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1.
Although the d-band correlated rare-earth nickelates (ReNiO3) exhibit broadly adjustable metal to insulator transitions (MIT) that enables emerging correlated electronic applications, it is yet difficult to regulate their associated critical temperature (TMIT) below 100 K. Herein, we extend the lower limit in TMIT of ReNiO3 down to 83 K while maintaining an abrupt switch in resistivity via partial La-substitution of PrNiO3. The near edge X-ray fine structure analysis and density function theory calculations indicate the strengthening in the metallic orbital configuration and reduction in the ground state band gap via La-substitution of Re in NdNiO3 and PrNiO3. In contrast, analogous Ce substitution cannot reduce the TMIT of ReNiO3 owing to its valance variability toward +4, while La partial substitution of ReNiO3 with middle or heavy rare-earth (e.g., Sm) easily disturb the co-occupation of the Re-site by the two rare-earths as one dispersive phase.  相似文献   

2.
Polycrystalline magneto-optical (Ho1-xPrx)2O3 (x = 0.05?0.2) ceramics were fabricated by vacuum sintering using layered rare-earth hydroxides as the precursors, among which the 5 at.% Pr doped specimen exhibits the highest in-line transmittance of ~76.1 % at 700 nm (~94.5 % of the theoretical value of defect-free Ho2O3 single crystal) and the largest Verdet constant of ?82 ± 6 rad?T?1 m?1 at 1064 nm (~2.3 times that of the commercial Tb3Ga5O12 crystal and ~1.8 times that of the pure Ho2O3 ceramic). More Pr addition not only leads to a higher thermal decomposition temperature for the precursor but also a decreasing particle size for the oxide. A 5 at.% Pr dopant in Ho2O3 matrix generally exists in the oxidation state of +3, while an increasing Pr concentration up to 10 at.% induces coexisting valences of +3 and +4. The grain growth was suppressed by the present Pr4+ based on interstitial mechanism. The substitution of Pr3+ for Ho3+ is helpful for the rising Verdet constant of the binary ceramic, but Pr4+ has little positive contribution to it.  相似文献   

3.
《Ceramics International》2016,42(5):6236-6243
Lanthanum–praseodymium hexaboride (LaxPr1−xB6) nanoawls have been fabricated via a simple flux-controlled method using lanthanum (La) powders, praseodymium (Pr) powders and boron trichloride (BCl3) gas as starting materials at 1050 °C. Scanning electron microscopy (SEM) shows that the tapered nanoawls have a length of 2–10 μm and a diameter ranging from 50 to 300 nm at the roots and 10–80 nm at the tips. Transmission electron microscopy (TEM) reveals that the nanoawls are single crystalline with the preferred growth direction along [110]. Raman spectra indicate that the T1u mode splitting effect occurs in this ternary rare-earth hexaboride. In addition, a concentration gradient is necessary to create these awl-like structures where the combination of self-catalyzed and vapor–solid growth is responsible for the growth of tapered LaxPr1−xB6 nanoawls.  相似文献   

4.
《Ceramics International》2022,48(11):15737-15747
Zn4O(BO2)6 based on the [B24O48] sodalite-cage structure fixed by the inside [Zn4O13] clusters is expected to be a new class of solid-state lighting material with perfect thermal and mechanical stability. Herein, in the current work, we have respectively introduced non-equivalent rare-earth cations Eu3+ and Pr3+ into Zn4O(BO2)6 host to design white and green emission materials by a novel solid-phase sintering method at lower temperatures. Zn2B6O11 replacing B2O3 or H3BO3 as raw materials can effectively avoid the impure products caused by the uncontrollable volatilization of B2O3 or H3BO3. The newly designed light-emitting materials of Zn4(1-x)O(BO2)6: xRe3+ (ReEu or Pr), including Zn4O(BO2)6 host, have good absorption capacity in the ultraviolet region. Under ultraviolet irradiation, Zn4O(BO2)6, Zn4(1-x)O(BO2)6: xEu3+and Zn4(1-x)O(BO2)6: xPr3+ emit the blue, white and green lights, respectively. In addition, all these materials can effectively degrade methylene blue, in which Zn4(1-x)O(BO2)6: xPr3+ has the highest efficiency. The luminescence and degradation mechanisms of Zn4O(BO2)6, Zn4(1-x)O(BO2)6: xEu3+and Zn4(1-x)O(BO2)6: xPr3+ have been adequately explained by their electronic structures based on the first principle calculations. The current study confirms that the doping of Eu3+/Pr3+ in Zn4O(BO2)6 can broaden its applications as photoluminescent and photocatalytic materials.  相似文献   

