Preparation and Electric Properties of Bi0.5Na0.5TiO3–Bi(Al0.5Ga0.5)O3 Lead‐Free Piezoceramics

A new lead‐free BNT‐based piezoelectric ceramics of (1 ? x)Bi_0.5Na_0.5TiO₃–xBi(Al_0.5Ga_0.5)O₃ (x = 0, 0.02, 0.03, 0.04, and 0.05) were synthesized using a conventional ceramic fabrication method. Their structures and electrical properties were investigated. All the samples show a typical ferroelectric P(E) loops and S(E) curves at room temperature. The optimal properties are obtained at the composition of the x = 0.03. The substitution of Bi(Al_0.5Ga_0.5)O₃ enhances piezoelectric constant and increases Curie temperature from 58 pC/N and 310°C of pure BNT to 93 pC/N and 325°C of the x = 0.03. The temperature‐dependent P(E) loops and S(E) curves of 0.97BNT–0.03BAG indicate that phase transition from ferroelectric to antiferroelectric takes place over a very wide temperature region from 80°C to 180°C. The results show that the introduction of BAG improves the electrical properties of BNT.     

Preparation and Electric Properties of Bi0.5Na0.5TiO3–Bi(Mg0.5Ti0.5)O3 Lead‐Free Piezoceramics

Lead‐free BNT‐based piezoceramics, (1?x)Bi_0.5Na_0.5TiO₃–xBi(Mg_0.5Ti_0.5)O₃ [(1?x)BNT–xBMT] (0.00 ≤ x ≤ 0.06) binary system, were synthesized using a conventional ceramic fabrication method. Effect of Bi(Mg_0.5Ti_0.5)O₃ (BMT) substitution on room temperature (RT) crystal structure, and temperature dependence of electric properties were investigated. The XRD indicates that a pure perovskite phase is formed. The introduction of BMT decreases E_C of BNT from 7.3 to 4.0 kV/mm, and increases d₃₃ from 58 pC/N to 110 pC/N for the x = 0.05. The system shows a typical ferroelectric (FE) polarization loop P(E) and butterfly bipolar strain‐electric S(E) curve at RT. For the composition of 0.95BNT–0.05BMT antiferroelectric (AFE) phase appears near 80°C, characterized by a constricted P(E) loop and altered bipolar S(E) butterfly, and gradually prevails with increasing temperature. Temperature dependence of dielectric constant shows that T_C increases from 310°C for pure BNT to 352°C for the x = 0.05. The results indicate that the piezoelectric properties of BNT have been improved by means of Bi(Mg_0.5Ti_0.5)O₃ substitution.     

Microstructure and electrical properties of 3-0 type composite of Na0.5Bi2.5Nb2O9-based bismuth-layered piezoceramics

The microstructure and electrical properties of 3-0 type composite of Na_0.5Bi_2.5Nb₂O₉-based bismuth layered piezoceramics modified by Al₂O₃ addition are investigated. The darker and plate-like grains, locating at the grain boundaries, are confirmed to be pure α-Al₂O₃ by high resolution transmission electron microscope, not a Bi₂AlNbO₇ pyrochlore phase. This 3-0 type Na_0.5Bi_2.5Nb₂O₉-Al₂O₃ composite piezoceramics have a large piezoelectric constant d₃₃ of 15.2pC/N with good temperature stability up to 600 °C, and good ferroelectric properties with a relatively large remnant polarization of ~11.6 μC/cm². These demonstrate that designing a 3-0 type composite structure would be an effective approach to tailor the microstructure and improve the electrical properties of bismuth layered piezoceremics for their potential applications at temperature up to 600 °C.     

Photoluminescence,photochromism, and reversible luminescence modulation behavior of Sm-doped Na0.5Bi2.5Nb2O9 ferroelectrics

Sm-modified Na_0.5Bi_2.5Nb₂O₉ ceramics can simultaneously exhibit both visible light-driven photochromism and photoluminescence. Upon visible light irradiation, these materials change their color from green to dark gray, while exhibiting a strong red emission at 603 nm due to the ⁴G_5/2 → ⁶H_7/2 transition, whose emission intensity strongly depends on the irradiation wavelength, intensity, and time, and significantly decreases with increasing irradiation time and intensity. By alternating visible light or sunlight (λ > 400 nm) irradiation and thermal stimulus, both luminescence and absorption intensity can be reversibly switched without any significant degradation between the two colored and bleached states, with excellent reproducibility. On the basis of the trapped charge carrier and exponential relaxation decay models, we herein provide a detailed understanding of the photochromism and luminescence modulation mechanisms.     

