Optical transmittance and energy storage properties of potassium sodium niobate glass-ceramics

In this work, 0.8(K₂O-Na₂O-2Nb₂O₅)?0.2((1-x)B₂O₃-xP₂O₅) (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) glass-ceramics have been fabricated. The effects of P₂O₅ on the microstructure and properties of the glass-ceramics were comprehensively studied. The addition of P₂O₅ promotes the transition of the glass network structure from a negatively charged [B?₄]^- tetrahedron to an electrically neutral [BP?₄] tetrahedron. With the increase of P₂O₅ content, the formation of K₂B₄O₇ is inhibited, with major phase of Na_0.9K_0.1NbO₃ and minor phase of K₂B₄O₇. It is found that the band gap width of the glass-ceramics increases from 3.34 eV to 3.52 eV firstly and then decreases to 3.43 eV. The grain size of the glass-ceramics decreases from 150 nm to 50 nm. High optical transmittance (63%), large discharge energy density (4.58 J/cm³) and large energy storage efficiency (98%) have been simultaneously obtained for K₂O-Na₂O-Nb₂O₅-B₂O₃-P₂O₅ glass-ceramics, which are potential for the applications of the transparent pulse capacitors.     

Tuning energy storage and light transmittance properties in ZrO2-modified Na2O–K2O–Nb2O5–SiO2 glass-ceramics

Crystallization kinetics in ZrO₂-modified glass-ceramics, (35-x)Na₂O–5K₂O–40Nb₂O₅–20SiO₂-xZrO₂ (x = 0, 1, 3, 5, 10 mol%), is analyzed by crystallization activation energy E_c and kinetic parameter k. A large kinetic parameter k of 1.657 × 10²⁵ is found for the sample with x = 1, which indicates a high tendency toward crystallization. NaNbO₃ is formed as the major phase, and its crystallinity changes significantly by the addition of ZrO₂. It is found that the dielectric permittivity and maximum polarization are affected by crystallinity. Large domains are formed, and a relaxation process appears at high frequencies. In addition, the breakdown strength (BDS) is affected by the strong electric field distortion rather than the resistance in this system. Complex impedance analysis shows that resistance decreases with the addition of ZrO₂. The electric field distortion of the glass-ceramics is simulated by COMSOL. A low interfacial polarization activation energy E_a of 0.821 eV is achieved by the addition of ZrO₂. The maximum pulse power density reaches 90 MW/cc at 350 kV/cm for the sample with x = 10, and the pulse energy density attains 0.91 J/cm³ at 300 kV/cm for the sample with x = 1. Light transmittance is achieved because of the low crystallinity and the disappearance of cristobalite SiO₂ in the Na₂O–K₂O–Nb₂O₅–SiO₂ glass-ceramics.     

Achieving high energy storage performance of Pb(Lu1/2Nb1/2)O3 antiferroelectric ceramics via equivalent A-site engineering

Manipulating the critical switching field between antiferroelectric (AFE) state and ferroelectric (FE) is an important concept for tuning the energy storage performance of AFEs. As one of the lead-based AFE systems, Pb(Lu_1/2Nb_1/2)O₃ promises high potential in the miniaturization of pulsed power capacitors, but the extremely high critical switching field and low induced saturated polarization demonstrate severe drawbacks with respect to temperature stability and flexibility. Here, A-site Ba²⁺ doping engineering is used to effectively reduce the critical switching field and improve the saturated polarization in Ba_xPb_1-x(Lu_1/2Nb_1/2)O₃ (0.01 ≤ x ≤ 0.08, abbreviated as xBa-PLN) ceramics. We found the AFE-FE phase transition can be occurred at 80ºC with a high energy storage density of 4.03 J/cm³ for Ba_0.06Pb_0.94(Lu_1/2Nb_1/2)O₃ ceramic. Our results show that Ba²⁺ additions destroy the antiparallel structure of AFE phase, and finally reduce the critical switching field, demonstrating a potential alternative to modulate the energy storage performance of AFEs.     