5.
《Ceramics International》2019,45(14):16886-16892
The series of La1-xPrxGa0.5Sb1.5O6 solid solutions (x = 0–1) with PbSb2O6 structure was synthesized. The comparative study of the La1-xPrxGa0.5Sb1.5O6 morphology showed all compounds have net microstructures. Herein the Pr concentration increasing leads to particles size decreasing from 400 up to 200 nm in the samples with low Pr content and to recrystallization and coarsening of the particles in Pr-rich ones. Using LaGa0.5Sb1.5O6 as an example, it was shown that the compounds have a wide transmission region in the visible and IR spectral ranges and are characterized by a low-energy phonon spectrum. An analysis of the spectral-luminescent characteristics revealed the presence of a cross-relaxation process (1D21G4) → (3H43F4) of Pr3+ ions for La1-xPrxGa0.5Sb1.5O6 at x ≥ 0.07. It was showed that a broadband radiation of thermal nature is observed under laser excitation with λ = 457 nm and a power density of J = 4.65 kW/cm2 for the samples with high (x = 0.4–1) praseodymium content.  相似文献   

6.
The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (PrxZr(1−y)Si(1−z)O4; y + z = x; 0.02 < x < 0.10) specimens prepared via sol–gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, PrxZr(1−y)Si(1−z)O4 materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical features denote that most of the Pr centers are originally in its 4+ oxidation state in the parent PrxZr(1−y)Si(1−z)O4 specimens. The variation of the catalytic performance of such specimens with potential scan rate, water concentration and Pr loading suggests that Pr is not uniformly distributed within the zircon grains, being concentrated in the outer region of such grains.  相似文献   

7.
Spray deposition followed by sintering of nickel oxide (NiO x ) nanoparticles (average diameter: 40 nm) has been chosen as method of deposition of mesoporous NiO x coatings onto indium tin oxide (ITO) substrates. This procedure allows the scalable preparation of NiO x samples with large surface area (~103 times the geometrical area) and its potential for applications such as electrocatalysis or electrochemical solar energy conversion, which require high electroactivity in confined systems. The potential of these NiO x films as semiconducting cathodes for dye-sensitized solar cell (DSC) purposes has been evaluated for 0.3–3-μm-thick films of NiO x sensitized with erythrosine B (ERY). The electrochemical processes involving the NiO x coatings in the pristine and sensitized states were examined and indicated surface confinement as demonstrated by the linear dependence of the current densities with the scan rate of the cyclic voltammetry. Cathodic polarization of NiO x on ITO can also lead to the irreversible reduction of the underlying ITO substrate because of the mesoporous nature of the sintered NiO x film that allows the shunting of ITO to the electrolyte. ITO-based reduction processes alter irreversibly the properties of charge transfer through the ITO/NiOx interface and limit the range of potential to NiO x coatings sintered for DSC purposes.  相似文献   