Bi(Zn2/3Nb1/3)O3–(K0.5Na0.5)NbO3 High‐Temperature Lead‐FreeFerroelectric Ceramics with Low Capacitance Variation in a Broad Temperature Usage Range

The xBi(Zn_2/3Nb_1/3)O₃–(1?x)(K_0.5Na_0.5)NbO₃ (abbreviated as xBZN–(1?x)KNN) ceramics have been synthesized using the conventional solid‐state sintering method. The phase structure, dielectric properties and “relaxorlike” behavior of the ceramics were investigated. The 0.03BZN–0.97KNN ceramics show a broad and stable permittivity maximum near 2000 and lower dielectric loss (≤5%) at a broad temperature usage range (100°C–400°C) and the capacitance variation (ΔC/C_150°C) is maintained smaller than ±15%. The 0.03BZN–0.97KNN ceramics only possess the diffuse phase transition and no frequency dispersion of dielectric permittivity, which indicates that 0.03BZN–0.97KNN ceramics is a high temperature “relaxorlike” ferroelectric ceramics. These results indicate that 0.03BZN–0.97KNN ceramics are excellent promising candidates for preparing high‐temperature multilayer ceramics capacitors.     

Influence of Co/W co-doping on structural and electrical properties of Na0.5Bi2.5Nb2O9 piezoelectric ceramics

Co/W co-doped Na_0.5Bi_2.5Nb_2-x(Co_1/3W_2/3)_xO₉ (NBNCW-x) ceramic samples were prepared by the conventional solid state reaction method. The electrical properties and crystal structure of the NBNCW-x ceramic samples were analyzed in detail. The XRD and Rietveld refinement results showed that the samples lattice distortion decreased with the increment of Co/W doping. The XPS results showed that the number of oxygen vacancies in the Na_0.5Bi_2.5Nb₂O₉ ceramics could be reduced by the substitution of a small amount of Co/W. The weakened lattice distortion and reduced number of oxygen vacancies of the Na_0.5Bi_2.5Nb₂O₉ ceramics synergistically contributed to its improved electrical properties. In particular, the Na_0.5Bi_2.5Nb_1.97(Co_1/3W_2/3)_0.03O₉ ceramic exhibited the best performance, and its T_c, d₃₃ and P_r were 780 °C, 24.9 pC/N and 12.6 μC/cm², respectively. The dielectric loss was only 3.3% at 550 °C. In addition, this ceramic exhibited excellent thermal stability, with the d₃₃ value of the ceramic being 95.2% of its original value when annealed at 750 °C. These properties indicate that the Co/W co-doped Na_0.5Bi_2.5Nb₂O₉-based ceramics have potential application in the high-temperature field.     

Defect Structure of Doped Lead‐Free 0.9(Bi0.5Na0.5)TiO3−0.1(Bi0.5K0.5)TiO3 Piezoceramics

Cu‐ and V‐doped BNKT10‐based piezoelectric ceramics with up to 0.5 at.% dopant concentration were synthesized and displayed more homogeneous grain growth compared to undoped BNKT10 ceramics. The defect chemistry and defect structure, studied by X‐ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR), indicate a slightly rhombic electronic environment with major unidirectional octahedral distortion of the local environment of Cu. The solubility limit of Cu²⁺ in this material system is lower than 0.05 at.% Cu; above this limit, a Cu segregation at the grain boundaries is prevalent, unlike in PZT and KNN. Here, V was shown to be incorporated into the perovskite lattice and possess oxidation states of +4 and +5, acting both as isovalent and donor dopant, predominantly compensated by A‐site vacancies. A trend toward higher ceramic densities, higher maximum polarization, and higher remanent polarization with increasing Cu concentration was observed. A maximum mechanical coupling factor could be obtained in the case of doping with 0.4 at.% V and 0.1 at.% Cu with a planar coupling of 0.19 and a thickness coupling factor of 0.56.     