Enhanced energy storage performance in Na(1-3x)BixNb0.85Ta0.15O3 relaxor ferroelectric ceramics

High-performance lead-free dielectric containers have excellent energy storage performance such as higher power density and energy density. While being eco-friendly materials, lead-free dielectric materials are more suitable for pulse power systems than other dielectric materials. In this study, Ta⁵⁺and Bi³⁺ ions were introduced into the A site and B site of the NaNbO₃ matrix. The introduction of Bi³⁺ ions induced the formation of a vacancy in the A site, yielding Na_(1-3x)Bi_xNb_0.85Ta_0.15O₃ (NBNT, x = 0.05, 0.08, 0.11, 0.14) ceramics. The recoverable energy density (W_rec) and the energy storage efficiency (η) were highest for the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic, with values of 3.37 J/cm³ and 89% respectively. Batteries employing the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic achieved a current density of 830.4 A/cm², an energy density of 49.8 MW/cm³ and 60.2 ns discharge time. These results show that the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic is an effective energy storage material with broad application prospects.     

High energy storage and ultrafast discharge in NaNbO3-based lead-free dielectric capacitors via a relaxor strategy

Dielectric capacitors with decent energy storage and fast charge-discharge performances are essential in advanced pulsed power systems. In this study, novel ceramics (1-x)NaNbO₃-xBi(Ni_2/3Nb_1/3)O₃(xBNN, x = 0.05, 0.1, 0.15 and 0.20) with high energy storage capability, large power density and ultrafast discharge speed were designed and prepared. The impedance analysis proves that the introducing an appropriate amount of Bi(Ni_0·5Nb_0.5)O₃ boosts the insulation ability, thus obtaining a high breakdown strength (E_b) of 440 kV/cm in xBNN ceramics. A high energy storage density (W_total) of 4.09 J/cm³, recoverable energy storage density (W_rec) of 3.31 J/cm³, and efficiency (η) of 80.9% were attained in the 0.15BNN ceramics. Furthermore, frequency and temperature stability (fluctuations of W_rec ≤ 0.4% over 5–100 Hz and W_rec ≤ 12.3% over 20–120 °C) were also observed. The 0.15BNN ceramics exhibited a large power density (19 MW/cm³) and ultrafast discharge time (~37 ns) over the range of ambient temperature to 120 °C. These enhanced performances may be attributed to the improved breakdown strength and relaxor behavior through the incorporation of BNN. In conclusion, these findings indicate that 0.15BNN ceramics may serve as promising materials for pulsed power systems.     

The electrical properties of (Ba,Ca, Ce,Ti, Zr)O3 thermistor for wide-temperature sensor architecture

A series of new negative temperature coefficient (NTC) thermal materials based on (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ (0.00 ≤ x ≤ 0.20) ceramics were synthesized by a solid-state method. X-ray diffraction, scanning electron microscope and X-ray photoelectron spectroscopy were used to demonstrate the crystal structure, morphology, and composition of the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics, which were composed of solid solution based on the BaTiO₃ phase. The average grain size of doped ceramic samples experienced the process of first decreasing and then increasing. The doping of Ce has reduced the sintering temperature. The temperature-dependent resistance analysis revealed that with the change of doping amount x, the thermal constant B_300/1200 (1.21 × 10⁴–1.13 × 10⁴ K) and the activation energy E_a300/1200 (0.9777–1.0471eV) was initially increased to maximum values at x = 0.05, followed by the decreasing when x > 0.05. It has been established that the concentration of oxygen vacancies is affected by the transition between Ce⁴⁺ and Ce³⁺ provided by high levels of Ce doping. (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics exhibited excellent negative temperature characteristics in the range of 300–1200 °C. Moreover, the temperature resistance linearity was improved after samples were aged. Hence, the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics were regarded as a promising material for high-temperature NTC thermistors in a wide temperature range.     

Dielectric temperature stability of Nb-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

In this study, the phase structure, microstructure and dielectric properties of Bi_0.5(Na_0.78K_0.22)_0.5(Ti_1-xNb_x)O₃ lead-free ceramics prepared by traditional solid phase sintering method were studied. The second phase pyrochlore bismuth titanate (Bi₂Ti₂O₇) was produced in the system after introduction of Nb⁵⁺. The dielectric constant of the sample (x = 0.03) sintered at 1130 °C at room temperature reached a maximum of 1841, and the dielectric loss was 0.045 minimum. It had been found that the K⁺ and Nb⁵⁺ co-doped Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics exhibited outstanding dielectric-temperature stability within 100–400 °C with T_cc ≤±15%. Result of this research provides a valuable reference for application of BNT based capacitors in high temperature field.     