8.
《Ceramics International》2015,41(7):8511-8519
Crystalline solid solution of Bi1−xPrxFeO3 (x=0.05, 0.1, and 0.15) ceramics has been successfully synthesized by a low temperature assisted co-precipitation method. Rietveld-refinement of the X-ray diffraction data reveals rhombohedral structure for Bi1−xPrxFeO3 (x=0.05, 0.10) and triclinic for Bi1−xPrxFeO3 (x=0.15). The crystallite sizes of the Bi1−xPrxFeO3 (x=0.05, 0.1 and 0.15) are found to be approximately 33, 27 and 22 nm respectively calculated using Debye–Scherrer equation. The SEM images of Bi1−xPrxFeO3 (x=0.05, 0.10 and 0.15) ceramics show grains with almost spherical morphology. 4A1 and 7E Raman modes have been observed in the range 100–650 cm−1 and two phonon modes centered around 1150–1450 cm−1 have also been observed corresponding to 2A4 (LO), 2E8 (TO) and 2E9 (TO) modes of Bi1−xPrxFeO3 (x=0.05, 0.1 and 0.15). The changes in Raman modes such as prominent frequency shift, line broadening and intensity have been noticed with the increase of Pr concentration in BiFeO3 (BFO) suggesting a structural transformation as revealed by the Rietveld refinement. An anomaly in the temperature dependent dielectric studies has been noticed in all the samples at the vicinity of Neel temperature (TN) indicating a magnetic ordering and an increase in magnetization with increase of Pr concentration is noticed from the room temperature magnetic studies. Further, the leakage current density is found to be reduced with increasing Pr concentration.  相似文献   

9.
Yellow inorganic pigments PrxZr1-xSiO4 (x?=?0–0.08) have been prepared by a novel non-hydrolytic sol-gel (NHSG) method at 750?°C for 2?h. Replacing Pr4+ for Zr4+ in ZrSiO4 increased the cell volume and changed the color from white to yellow gradually. The Si―O―Zr and Si―O―Pr bands were observed in the FT-IR spectra of xerogel, indicating it could reach homogeneous mixing at the atomic level. Therefore, it promoted the solid solution reaction between Pr and zircon at low temperature. The samples exhibit high doping limitation (x?=?0.08) and brilliant yellow hue (b*?=?69.48) in contrast with the previously reported praseodymium zircon yellow pigments. The intense of yellow hue was increased with increasing the Pr doping content due to the increase of Pr4+/Pr3+ species. After applying on bisque ceramic tiles, the pigment exhibited excellent coloration, high thermal stability and low solubility in molten glazes, indicating its potential application in ceramic decoration.  相似文献   

10.
Gd0.2-xPrxCe0.8O1.90, (x?=?0, 0.02, 0.04, 0.06, 0.08, 0.10) has been synthesized by means of a simple co-precipitation route based on ammonium carbonate as the precipitating agent. The as-synthesized precursors are cerium-gadolinium-praseodymium amorphous hydroxycarbonates, which are nanometric in size with highly homogeneous morphology, leading to reactive doped and co-doped nanocrystalline (≈13?nm) ceria after a mild thermal treatment (2?h at 600?°C). The obtained results highlight the very positive effect of Pr on the powders’ sintering behaviour, which favour a better densification of the final pellets, thus improving both their microstructure (with relative densities of 97–99% after sintering at 1250?°C for 3?h) and electrochemical properties (up to 1.25·10–1?S?cm?1 at 800?°C for sample 6Pr) compared to the state-of-art ceria-based electrolytes. Through a comprehensive characterization, a relation was formed between the Pr content and the microstructural features of the sintered pellets and their electrical behaviour. The amount of Pr doping was investigated over a wide range and 6?mol% has been established to be optimal (possessing the lowest electronic conductivity contribution). Definitely, these results indicate that Gd0.2-xPrxCe0.8O1.90 has an excellent set of characteristics, both microstructural and electrical, and a convenient fabrication process, thus making it perfectly suitable for IT-SOFC practical applications.  相似文献   

11.
In this work, polycrystalline Pr1-xBaxMnO3 (0.25 ≤ x ≤ 0.36) ceramics were synthesized, and their magnetic and electrical transport properties were systematically studied. All samples show two metal-insulator transitions (MITs) corresponding to the high temperature TMI1 and low temperature TMI2, respectively, besides the non-Griffith phase above the ferromagnetic (FM) transition temperature TC. Combining the results of the transport and magnetic properties, it is found that the FM transition temperature TC coincides with the temperature TMI1, which is linearly related to the A-site ionic radius mismatch variance σ2, indicating the enhancement of FM interactions due to the increase of the degree of B-site ordering of Mn3+/Mn4+ ions. The positive correlation between ferromagnetic insulators (FMI) and magnetic interactions, including the FM and short-range antiferromagnetic (AFM) interactions, is confirmed. It is suggested that the first MIT at TMI1 is attributed to the Mn3+/Mn4+ double exchange interactions and the second MIT at TMI2 is closely related to the suppression of the AFM interactions under the internal FM field induced by the Mn3+/Mn4+ DE interactions. This work provides not only a theoretical understanding on the origin of MIT at low temperature, but also a new way for adjusting the FMI in perovskite manganese oxide Pr1-xBaxMnO3 for application.  相似文献   