Frequency and Temperature‐Independent Electrical Transport Properties of 2BaO–0.5Na2O–2.5Nb2O5–4.5B2O3 Glass‐Ceramics

The temperature (300–973 K) and frequency (100 Hz–10 MHz) response of the dielectric and impedance characteristics of 2BaO‐0.5Na₂O–2.5Nb₂O₅–4.5B₂O₃ glasses and glass nanocrystal composites were studied. The dielectric constant of the glass was found to be almost independent of frequency (100 Hz–10 MHz) and temperature (300–600 K). The temperature coefficient of dielectric constant was 8 ± 3 ppm/K in the 300–600 K temperature range. The relaxation and conduction phenomena were rationalized using modulus formalism and universal AC conductivity exponential power law, respectively. The observed relaxation behavior was found to be thermally activated. The complex impedance data were fitted using the least square method. Dispersion of Barium Sodium Niobate (BNN) phase at nanoscale in a glass matrix resulted in the formation of space charge around crystal‐glass interface, leading to a high value of effective dielectric constant especially for the samples heat‐treated at higher temperatures. The fabricated glass nanocrystal composites exhibited P versus E hysteresis loops at room temperature and the remnant polarization (P_r) increased with the increase in crystallite size.     

Photoluminescence and Temperature Dependent Electrical Properties of Er‐Doped 0.94Bi0.5Na0.5TiO3‐0.06BaTiO3 Ceramics

Er‐doped 0.94Bi_0.5Na_0.5TiO₃‐0.06BaTiO₃ (BNT‐6BT: xEr, x is the molar ratio of Er³⁺ doping) lead‐free piezoceramics with x = 0–0.02 were prepared and their multifunctional properties have been comprehensively investigated. Our results show that Er‐doping has significant effects on morphology of grain, photoluminescence, dielectric, and ferroelectric properties of the ceramics. At room temperature, the green (550 nm) and red (670 nm) emissions are enhanced by Er‐doping, reaching the strongest emission intensity when x = 0.0075. The complex and composition‐dependent effects of electric poling on photoluminescence also have been measured. As for electrical properties, on the one hand, Er‐doping tends to flatten the dielectric constant‐temperature (ε_r‐T) curves, leading to temperature‐insensitive dielectric constant in a wide temperature range (50°C–300°C). On the other hand, Er‐doping significantly decreases the ferroelectric‐relaxor transition temperature (T_F–R) and depolarization temperature (T_d), with the T_F–R decreasing from 76°C to 42°C for x = 0–0.02. As a result, significant composition‐dependent electrical features were found in ferroelectric and piezoelectric properties at room temperature. In general, piezoelectric and ferroelectric properties tend to become weaker, as confirmed by the composition‐dependent piezoelectric coefficient (d₃₃), planar coupling factor (k_p), and the shape of polarization‐electric field (P–E), current‐electric field (J–E), bipolar/unipolar strain‐electric field (S–E) curves. Furthermore, to understand the relationship between the T_F–R/T_d and the electrical properties, the composition of x = 0.0075 has been intensively studied. Our results indicate that the BNT‐6BT: xEr with appropriate Er‐doping may be a promising multifunctional material with integrated photoluminescence and electrical properties for practical applications.     

Enhanced energy storage in temperature stable Bi0.5Na0.5TiO3-modified BaTiO3-Bi(Zn2/3Nb1/3)O3 ceramics