Large electro-strain with excellent fatigue resistance of lead-free (Bi0.5Na0.5)0.94Ba0.06Ti1-x(Y0.5Nb0.5)xO3 perovskite ceramics

A series of lead-free (Bi_0.5Na_0.5)_0.94Ba_0.06Ti_1-x(Y_0.5Nb_0.5)_xO₃ (for 0 ≤ x ≤ 0.03) perovskite ceramics were fabricated using a solid-state reaction technique. The effects of (Y_0.5Nb_0.5)⁴⁺ ions doping on phase structure, piezoelectric properties, AC impedance, and fatigue resistance were systematically studied. Crystal structure as a function of the composition revealed a single perovskite lattice structure with dense micromorphology. The transition temperature of the non-ergodic and ergodic relaxor ferroelectric phase shifted to near ambient temperature with increasing composition, which was related to the destruction of the long-range ordered ferroelectric domains. Hence, the transformation of ferroelectric-to-relaxor phase was easier under applied electric field at room temperature. The ceramic for x = 0.01 composition attained a large unipolar strain of ~ 0.452% with a corresponding normalized strain (d₃₃*) of ~ 603 pm/V under applied 75 kV/cm field. Besides, the excellent fatigue resistance of the sample was obtained after 10⁵ switching cycles under 70 kV/cm. These phenomena demonstrated that (Bi_0.5Na_0.5)_0.94Ba_0.06Ti_1-x(Y_0.5Nb_0.5)_xO₃ ceramics might be suitable for a wide range of electronic equipment applications such as actuators and sensors.     

Electrical properties of [Li0.04(K0.5Na0.5)0.96−xAgx](Nb1−ySby)O3 ceramics

Dependence of electrical properties on the structural characteristics of Li_0.04(K_0.5Na_0.5)_0.96(Nb_1?ySb_y)O₃ (LKNNS (x = 0, 0.00 ≤ y ≤ 0.10)) and [Li_0.04(K_0.5Na_0.5)_0.96?xAg_x](Nb_0.925Sb_0.075)O₃ (LKNANS (0.01 ≤ x ≤ 0.05, y = 0.075)) were investigated. The oxygen octahedral distortion was dependent on Ag⁺ and/or Sb⁵⁺ content which affected to the phase transition temperature of LKNNS and LKNANS ceramics. The orthorhombic–tetragonal and tetragonal–cubic phase transition temperatures (T_O–T, T_C) of the specimens were decreased with increasing of average octahedral distortion. With increasing of Sb⁵⁺ content, the electromechanical coupling factor (k_p), piezoelectric constant (d₃₃) and dielectric constant (?_r) of the sintered specimens were increased up to y = 0.075, and then decreased. These results could be attributed to the shift of T_O–T to near room temperature for Li_0.04(K_0.5Na_0.5)_0.96(Nb_0.0925Sb_0.075)O₃.     

Ferroelectric‒to‒relaxor crossover in KNN‒based lead‒free piezoceramics

This study investigated the phase transition behavior and electrical properties of (K_0.5Na_0.5)(Nb_1-xZr_x)O₃ (KNN?100xZ) and (K_0.5Na_0.5)NbO₃–yBaZrO₃ (KNN–100yBZ) lead–free piezoelectric ceramics. The phase transitions in crystal structures were compared in KNN ceramics between single Zr⁴⁺ doping and Ba²⁺Zr⁴⁺ co?doping. Piezoelectric properties such as the piezoelectric constant (d₃₃) and electromechanical coupling factor (k_p) are optimized for KNN?6BZ ceramics and were clarified via the polymorphic phase transition from the orthorhombic to pseudocubic phase. The fitted degree of diffuseness (γ) for a phase transition from the modified Curie–Weiss law indicated that KNN ceramics as ferroelectrics are gradually transformed through BaZrO₃ modification. Accordingly, the enhanced strain properties at y = 0.08 consist of coexisting ferroelectric domains and polar nanoregions that are supported by ferroelectric–to–relaxor crossover in KNN?100BZ ceramics.     

Ordering structure of barium magnesium niobate ceramic with A-site substitution

The ordering behaviour of Ba(Mg_1/3Nb_2/3)O₃ ceramics (BMN) substituted by La³⁺, Na⁺, K⁺ was investigated using X-ray powder diffraction and transmission electron microscopy. The 1:2 ordered structure of BMN can be transformed to 1:1 ordered structure by substituting a small amount of La cation ion into the A-site. Moreover, the degree of ordering was increased with La content in the compound, and reached almost unity at [La] = 50 mol%. When the La ion in (Ba_1−xLa_x)(Mg_(1+x)/3Nb_(2−x)/3)O₃ (BLMN) was substituted by Na or K ions, the 1:1 ordered structure of BLMN was transformed into the 1:2 ordered structure. The degree of 1:2 ordering was influenced by the sintering temperature and the size difference between the A and B site ions.     

