical density was calculated from crystal structure data. Grain size was obtained from SEM micrographs using ImageJ. Pellets processed by TSS have been found to be denser (98 %) with less grain growth (1.29 μm) as compared to the pellets processed using SSS process. Ionic conductivity of Ho₂Zr₂O₇ pellets sintered by two different processes was measured using ac impedance spectroscopy technique over the temperature range of 350 °C–750 °C in the frequency range of 100 mHz–100 MHz for both heating and cooling cycles. The temperature dependence of bulk (2.67⨯10⁻³ Scm⁻¹) and grain boundary (2.50⨯10⁻³ Scm⁻¹) conductivities of Ho₂Zr₂O₇ prepared by TSS process are greater than those processed by SSS process suggesting the strong influence of processing conditions and grain size. Results of this study, indicates that the TSS is the preferable route for processing the holmium zirconate as it can be sintered to exceptionally high densities at lower temperature, exhibits less grain growth and enhanced ionic conductivity compared with the samples processed by SSS process. Hence, holmium zirconate can be considered as a promising new oxide ion conducting solid electrolyte for intermediate temperature SOFC applications between 350 °C and 750 °C temperature range.     

Thermo-physical and mechanical properties of Yb2O3 and Sc2O3 co-doped Gd2Zr2O7 ceramics

Ceramic materials for the thermal barrier coating (TBC) application of Gd₂Zr₂O₇ (GZO), (Gd_0.94Yb_0.06)₂Zr₂O₇ (GYb_0.06Z), (Gd_0.925Sc_0.075)₂Zr₂O₇ (GSc_0.075Z), (Gd_0.865Sc_0.075Yb_0.06)₂Zr₂O₇ (GSc_0.075Yb_0.06Z), and (Gd_0.8Sc_0.1Yb_0.1)₂Zr₂O₇ (GSc_0.1Yb_0.1Z) were successfully synthesized by chemical co-precipitation. The effects of the doping of Sc₂O₃ and Yb₂O₃ on the phases, thermo-physical and mechanical properties of the ceramics were investigated. The results show that both Yb₂O₃ and Sc₂O₃ doping promoted the phase transition of GZO from pyrochlore to fluorite. All the Sc₂O₃-doped samples exhibited enhanced fracture toughness, as compared to the undoped sample. Furthermore, the GSc_0.075Yb_0.06Z sample revealed a thermal conductivity of ~0.8 W/mK at 1200 °C, which was nearly 30% lower than that of the undoped sample. The associated mechanisms related to the effects of the doping on the thermophysical and mechanical properties are discussed.     

Temporal stability of oxygen-ion conductivity in 1Nb2O5-10Sc2O3-89ZrO2

A slight Nb₂O₅ co-doping in 11Sc₂O₃-89ZrO₂ was earlier reported to stabilize the high-symmetry cubic phase completely and enhances the conductivity significantly. The present work looked at the temporal stability of conductivity in 1Nb₂O₅-10Sc₂O₃-89ZrO₂ (1Nb10ScSZ) for the electrolyte application in solid oxide fuel cells. In-situ conductivity measurement was done using impedance spectroscopy at 650 °C in the air for 2000 h. A substantial conductivity loss (29%) was observed in the first 1000 h. Following which, conductivity remained relatively stable for the next 1000 h. Impedance analysis showed that the main contribution to the conductivity degradation was from grain conductivity. Phase analysis performed using XRD, TEM and Raman spectroscopy revealed that both the unaged and aged 1Nb10ScSZ samples consisted of metastable t″-phase. However, the extent of tetragonality was found to increase after ageing. The formation of low-symmetry phase was suggested to be the reason for the grain conductivity loss in 1Nb10ScSZ.     