Recently, BaTiO₃-BiMeO₃ ceramics have garnered focused research attention due to their outstanding performance, such as thermal stability, energy efficiency and rapid charge-discharge behavior, however, a lower recoverable energy storage density (W_rec) caused by a relatively low P_max (<30 μC/cm²) mainly hinders practical applications. Herein, the energy density and thermal stability are improved by adding a tertiary component, i.e., Bi_0.5Na_0.5TiO₃, into BaTiO₃-BiMeO₃, resulting in xBi_0.5Na_0.5TiO₃-modified 0.88BaTiO₃-0.12Bi(Zn_2/3Nb_1/3)O₃ ceramics, with x = 0, 0.1, 0.2, 0.3 and 0.4, with superior dielectric properties and eco-friendly impact. Incorporating Bi_0.5Na_0.5TiO₃ with a high saturation polarization and Curie temperature not only significantly enhances P_max of BaTiO₃-Bi(Zn_2/3Nb_1/3)O₃ but also improves Curie temperature of (1-x)[0.88BaTiO₃-0.12Bi(Zn_2/3Nb_1/3)O₃]-xBi_0.5Na_0.5TiO₃ system. Combined with complementary advantages, modified ceramics render a superior energy storage performance (ESP) with a high W_rec of 3.82 J/cm³, efficiency η of 94.4% and prominent temperature tolerance of 25–200 °C at x = 0.3. Moreover, this ceramic exhibit excellent pulse performance, realizing discharge energy storage density W_dis of 2.31 J/cm³ and t_0.9 of 244 ns. Overall, the proposed strategy effectively improved comprehensive properties of BaTiO₃-based ceramics, showing promise in next-generation pulse applications.     

Low‐Temperature Dielectric Relaxations Associated with Mixed‐Valent Structure in Na0.5Bi0.5Cu3Ti4O12

We, herein, present comparative investigations on the Na_0.5Bi_0.5Cu₃Ti₄O₁₂ ceramic samples with and without 10 mol% excess of Na/Bi. The samples were prepared by the standard solid‐state reaction technique. The dielectric properties of the sample were investigated in the temperature (93–320 K) and frequency (20 Hz–10 MHz) windows. Three thermally activated dielectric relaxations observed in Na_0.5Bi_0.5Cu₃Ti₄O₁₂ with the activation energies of 0.104, 0.267, and 0.365 eV for the low‐, middle‐, and high‐temperature dielectric relaxations, respectively. Only the low‐temperature relaxation was observed in both Na and Bi excessive samples. X‐ray photoemission spectroscopy results revealed the mixed‐valent structures of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ in Na_0.5Bi_0.5Cu₃Ti₄O₁₂ sample, but only Ti³⁺/Ti⁴⁺ in Na and Bi excessive samples. Our results showed that the dielectric properties of the investigated samples are strongly linked with these mixed‐valent structures. The high‐ and low‐temperature relaxations were attributed to be a polaron‐type relaxation due to localized carriers hopping between Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺, respectively. The middle‐temperature relaxation is suggested to be a dipole‐type relaxation caused by the defect complex of bismuth and oxygen vacancies.     

Effect of Oxygen Vacancy on Electrical Property of Acceptor Doped BaTiO3–Na0.5Bi0.5TiO3–Nb2O5 X8R Systems

In this study, we reported a new BaTiO₃–Na_0.5Bi_0.5TiO₃–Nb₂O₅–Mn₂O₃/Fe₂O₃/Co₃O₄/In₂O₃ X8R system with high dielectric constant (>2100) at room temperature. The impacts of oxygen vacancy ( ) on dielectric, electrical conductivity, and ferroelectric properties were systematically studied. The Curie point is largely depended on the concentration, which can be confirmed by the dielectric behavior and A_1g octahedral breathing modes in Raman spectrum. In addition, the activation energy of diffusion is greatly reduced with the increase in concentration. It was found that the remnant polarization and coercive field were both decreased with increasing concentration, due to the facilitated defect dipoles reorientation and domain switching.     

BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for High‐Temperature Capacitor Applications

Solid solutions of (1?x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (0 ≤ x ≤ 0.6) were prepared via a standard mixed‐oxide solid‐state sintering route and investigated for potential use in high‐temperature capacitor applications. Samples with 0.4 ≤ x ≤ 0.6 showed a temperature independent plateau in permittivity (ε_r). Optimum properties were obtained for x = 0.5 which exhibited a broad and stable relative ε_r ~940 ± 15% from ~25°C to 550°C with a loss tangent <0.025 from 74°C to 455°C. The resistivity of samples increased with increasing Bi(Mg_2/3Nb_1/3)O₃ concentration. The activation energies of the bulk were observed to increase from 1.18 to 2.25 eV with an increase in x from 0 to 0.6. These ceramics exhibited excellent temperature stable dielectric properties and are promising candidates for high‐temperature multilayer ceramic capacitors for automotive applications.     