Optical and electrical properties of pressureless sintered transparent (K0.37Na0.63)NbO3-based ceramics

Lead-free (1−x)(K_0.37Na_0.63)NbO₃-xCa(Sc_0.5Nb_0.5)O₃ (x=0.050, 0.070, 0.090, 0.095 and 0.100) transparent ferroelectric ceramics have been fabricated by pressureless sintering procedure. Transmittance of 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ ceramics sintered in sealed alumina crucible was 15% higher than those sintered unsealed in air. By increasing the content of Ca(Sc_0.5Nb_0.5)O₃, the phase structure of (K_0.37Na_0.63)NbO₃ ceramics transformed from orthorhombic to tetragonal symmetry first and then to pseudo cubic symmetry. The 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ ceramics exhibited high density (98%), high transmittance (60%) in the near-IR region and relatively good electrical properties (ε_r=1914, tanδ=0.037, T_c=147 °C, P_r=6.88 μC/cm², E_c=8.49 kV/cm). Meanwhile, the introduction of Ca(Sc_0.5Nb_0.5)O₃ induced a composition fluctuation in the (K_0.37Na_0.63)NbO₃ lattice and made the ceramics more relaxor-like, which would lead to a further reduction of light scattering. These results demonstrated that 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ could be promising lead-free transparent ferroelectric ceramics.     

Giant field-induced strain in Nb2O5-modified (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

Lead-free piezoceramics (Na_(1+x)/2Bi_(1-x)/2)_0.94Ba_0.06Ti_1-xNb_xO₃ (BTN100x) were prepared using conventional solid-state reaction method. The structures, field- induced strain, AC impedance of sintered ceramics were investigated. The pure perovskite solid solution BTN3 exhibited giant electric-field-induced strain of 0.478% under an electric field of 70 kV/cm at ambient temperature, meanwhile, the normalized strain (S_max/E_max) reached up to 654 pm/V. The giant strain was insensitive to temperature and exhibited excellent fatigue resistance performance within 10⁶ switching cycles, making it a promising candidate material for actuator applications. Complex AC impedance spectra confirmed the contribution of grain effect to resistivity behavior. The field-induced giant strain was attributed to the phase transition between ferroelectrics and relaxor ferroelectrics induced by introducing Nb₂O₅.     

High recoverable energy storage density in nominal (0.67-x)BiFeO3-0.33BaTiO3-xBaBi2Nb2O9 lead-free composite ceramics

A series of novel lead-free energy storage ceramics, (0.67-x)BiFeO₃-0.33BaTiO₃-xBaBi₂Nb₂O₉ (BF-BT-xBBN), were fabricated by traditional solid-state reaction, where bismuth layer-structured BaBiNb₂O₉ was incorporated into perovskite-structured BiFeO₃–BaTiO₃ ceramic as an additive. The addition of BaBi₂Nb₂O₉ increased the relaxor behavior and breakdown strength of BF-BT ceramics due to the formation of polar nanoregionals (PNRs), inducing enhanced energy storage performance. The composite ceramics, with x = 0.08, showed a large recoverable energy density (W_rec) of 3.08 J/cm³ and an outstanding energy storage efficiency (η) of 85.57% under an applied electric field of 230 kV/cm. Moreover, the composite ceramics exhibited excellent thermal stability and high stability toward different frequencies in a temperature range of 20–100 °C and a frequency range of 0.1–1500 Hz. These results demonstrate great potential of novel BF-BT-xBBN composite ceramics for next-generation energy storage applications.     