Effect of point defects on the thermal conductivity of Sc2O3-Y2O3 co-stabilized tetragonal ZrO2 ceramic materials

In this paper, the reduction mechanism in thermal conductivity of a series of Sc₂O₃-Y₂O₃ co-stabilized tetragonal ZrO₂ ceramics is systematically discussed. The thermal conductivity is approximately 20–28% lower than that of 6–8 wt.% yttria-stabilized zirconia (YSZ). A phonon scattering model, on account of the influence of oxygen vacancy variation and cation mass fluctuation, is optimized and utilized to depict the thermal conductivity of these materials. For the samples with the same amount of oxygen vacancy, Sc³⁺ is more effective in lowering thermal conductivity than Y³⁺ due to the large mass difference with Zr⁴⁺, as evidenced by the scattering model and phonon vibrational density of states. The experimental and calculation results suggest that this optimized model is proved to be more effective in predicting the thermal conductivity of binary or multiple rare earth oxides co-doped tetragonal ZrO₂ and guiding the compositional design of thermal barrier materials.     

Influence of Fe2O3 addition on the densification and oxygen ion conductivity of the GdSmZr2O7 ceramic

The influence of Fe₂O₃ addition as a sintering aid on the microstructure and electrical properties of the GdSmZr₂O₇ ceramic has been studied. The GdSmZr₂O₇ ceramic with 1 wt.% Fe₂O₃ is composed of a pyrochlore-type phase and a small amount of Gd_0.5Sm_0.5FeO₃. Fe₂O₃ is found to be an effective sintering aid for the GdSmZr₂O₇ ceramic, and a reduction in the sintering temperature of about 200 K is achieved. The total conductivity of the GdSmZr₂O₇ ceramic incorporated with or without 1 wt.% Fe₂O₃ obeys the Arrhenius relation. At 1173 K, the highest total conductivity of the GdSmZr₂O₇ ceramic with 1 wt.% Fe₂O₃ is about 20% higher than that of the GdSmZr₂O₇ ceramic. The GdSmZr₂O₇ ceramic with or without 1 wt.% Fe₂O₃ is an oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels.     

Enhanced Li-ion conductivity of strontium doped Li-excess garnet-type Li7+xLa3-xSrxZr2O12

The mechanism underlying the enhancement of the conductivity of Li₇La₃Zr₂O₁₂ (LLZO), an oxide-based solid electrolyte that contains excess Li, was experimentally investigated through subvalent cation substitution. We prepared Sr-substituted Li-rich LLZO with high conductivity of the order of 10⁻⁴ S/cm by using a solid-state method. We investigated the mechanism underlying the conductivity enhancement via detailed structural analysis through Sr K-edge X-ray absorption near edge spectroscopy and X-ray diffraction and neutron powder diffraction analyses. The results suggested that the conductivity enhancement is due to the change in Li⁺ arrangement caused by the incorporation of excess Li into the LLZO lattice.     

Electrical conductivity and nonstoichiometry in doped Sr3Ti2O7

A series of doped Ruddlesden–Popper phases, of general formula Sr₃Ti_2-xM_xO_7-δ (M=Al, Ga, Co), were synthesized and their electrical conductivity characterized as a function of temperature and oxygen partial pressure. For fixed-valent dopants, p-type conductivity predominates at p(O₂)> 10⁻⁵ atm, followed by a p(O₂)-independent electrolytic regime, and n-type electronic conductivity at very low p(O₂). The electrolytic regime exhibits activation energies in the range 1·7–1·8 eV. Doping with transition metals such as Co results in a very significant increase in total conductivity with a p-type conductivity at high p(O₂). Furthermore, an apparent ionic regime at intermediate p(O₂) is observed, characterized by high conductivity (> 10⁻² S/cm at 700°C) and low activation energy (0·6 eV). This interpretation is consistent with iodometric measurements as interpreted by a defect chemical model. Other measurements are in progress to confirm this conclusion.     

Effects of Gd3+ substitution on the structure,photoluminescence, scintillation,and thermometric features of Pr3+:Lu2Zr2O7 phosphors