Dielectric Relaxor Evolution and Frequency‐Insensitive Giant Strains in (Bi0.5Na0.5)TiO3‐Modified Bi(Mg0.5Ti0.5)O3–PbTiO3 Ferroelectric Ceramics

The 0.45Bi(Mg_0.5Ti_0.5)O₃–(0.55 ? x)PbTiO₃–x(Bi_0.5Na_0.5)TiO₃ (BMT–PT–xBNT) ternary solid solution ceramics were prepared via a conventional solid‐state reaction method; the evolution of dielectric relaxor behavior and the electrostrain features were investigated. The XRD and dielectric measurements showed that all studied compositions own a single pseudocubic perovskite structure and undergo a diffuse‐to‐relaxor phase transition owing to the evolution of the domain from a frozen state to a dynamic state. The formation of the above dielectric relaxor behavior was further confirmed by a couple of measurements such as polarization loops, polarization current density curves, as well as bipolar strain loops. A large strain value of ~0.41% at a driving field of 7 kV/mm (normalized strain d₃₃* of ~590 pm/V) was obtained at room temperature for the composition with x = 0.32, which is located near the boundary between ergodic and nonergodic relaxor. Moreover, this electric field‐induced large strain was found to own a frequency‐insensitive characteristic.     

Enhanced dielectric characteristics of Ba0.94Bi0.04(Fe0.5Nb0.5)O3 coated with SiO2 and SiO2/Al2O3 over a broad frequency and temperature range

Pure phase of Ba_0.94Bi_0.04(Fe_0.5Nb_0.5)O₃ (BBFN) nano-particles were obtained by chemical co-precipitation method. The core-shell structure of BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ particles and the target ceramics were successfully prepared by aqueous chemical coating approach. The microstructures and dielectric properties of BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ were studied. Both the BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ samples show significantly decreased dielectric loss and good frequency and temperature stability on relative permittivity. Compared to the rapid decline of relative permittivity of BBFN@SiO₂, the synergistic effect of SiO₂ and Al₂O₃ in BBFN@SiO₂/Al₂O₃ ceramics made the relative permittivity of which remains a relatively high level with very low dielectric loss, making it more suitable in colossal permittivity applications. Based on the impedance analysis, the grain boundary effect and IBLC models play the important role for the improvement of dielectric properties of BBFN@SiO₂/Al₂O₃ samples.     

High-temperature dielectric and energy storage properties of Bi0.5Na0.5TiO3-based ceramics modified by Sr0.8Na0.4Nb2O6

Sr_0.8Na_0.4Nb₂O₆ with a tungsten bronze structure is introduced into perovskite-structured 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ composition (abbreviated as BNT-BT-xSNN, x = 0-0.04). The temperature stability of dielectric properties and energy storage performance is found to be effectively enhanced by Sr_0.8Na_0.4Nb₂O₆ dopant. When x is 0.03, the temperature ranges covering |ε'-ε'_150°C|/ε'_150°C ≤15% and tanδ ≤ 0.02 are 43°C-404°C and 90°C-422°C, respectively. More importantly, ε′ can be retained as high as 3304 at 150°C. Besides, the variances of energy storage density and its efficiency are 6.4% and 5.3%, respectively, in the temperature range from room temperature (RT) to 180°C. Therefore, this work provides a new method of compositional modification in BNT-based materials to improve their temperature stability of dielectric and energy storage properties.     

Effect of Texture on Temperature‐Dependent Properties of K0.5Na0.5NbO3 Modified Bi1/2Na1/2TiO3–xBaTiO3

Textured (1?x?y)Bi_1/2Na_1/2TiO₃–xBaTiO₃–yK_0.5Na_0.5NbO₃ (BNT–100xBT–100yKNN) ceramics with a {001} pseudocubic (pc) orientation were fabricated by templated grain growth using Bi_1/2Na_1/2TiO₃ templates. Temperature‐dependent electromechanical results demonstrate that the strain response of templated BNT–xBT–yKNN ceramics is stable from room temperature (RT) to 125°C. The temperature‐dependent strain and polarization response are compared to randomly oriented ceramics, for BNT–100xBT–2KNN (0.05 ≤ x ≤ 0.07). Textured BNT–7BT–2KNN reached a maximum 0.47% strain response at 5 kV/mm, an almost 50% increase compared to randomly oriented BNT–7BT–2KNN. Over the temperature range RT–125°C, the strain response of templated BNT–6BT–2KNN degraded from 0.38% to 0.22% (?42.1%) compared to 0.37% to 0.18% (?51.4%) for randomly oriented ceramics. The temperature‐dependent strain response suggests that templated BNT–100xBT–100yKNN ceramics are well suited for elevated temperature applications.     