12.
《Ceramics International》2023,49(5):7333-7340
Transparent Pr3+ doped Ca1-xGdxF2+x (x = 0, 0.01, 0.03, 0.06, 0.10, 0.15) polycrystalline ceramics with fine-grained microstructures were prepared by the hot-pressing method. The dependence of microstructure, optical transmittance, luminescence performances and mechanical properties on the Gd3+ concentrations for Pr3+:Ca1-xGdxF2+x transparent ceramics were investigated. The Gd3+ ions show positive effects on the microhardness of Pr3+:Ca1-xGdxF2+x transparent ceramics as a result of the decrease in the grain sizes. Excited by the Xenon lamp of 444 nm, typical visible emissions located at 484 nm, 598 nm and 642 nm were observed. Furthermore, the incorporation of Gd3+ ions can greatly enhance the photoluminescence performance owing to the improvement in the concentration quenching effect. The quenching concentration of Pr3+ ions in CaF2 transparent ceramics increased to 1 at.% as a result of the positive effect of Gd3+ codoping. The energy transfer mechanism of Pr3+ in the Pr3+:Ca1-xGdxF2+x transparent ceramics has been investigated and discussed.  相似文献   

13.
《Ceramics International》2020,46(8):11474-11483
High permittivity Ba4(Pr1-xSmx)28/3Ti18-yAl4y/3O54(0.4≤x ≤ 0.7, 0≤y ≤ 1.5) ceramics were synthesized using a standard solid-state method. The effects of Sm3+ substitution into the A-site and Sm3+/Al3+ cosubstitution into the A/B-sites on the microstructure, crystal structure, Raman spectra, infrared reflectivity (IR) spectra and dielectric characteristics were investigated in a Ba4Pr28/3Ti18O54 solid solution. In the ceramic samples of Ba4(Pr1-xSmx)28/3Ti18O54(0.4≤x ≤ 0.7), Sm3+ partial substitution for Pr3+ could improve the quality factor (Qf) value and reduce the TCF value. Nevertheless, the quality factor (Qf~10,000GHz) needed further improvement and the TCF values (+12.3~+35.4 ppm/°C) were still too large. Therefore, Al3+ was introduced for further optimization of the TCF values and Qf values of the Ba4(Pr1-xSmx)28/3Ti18O54 ceramics. Sm/Al cosubstitution led to a good combination of high εr (εr ≥ 70), high Qf (Qf ≥ 12,000 GHz), and near-zero TCF (−10 < TCF < +10 ppm/°C) in a wide range (0.4≤x ≤ 0.7). Infrared reflectivity (IR) spectra indicated that A-TiO6 vibration modes gave the primary contribution rather than Ti–O bending and stretching modes. The decrease in the degree of B-site cations order could be confirmed by Raman spectra. XPS results demonstrated that the improvement of quality factor (Qf) value was strongly related to the suppression of Ti3+. Excellent dielectric properties were achieved in Ba4(Pr1-xSmx)28/3Ti18-yAl4y/3O54 microwave ceramics with x = 0.5 and y = 1.25: εr = 72.5, Qf = 13,900GHz, TCF = +1.3 ppm/°C.  相似文献   