In this study, it is shown how the photoluminescence, scintillation, and optical thermometric properties are managed via the introduction of Gd³⁺ ions into Pr³⁺:Lu₂Zr₂O₇. Raman spectra validate that partial replacement of Lu³⁺ with Gd³⁺ can promote the phase transition of Lu₂Zr₂O₇ host from the defective fluorite structure to the ordered pyrochlore one. Upon 289 nm excitation, all the samples emit the 483 (³P₀ → ³H₄), 581 (¹D₂ → ³H₄), 611 (³P₀ → ³H₆), 636 (³P₀ → ³F₂), and 714 nm (³P₀ → ³F₄) emissions from Pr³⁺ ions, which are enhanced with the addition of Gd³⁺ ions due to the modification of crystal structure. Dissimilarly, the X-ray excited luminescence spectra consist of a strong emission located at 314 nm from Gd³⁺ ions (⁶P_7/2 → ⁸S_7/2), together with the typical emissions from Pr³⁺ ions, which exhibit different dependences on the Gd³⁺ concentration. When the luminescence intensity ratio between the ³P₀ → ³H₆ (611 nm) and ¹D₂ → ³H₄ (581 nm) transitions is selected for temperature sensing, Pr³⁺:(Lu_0.75Gd_0.25)₂Zr₂O₇ shows the optimal relative sensing sensitivity of 0.78% K⁻¹ at 303 K, which is higher than that of the Gd³⁺-free sample. Therefore, the developed Pr³⁺:(Lu, Gd)₂Zr₂O₇ phosphors have the applicative potential for optical thermometry, X-ray detection, and photodynamic therapy.     

Ceria‐doped scandia‐stabilized zirconia (10Sc2O3·1CeO2·89ZrO2) as electrolyte for SOFCs: Sintering and ionic conductivity of thin,flat sheets

In this study, thin, flat sheets, about 90 μm thick, were prepared from ceria‐doped scandia‐stabilized zirconia with molecular formula 10Sc₂O₃·1CeO₂·89 ZrO₂ (10Sc1CeSZ) by tape casting and subsequent sintering at different thermal cycles. A sintering thermal cycle was selected that yielded defect‐free flat sheets, with practically negligible porosity (between 0.35% and 0.10%) and average grain diameters ranging from 1.32 to 6.30 μm. Ionic conductivity at 600°C was as high as 21 mS/cm. Ionic conductivity increased with average grain diameters up to 2.7 μm. At higher average grain diameters, conductivity remained practically constant.     

Improved ionic conductivity of nitrile rubber/ionic liquid composites

Polymer electrolytes with high ionic conductivity and good elasticity were prepared by mixing nitrile rubber (poly(acrylonitrile-co-butadiene) rubber; NBR) with ionic liquid, N-ethylimidazolium bis(trifluoromethanesulfonyl)imide (EImTFSI). The NBR/EImTFSI composites were obtained as homogeneous and transparent films when the ionic liquid content was less than 60 wt%. Raman spectroscopy suggested the interaction between nitrile group of NBR and TFSI anion. Sample with ionic liquid content of 50 wt% showed the ionic conductivity of 1.2×10⁻⁵ S cm⁻¹ at 30 °C. Addition of lithium salt to this NBR/EImTFSI composite further enhanced the ionic conductivity to about 10⁻⁴ S cm⁻¹ without spoiling mechanical properties. DSC studies showed two glass transition temperatures for composites indicating microphase separation.     

One-step synthesis of Sc2W3O12:Eu3+ phosphors with tunable luminescence for WLED

Sc₂W₃O₁₂ is an important host matrix for rare-earth doped luminescence. However, the conventional method to prepare the material is solid-state reaction, which results into coarse and irregular morphologies. In this work, Eu³⁺ doped Sc₂W₃O₁₂ phosphors with high crystallinity and pure phase were successfully synthesized via one-step hydrothermal method. It was found that the crystalline phase changed from Sc₂W₃O₁₂ phase to Na₄Sc₂(WO₄)₅ phase when the molar ratio between Sc(NO₃)₃ and Na₂WO₄ decreased. The temperature-dependent X-ray diffraction analysis was performed to prove the negative thermal expansion property of Sc₂W₃O₁₂. A systematic study on the effect of reaction time, temperature and Eu³⁺ doping concentration was explored. It was also found that the as-prepared samples displayed tunable emission colors, ranging from blueish white to orange red. Particularly, the white light emission with the chromaticity coordinate of (0.3395, 0.3289) can be realized in Sc₂W₃O₁₂: 5% Eu³⁺. What's more, the photoluminescence properties of the samples were investigated under different ambient temperatures between 97 and 280?K. The result clearly showed energy transfer between Eu³⁺ and WO₄^2?. The above results suggested that Sc₂W₃O₁₂:Eu³⁺ can be excellent candidate for solid-state lasing, panel display and WLEDs.     