The effect of B site doping of Nb5+ and aging process on the properties of BNKT-BT lead-free piezoelectric ceramics

This research explored the influence of Nb⁵⁺ doping on the electrical properties and microstructure of [0.852(Bi_0.5Na_0.5)-0.11(Bi_0.5K_0.5)-0.038Ba]Ti_(1-x)Nb_xO₃ (designated as BNKT-BT). The BNKT-BT samples were fabricated and the XRD results showed that the doping of Nb⁵⁺ ions induced a transformation from the coexistence of both rhombohedral and tetragonal phase to a single pseudo cubic phase. Also, the doping of Nb⁵⁺ ions caused the temperature of ferroelectric state-ergodic relaxor state transition to decrease below the room temperature (RT). The SEM observations showed that the Nb⁵⁺ doping had a minor effect on the grain size of BNKT-BT samples. In addition, the samples achieved a large electrostrain of 0.43% (d*₃₃ = S_max/E_max = 614 pm/V) under 7 kV/mm at RT. Moreover, the aging process employed at 80 °C for two weeks in air could effectively increase the electrostrain from 0.38% to 0.41% under 6 kV/mm (d*₃₃ = 683 pm/V) and reduce the strain hysteresis from 57% to 34%. These results indicated that the B site doping, combined with the aging process, could provide an effective way to enhance the electrostrain performance of lead-free piezoelectric ceramics.     

Investigation on phase structure,spectral characteristics,microstructure and microwave dielectric properties of Li2Zn[Ti1-x(Co1/3Nb2/3)x]3O8 (0.0 ≤ x ≤ 0.4) ceramics

In this paper, a series of Li₂Zn[Ti_1-x(Co_1/3Nb_2/3)_x]₃O₈ (0.0 ≤ x ≤ 0.4) ceramics were prepared via the conventional solid-state method. The influences of (Co_1/3Nb_2/3)⁴⁺ complex ions on the phase composition, spectral characteristics, microstructure, and microwave dielectric properties of Li₂Zn[Ti_1-x(Co_1/3Nb_2/3)_x]₃O₈ ceramics were studied systematically. XRD analysis accompanied with Rietveld refinements showed that pure Li₂ZnTi₃O₈ solid solution ceramics with the cubic spinel structure were obtained at x = 0.2–0.4. New Raman-active mode of about 858 cm⁻¹ should be attributed to the vibrations of NbO₆ due to the high bond energy of Nb–O bonds, exerting a certain impact on the structure and performance of Li₂Zn[Ti_1-x(Co_1/3Nb_2/3)_x]₃O₈ ceramics. XPS results indicated that Nb⁵⁺ ion donor suppressed the deoxidation process and therefore resulted in the disappearance of Ti³⁺ ion and oxygen vacancy. The downward trend variation in the ε_r value with the increase of (Co_1/3Nb_2/3)⁴⁺ content could be explained by the presence of “compressed” cations and “rattling” cations effect. In addition, the Q × f of the current ceramics was closely dependent on relative density, grain size, FWHM, and oxygen vacancy. Good combined microwave dielectric properties of ε_r = 24.5, Q × f = 91,250 GHz, and τ_f = −16.8 ppm/°C were achieved for the Li₂Zn[Ti_0.8(Co_1/3Nb_2/3)_0.2]₃O₈ ceramic sintered at 1120 °C. High quality factor gives evidence that the Li₂Zn[Ti_0.8(Co_1/3Nb_2/3)_0.2]₃O₈ ceramic is an appealing candidate for highly selective microwave devices.     

Improved energy storage properties of Sr(Zr0.8Nb0.16)O3-doped Bi0.47Na0.47Ba0.06TiO3 ceramics with excellent temperature/frequency stability

Lead-free perovskite dielectric materials for capacitors have received wide concern in recent years, but their energy storage density and efficiency still cannot meet the growing application demand for practical applications. In this work, we prepared a lead-free relaxor ferroelectric ceramic of (1-x)Bi_0.47Na_0.47Ba_0.06TiO₃-xSr(Zr_0.8Nb_0.16)O₃, which was synthesized via a normal solid-state route. The microstructure, dielectric properties and energy storage behavior of the ceramics were explored. The ceramics can be well sintered and situated in the region where rhombohedral and tetragonal phases coexist. The addition of Sr(Zr_0.8Nb_0.16)O₃ (SZN) significantly extends the dielectric-temperature plateau between T_s and T_m and reduces the remnant polarization P_r, but the large saturation polarization P_s is still maintained. Besides, the doping of SZN enhances the relaxation of the material and increases the dielectric breakdown strength (DBS) from 50 kV/cm (x = 0) to 100 kV/cm (x = 0.04 and 0.06). Therefore, the ceramic with x = 0.06 exhibits a high discharging efficiency (η) of 71.1% and energy density (W) of 1.56 J/cm³ at 100 kV/cm and shows the superior thermal stability with the changes in recoverable energy density (W_rec) and η of less than 10% and 30% at the temperature range of 25–180 °C and the excellent frequency stability with the variations of W_rec and η of less than 1.8% and 1% at the frequency range of 10 Hz–100 Hz.     