14.
《Ceramics International》2016,42(16):18692-18699
Bi1−xPrxFe0.97Mn0.03O3 (x=0.00, 0.05, 0.10, 0.15, 0.20) thin films were deposited on FTO/glass substrate using chemical solution deposition. The influences of Pr doping on the crystalline structure and multiferroic properties were investigated. In the X-ray diffraction and Raman spectra results, the crystal structures of Bi1−xPrxFe0.97Mn0.03O3 films revealed a gradual transformation from the trigonal structure to the tetragonal structure. The leakage current densities of Bi1−xPrxFe0.97Mn0.03O3 films are one order of magnitude lower than that of BiFeO3. Compared with unsaturated polarization-electric field hysteresis loop of BiFeO3 film, the Pr and Mn co-doped BFO films have significantly improved ferroelectric properties. The improved remnant polarization (Pr=91.3 µC/cm2) and the positive switching current (I=0.028 A) have been observed in Bi0.85Pr0.15Fe0.97Mn0.03O3 film. The improved electrical properties are attributed to the structure transformation, increasing grain boundaries, low oxygen vacancies ratio and increasing Fe3+ concentration. In addition, the saturation magnetization of Bi0.85Pr0.15Fe0.97Mn0.03O3 film is 1.81 emu/cm3, which is approximately three times higher than pure BiFeO3 (Ms=0.67 emu/cm3).  相似文献   

15.
The annealing temperature (Ta) dependent development in phase purity, morphology and magnetic properties of BaxPb1-xFe12O19 (x?=?0, 0.2, 0.4, 0.6, 0.8 and 1) powders synthesized via sol-gel auto-combustion route were studied. The hexagonal phase of PbFe12O19 forms directly via solid-state-reaction between α-Fe2O3 and PbO during annealing of the combustion product at Ta ~ 900?°C, but the BaFe12O19 phase forms at Ta ~ 1200?°C through the formation of BaFe2O4 and α-Fe2O3 as intermediate-phases at low Ta. The BaxPb1-x Fe12O19-phase purity of the samples depend on Ta. For Ta >?1000?°C, PbO evaporates from Pb-containing samples. With increasing Ta, growth of hexagonal-shaped sharp-edged particles was observed for Barium-rich samples, however, the sharp-edges dissolute for Lead-rich samples. High saturation magnetization was observed for Ba-rich samples annealed at 1100?°C. For all the studied samples, magnetic coercivity increases with x but decreases with Ta. The magnetic properties were correlated with the structure, microstructure and grain-size of the samples.  相似文献   

16.
《Ceramics International》2022,48(24):36046-36055
In this paper, nanopowders based on iron-deficient Sc2-xFexO3 (x = 0.17–0.47) nanocrystals with bixbyite structure and crystallite size of 3.7–38.9 nm were successfully synthesized via solution combustion. Variable glycine-to-nitrate (G/N) ratio was the main controlling factor. A wide range of experimental and computational methods were used to analyze the impact of spatial constraints on the resulting solid-state products. It was found that solution combustion mode greatly influenced on the temperature and gaseous products in the reaction zone. Volume (G/N = 0.4–0.8, Tmax = 1179–1511 °C), self-propagating (G/N = 1.0–1.4, Tmax = 614–957 °C) or smoldering (G/N = 0.2, Tmax = 443 °C) combustion modes were acquired during the synthesis depending on G/N ratio. It was shown that the formation of impurity phases of am-Fe2O3 (Tmax < 850 °C), c-Fe3O4 (900 °C < Tmax < 1500 °C) or c-FeO (Tmax > 1500 °C) was possible, depending on the combustion temperature. Besides, the combustion mode affected the porous and surfacial structure of resulting mesoporous nanopowders – specific surface area and total pore volume varied in ranges of 1.7–82.8 m2/g and 0.0088–0.1538 cm3/g, consequently. Chemical composition and unit cell parameters of Sc2-xFexO3 showed the positive deviation from Vegard's law. The average sizes of the interpore thickness (h) depending on G/N ratio were found from values of specific surface area and pycnometric density of nanopowders, which made it possible to establish the presence of spatial constraints for the crystals' growth of Sc2-xFexO3 at h values below 10 nm. Analysis of aspect (h/D) ratio allowed to determine synthetic parameters which led to mono- or polycrystalline structure of interpore space in resulting Sc2-xFexO3-based nanopowders. The results and patterns established in this paper allowed to synthesize a new type of foam-like functional materials based on rare-earth ferrites.  相似文献   