Synthesis of Ga-doped Li7La3Zr2O12 solid electrolyte with high Li+ ion conductivity

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) Li⁺ ion solid electrolyte is a promising candidate for next generation high-safety solid-state batteries. Ga-doped LLZO exhibits excellent Li⁺ ion conductivity, higher than 1 × 10^?3 S cm^?1. In this research, the doping amount of Ga, the calcination temperature of Ga-LLZO primary powders, the sintering conditions and the evolution of grains are explored to demonstrate the optimum parameters to obtain a highly conductive ceramics reproducibly via conventional solid-state reaction methods under ambient air sintering atmosphere. Cubic LLZO phase is obtained for Li_6.4Ga_0.2La₃Zr₂O₁₂ powder calcined at low temperature 850 °C. In addition, ceramic pellets sintered at 1100 °C for 320 min using this powder have relative densities higher than 94% and conductivities higher than 1.2 × 10^?3 S cm^?1 at 25 °C.     

Improved ionic conductivity of zirconia-scandia with niobia addition

The ionic conductivity and the crystalline structure of ZrO₂−10 mol% Sc₂O₃- x mol% Nb₂O₅ solid electrolytes were investigated for x=0.25, 0.5 and 1. Dense specimens with relative densities higher than 95% were prepared by solid state reaction and sintered at 1500 °C for 5 h. Full stabilization of the cubic structure at room temperature was obtained for compounds with x=0.5 and 1, whereas the cubic and rhombohedric structures coexist for x=0.25. The highest ionic conductivity in codoped system was found for specimen containing 0.5 mol% niobium pentoxide, with the same order of magnitude as that of the parent solid electrolyte (zirconia-10 mol% scandia) in the high temperature range (above 600 °C). Preliminary investigation on phase stability shows that the isothermal conductivity of the new solid electrolyte remained constant up to 100 h at 600 °C. Niobium pentoxide addition was found to improve the overall ionic conductivity of zirconia-scandia solid electrolyte.     

Enhanced electromagnetic absorption properties of Fe-doped Sc2Si2O7 ceramics

Doping transition metal elements in a crystal causes distortion and defects in the lattice structure, which change the electronic structure and magnetic moment, thereby adjusting the electrical conductivity and electromagnetic properties of the material. Fe-doped Sc₂Si₂O₇ ceramics were synthesized using the sol-gel method for application to microwave absorption. The effect of Fe-doped content on the electromagnetic (EM) and microwave absorption properties was investigated in the Ku-band (12.4–18 GHz). As expected, the dielectric and magnetic properties improve substantially with increasing Fe content. Fe doping causes defects and impurity levels, which enhance polarization loss and conductance loss, respectively. Fe replaces Sc atoms in the ScO₆ octahedral structure, creating a difference in spin magnetic moments, which increases the magnetic moment. Moreover, the magnetic coupling of Fe and O atoms occurs at the Fermi level, which benefits magnetic loss. In particular, when the Fe content is 6%, the fabricated Fe-doped Sc₂Si₂O₇ ceramics show an absorption property with absorption peaks located at 14.5 GHz and a minimum reflection loss (RL_min) of ?12.8 dB. Therefore, Fe-doped Sc₂Si₂O₇ ceramics with anti-oxidation and good microwave absorption performance have a greater potential for application in high-temperature and water-vapor environments.     

Ca3Sc2Si3O12:Ce3+,Nd3+近红外荧光粉的制备和发光性质

利用高温固相法在弱还原气氛中制备了Ca3-x-ySc2Si3O12:xCe3+,yNd3+近红外发光荧光粉。用X射线衍射确定了样品的相结构,并研究了样品的可见及近红外激发和发射光谱,发光强度,荧光寿命等随Ce3+,Nd3+掺杂量的变化。结果表明:Ca3-x-ySc2Si3O12:xCe3+,yNd3+体系中Ce3+的发射光谱和Nd3+的激发光谱的有效重叠,说明存在Ce3+到Nd3+的高效能量传递,Ce3+,Nd3+的掺杂量分别为x=0.1和y=0.07时,Ca3-x-ySc2Si3O12:xCe3+,yNd3+粉体具有最强的近红外发射。与单掺Na3+的样品相比,Ca3Sc2Si3O12中掺杂Ce3+和Nd3+后,样品的近红外发光增强近400倍。此外,初步分析了Ca3-x-ySc2Si3O12:xCe3+,yNd3+中Ce3+到Nd3+的能量传递机理。     