Effect of niobium valence on the mechanochemical activation of niobium oxides–hematite magnetic ceramic nanoparticles

Three types of nanostructured systems: xNbO·(1?x)α-Fe₂O₃, xNbO₂·(1?x)α-Fe₂O₃, and xNb₂O₅·(1?x)α-Fe₂O₃ were synthesized by ball milling at different molar concentrations (x=0.1, 0.3, 0.5, and 0.7). The effect of Nb valence and milling time on mechanochemical activation of these systems were studied by X-ray diffraction and the Mössbauer spectroscopy measurements. In general, Nb-substituted hematite was obtained at lower molar concentrations for all Nb oxides. For the NbO–Fe₂O₃ system the favorable substitution of Fe²⁺ for Nb²⁺ in the octahedral sites in the NbO lattice was observed after 12 h milling for x=0.7. In the case of the NbO₂–Fe₂O₃ and Nb₂O₅–Fe₂O₃ systems a formation of orthorhombic FeNbO₄ compound was observed, in which Fe³⁺ cations were detected. For the highest concentration of NbO₂ (x=0.7) iron was completely incorporated into the FeNbO₄ phase after 12 h milling. The molar concentrations of x=0.3 and 0.5 were the most favorable for the formation of ternary FeNbO₄ compound in the Nb₂O₅–Fe₂O₃ system. Influence of ball milling on thermal behavior of the powders was investigated by simultaneous DSC–TG measurements up to 800 °C.     

Transport of potassium ions in niobium phosphate glasses

The influence of Nb₂O₅ on the structure and ionic conductivity of potassium phosphate glasses was investigated in glasses with composition xNb₂O₅–(100-x)[0.45K₂O–0.55P₂O₅], x = 10–47 mol%. The Raman spectra of glasses reveal a transition from predominantly orthophosphate to predominantly niobate glass network with increasing Nb₂O₅ content. In the glass structure, niobium forms NbO₆ octahedra which are interlinked with phosphate units for the glass containing 10 mol% Nb₂O₅, but for higher Nb₂O₅ content they become mutually interconnected via Nb-O-Nb bonds. The transport of potassium ions was found to be strongly dependent on the structural characteristics of the glass network. While the mixed niobate-phosphate glass network hinders the diffusion of potassium ions by providing traps that immobilize them and/or by blocking the conduction pathways, predominantly niobate glass network exhibits a rather facilitating effect which is evidenced in the trend of DC conductivity as well as in the features of the frequency-dependent conductivity and typical hopping lengths of potassium ions.     

Thermal,Structural, and Crystallization Properties of New Tantalum Alkali‐Germanate Glasses

In this work, new glass compositions were prepared in the ternary system GeO₂–K₂O–Ta₂O₅. Potassium oxide was added to reach the complete melt of the starting mixture and two composition series were investigated: the first one with a constant K₂O molar content of 10% in the ternary system (90–x)GeO₂–10K₂O–xTa₂O₅ and the second one with the same molar content of K₂O and Ta₂O₅ in the ternary system (100–2x)GeO₂–xK₂O–xTa₂O₅. Homogeneous and transparent glasses could be obtained between x = 0 and 20. X‐ray diffraction analyzes of samples with x = 25 identified orthorhombic Ta₂O₅ in the first series and an isostructure of K_3.8Ge₃Nb₅O_20.4 in the second series where it is assumed that Ta⁵⁺ ions are inserted in the Nb⁵⁺ sites. As one of our goal with these materials is related with the preparation of glass‐ceramics containing Ta₂O₅ nanocrystals, the first series has been selected for further characterizations. An increase in glass‐transition temperatures with increasing Ta₂O₅ content as well as an increase of the thermal stability from x = 0 to 10 has been identified by differential scanning calorimetry. For higher contents, crystallization events were identified. Fourier transform infrared and Raman spectroscopic characterizations allowed to point out the intermediary behavior of Ta₂O₅ in the vitreous network where TaO₆ octahedra are inserted inside the germanate network with TaO₆ clusters identified at higher Ta₂O₅ contents. Heat‐treated samples with high tantalum contents (x = 15 and 20) exhibit preferential precipitation of orthorhombic Ta₂O₅ with nanometric size, suggesting the possibility of obtaining transparent glass‐ceramics for optical applications.