17.
The bismuth layer-structured Na0.5Bi4.5-xPrxTi4O15 (x?=?0, 0.1, 0.2, 0.3, 0.4, and 0.5) (NBT-xPr3+) ceramics were fabricated using the traditional solid reaction process. The effect of different Pr3+ contents on dielectric, ferroelectric and piezoelectric properties of Na0.5Bi4.5Ti4O15 ceramics were investigated. The grain size of Pr3+-doping ceramics was found to be smaller than that of pure one, the maximum dielectric constant and Curie temperature Tc gradually decreased with increasing Pr3+ contents, and the dielectric loss decreased at high temperature by Pr3+-doping. Moreover, the activation energy (Ea), resistivity (Z’), remanent polarization (2Pr) and piezoelectric constant (d33) increased by Pr3+-doping. The NBT-xPr3+ ceramics with x?=?0.3 achieved the optimal properties with the maximum dielectric constant of 1109.18, minimum loss of 0.00822 (250?kHz), Ea of 1.122?eV, Z’ of 7.9?kΩ?cm (725 ºC), d33 of 18 pC/N, 2Pr of 12.04 μC/cm2. The enhancement was due to the addition of Pr3+ which suppressed the decreasing of resistivity at high temperature and made it possible for NBT-xPr3+ ceramics to be poled in perpendicular direction, implying that it is a great improvement for Na0.5Bi4.5Ti4O15 ceramics in electrical properties.  相似文献   

18.
The discovery of superconductivity in copper oxide compounds has attracted considerable attention over the past three decades. The high transition temperature (Tc) in these compounds, exhibiting proximity to an antiferromagnetic order in their phase diagrams, remains one of the main areas of research. It is believed that magnetic fluctuations provide substance for the exotic superconductivity observed in these compounds. The present study attempts to introduce Fe, Co and Ni magnetic impurities into the superconducting cuprate YBa2Cu3O7-δ with the aim of exploring the Tc behavior. The solid-state synthesis method is exploited to prepare fully oxygenated Y1-xMxBa2Cu3O7-δ (Y1-xMx-123) (M = Co, Fe, Ni) samples with low levels of doping (0.00000 ≤ x ≤ 0.03000). Systematic measurements are then employed to assess the synthesized samples using AC magnetic susceptibility, electrical resistivity and X-ray diffraction (XRD). The measurements revealed an increase in Tc as a result of magnetic substitution for Y. However, the study of non-magnetic dopings on the fully oxygenated Y1-xM'xBa2Cu3O7-δ (Y1-xM'x-123) (M' = Ca, Sr) samples showed a decrease in Tc. Quantitative XRD analysis further suggested that the internal pressure could have minor effects on the increase in Tc. The normal state resistivity vs temperature showed a linear profile, confirming that the samples are at an optimal doping of the carrier concentration.  相似文献   

19.
20.
It is highly significant to develop multifunctional optical materials to meet the huge demand of modern optics. Usually, it is difficult to realize multiple optical properties in one single material. In this study, we choose ferroelectric (KxNa1-x)NbO3:Pr3+ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) as hosts, and the rare earth ions Pr3+ are doped in them. For the first time, the integration of photoluminescence, photochromism, luminescence modulation and thermoluminescence and has been achieved in the Pr3+ doped (KxNa1-x)NbO3:Pr3+ ferroelectric ceramics. Upon 337- or 448-nm light irradiation, all samples show strong red emissions centered at 610 nm. The photochromic reaction increases with the increasing K+ content in the (KxNa1-x)NbO3:Pr3+ ceramics. A strong photochromic reaction has been found in the (K0.5Na0.5)NbO3:Pr3+ ceramics. Accordingly, a large and reversible photoluminescence modulation (ΔRt = 50.71%) is achieved via altering 395-nm-light irradiation and 200 °C thermal stimulus. All the prepared ceramics show a visible thermoluminescence when stimulated at 200 °C. The mechanisms of luminescence modulation and thermoluminescence are discussed. Present study could provide a feasible paradigm to realize multiple optical properties in one single material.  相似文献   

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