Enhanced ionic conductivity and thermal shock resistance of MgO stabilized ZrO2 doped with Y2O3

The present work focused on the effect of Y₂O₃ co-doping on the phase composition, microstructure, ionic conductivity and thermal shock resistance of 8 mol% MgO stabilized ZrO₂ (Mg-PSZ) electrolyte ceramics for high temperature applications. The addition of Y₂O₃ could promote the process of monoclinic-to-cubic/tetragonal phase transformation and became the metastable phase at room temperature. Meanwhile, the grain size of Mg-PSZ decreased. It was demonstrated that an appreciable increase in the ionic conductivity and compressive strength occurred on substituting MgO with Y₂O₃ in the Mg-PSZ electrolyte ceramics across the measured temperature range. Moreover, the Y₂O₃ addition could restrain the adverse effect of the cyclic thermal shock on the ionic conductivity and compressive strength of Mg-PSZ. The main reason was that the increase of the amount of monoclinic phase caused by cubic/tetragonal-to-monoclinic phase transformation by the cyclic thermal shock was restrained after the Y₂O₃ addition.     

Comparison of hot corrosion resistance of Sm2Zr2O7 and (Sm0.5Sc0.5)2Zr2O7 ceramics in Na2SO4+V2O5 molten salt

Sm₂Zr₂O₇ and (Sm_0.5Sc_0.5)₂Zr₂O₇ ceramics were fabricated by a chemical co-precipitation and calcination method, and their hot corrosion behaviors in Na₂SO₄+V₂O₅ molten salt were investigated. Hot corrosion tests were carried at 700 °C, 800 °C and 900 °C for 4 h, and corroded surfaces were investigated using X-ray diffractometer and scanning electron microscopy. The corrosion products of Sm₂Zr₂O₇ ceramics were composed of SmVO₄ and monoclinic-ZrO₂, while those of (Sm_0.5Sc_0.5)₂Zr₂O₇ ceramic consisted of SmVO₄ and Zr₅Sc₂O₁₃. Considering the fact that Zr₅Sc₂O₁₃ is more desirable than monoclinic-ZrO₂ for thermal barrier coating applications, (Sm_0.5Sc_0.5)₂Zr₂O₇ showed better corrosion resistance to Na₂SO₄+V₂O₅ salt than Sm₂Zr₂O₇. The hot corrosion mechanisms of Sm₂Zr₂O₇ and (Sm_0.5Sc_0.5)₂Zr₂O₇ in Na₂SO₄+ V₂O₅ salt were discussed in detail.     

Influence of magnesia doping on structure and electrical conductivity of pyrochlore type GdSmZr2O7

Abstract

Polycrystalline ceramic samples of magnesia doped GdSm_1–xMg_xZr₂O_7–x/2 have been prepared by conventional solid state reaction method using high purity oxides. The influence of magnesia dopant content on densification, microstructure and electrical properties of GdSm_1–xMg_xZr₂O_7–x/2 ceramics are investigated. Magnesia doping promotes the sintering densification behaviour of GdSm_1–xMg_xZr₂O_7–x/2 ceramics. GdSm_1–xMg_xZr₂O_7–x/2 (x?=?0, 0·05, 0·10) ceramics have a single phase of the pyrochlore type structure, while GdSm_1–xMg_xZr₂O_7–x/2 (x?=?0·15, 0·20) ceramics consist of the pyrochlore type structure and a small amount of magnesia as the second phase. The total conductivity of GdSm_1–xMg_xZr₂O_7–x/2 ceramics obeys the Arrhenius relation, and gradually increases with increasing temperature from 723 to 1173 K. GdSm_1–xMg_xZr₂O_7–x/2 ceramics are oxide-ion conductors in the oxygen partial pressure range of 1·0×10^–4 to 1·0 atm at each test temperature. The maximum value of the total conductivity is 1·29×10^–2 S cm^–1 at 1173 K for the GdSm_0·85Mg_0·15Zr₂O_6·925 ceramic.