Physical and electrical properties of Nb doped Bi0.5Na0.5[Zr0.59Ti0.41]O3

This research studied the effect of Nb doping on Bi_0.5Na_0.5[Ti_0.41Zr_0.59]O₃ (when Nb concentration = 0.00, 0.01, 0.03, 0.05, 0.07 and 0.09 mol fraction). Nb doped BNTZ ceramics were fabricated using a conventional mixed-oxide method. All samples were calcined at a temperature of 700 °C for 2 h and sintered at a temperature of 900 °C for 2 h. X-ray diffraction patterns suggested that the compounds possessed rhombohedral perovskite structure. SEM micrographs indicated that average grain size decreased as the amount of Nb additives increased. The electrical resistivity showed a decreasing trend with increasing Nb concentration due to excess charge present in the sample. The dielectric constant and dielectric loss of samples showed no particular trend when Nb was added but the optimum was observed when 0.05–0.07 Nb mol fraction was present in BNTZ ceramics. In this study, both microstructure and donor-type effects played an important role in determining electrical resistivity and dielectric properties of these ceramics.     

Ultra‐Wide Temperature Stable Dielectrics Based on Bi0.5Na0.5TiO3–NaNbO3 System

The microstructure, phase structure, ferroelectric, and dielectric properties of (1?x)Bi_0.5Na_0.5TiO₃‐xNaNbO₃ [(1?x)BNT‐xNN] ceramics conventionally sintered in the temperature range of 1080°C–1120°C were investigated as a candidate for capacitor dielectrics with wide temperature stability. Perovskite phase with no secondary impurity was observed by XRD measurement. With increasing NN content, (1?x)BNT‐xNN was found to gradually transform from ferroelectric (x = 0–0.05) to relaxor (x = 0.10–0.20) and then to paraelectric state (x = 0.25–0.35) at room temperature, indicated by P–I–E loops analysis, associated with greatly enhanced dielectric temperature stability. For the samples with x = 0.25–0.35, the temperature coefficient of capacitance (TCC) was found <11% in an ultra‐wide temperature range of ?60°C–400°C with moderate dielectric constant and low dielectric loss, promising for temperature stable capacitor applications.     

Effect of Na2O on the High‐Temperature Thermal Conductivity and Structure of Na2O–B2O3 Melts

The effect of Na₂O and temperature on the thermal conductivity of the Na₂O–B₂O₃ binary system has been measured using the hot‐wire method to examine the relationship between the thermal conductivity and structure in high‐temperature melts. The thermal conductivity of the binary melt is measured from 1173 to 1473 K in the fully liquid state. The thermal conductivity slightly increases with Na₂O content up to 20 wt%. Above 20 wt% Na₂O, the thermal conductivity decreases with increasing Na₂O. The network structure of molten glass was analyzed using Fourier transform infrared (FTIR), Raman spectroscopy, and XPS. The FTIR analysis shows that 3‐D complex borate structures, such as tri‐, tetra‐, and pentaborate are made by [BO₄] tetrahedral units interconnected with 2‐D structure boroxol rings in the low Na₂O region. Above 20 wt% Na₂O content, nonbridged oxygen in [BO₂O^?] units and diborate groups increase with increase in Na₂O. The same tendency is shown by the Raman spectroscopy and XPS analyses. The Raman analysis shows that boroxol rings disappeared with large [BO₄] groups, such as tri‐, tetra‐, and pentaborate structures, which increase at low Na₂O content. Isolated diborate groups and nonbridged oxygen in [BO₂O^?] units increase at high Na₂O content. It can be inferred that single structure units, such as isolated diborate groups, interfere with conduction. The XPS analysis results show that free oxygen produced by the interconnection of Na₂O in the borate structure does not cause significant changes to O^2? in the low Na₂O region, but increases the O^o and decreases the O^?. Above 20 wt% Na₂O, O^? slightly increases and O^o shows a decreasing trend.