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1.
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.  相似文献   

2.
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)GeO2xK2O–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 K3.8Ge3Nb5O20.4 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.  相似文献   

3.
In this study, we have investigated the use of silver cation as nucleating agent in germanotellurite glass matrix of compositions (100?x) [70TeO2–10GeO2–10Nb2O5–10K2O]–xAg2O (x=0‐6 mol%), in order to promote bulk crystallization. Density measurements, differential scanning calorimetry, X‐ray diffraction, UV‐Vis, and Raman spectroscopies have been performed to study the crystallization process. We have observed bulk crystallization of a unique noncentrosymmetric phase, K[Nb1/3Te2/3]2O4.8, which has been investigated for its second‐order optical activity. Transparent to translucent glass‐ceramics have been successfully tailored under thermal treatment and second harmonic generation signals were recorded on the glass‐ceramic samples as a function of their synthesis procedure. It is suggested that the second‐order optical properties observed are strongly related to the organization of crystallites within phase‐separated domains.  相似文献   

4.
Germanate laser glasses have received much attention as a promising host materials for mid-infrared fiber lasers in recent years because of the outstanding infrared transparency, low phonon energy, and high rare earth solubility of such glasses. However, the development of high-performance germanate laser glasses is usually based on intuition and a trial-and-error method, which can involve long experimental periods and high costs, and thus, this approach is highly inefficient. Recently, with proposals for materials genome engineering, the concept of the “glass genome” has grown of interest to us. Herein, the structures of Tm3+-doped germanate laser glasses (BaO–GeO2 and BaO–La2O3–GeO2) were investigated by Fourier transform infrared spectra (FTIR) and Raman spectra analyses, which revealed that the resulting glass contains similar structural groups to the neighboring congruently melted glassy compounds (NCMGCs) in the composition diagram. What is more, the structure and properties of the resulting laser glasses largely depend on NCMGCs. Then, the glass-forming region, physical properties, and luminescence properties were calculated via the use of NCMGCs in Tm3+-doped BaO–GeO2 binary and BaO–La2O3–GeO2 ternary laser glass systems. The calculated results were in good agreement with the experimental results, thus demonstrating that our approach is practical for predicting the glass-forming region, physical properties, and luminescence properties in Tm3+-doped BaO–GeO2 binary and BaO–La2O3–GeO2 ternary laser glass systems. This work may provide an effective method to develop Tm3+-doped germanate laser glasses rapidly and at low cost.  相似文献   

5.
Glasses in the 30La2O3-40TiO2-30Nb2O5 system are known to have excellent optical properties such as refractive indices over 2.25 and wide transmittance within the visible to mid-infrared (MIR) region. However, titanoniobate glasses also tend to crystallize easily, significantly limiting their applications in optical glasses due to processing challenges. Therefore, the 30La2O3-40TiO2-(30−x) Nb2O5-xAl2O3 (LTNA) glass system was successfully synthesized using a aerodynamic containerless technique, which improves glass thermal stability and expands the glass-forming region. The effects of Al2O3 on the structure, thermal, and optical properties of base composition glasses were investigated by XRD, DSC, NMR, Raman spectroscopy, and optical measurements. DSC results indicated that as the content of Al2O3 increased, the thermal stability of the glasses and glass-forming ability increased, as the 30La2O3-40TiO2-25Nb2O5-5Al2O3 (Nb-Al-5) glass obtained the highest ΔT value (103.5°C). Structural analysis indicates that the proportion of [AlO4] units increases gradually and participates in the glass network structure to increase connectivity, promoting more oxygen to become bridging oxygen and form [AlO4] tetrahedral linkages to [TiO5] and [NbO6] groups. The refractive index values of amorphous glasses remained above 2.1 upon Al2O3 substitution, and a transmittance exceeding 65% in the visible and mid-infrared range. The crystallization activation energies of 30La2O3-40TiO2-30Nb2O5 (Nb-Al-0) and Nb-Al-5 glasses were calculated to be 611.7 and 561.4 kJ/mol, and the Avrami parameters are 5.28 and 4.96, respectively. These results are useful to design new optical glass with good thermal stability, high refractive index and low wavelength dispersion for optical applications such as lenses, endoscopes, mini size lasers, and optical couplers.  相似文献   

6.
Zinc borate glasses with different concentrations of Nb2O5 were prepared and later were heat treated for prolonged times. Prepared samples were characterized by XRD, SEM, DSC, IR and optical transmission spectroscopy techniques. Later, dielectric properties viz., dielectric constant, loss tangent, electric modulii, electrical impedance and a.c. conductivity over wide ranges of frequency and temperature, were investigated as a function of Nb2O5 concentration. Finally, the dielectric breakdown strength was measured in air medium at ambient temperature. The results of characterization techniques viz., XRD, SEM and DSC indicated that multiple crystal grains (with sizes varying from 0.1 to 1 μm) are dispersed in the residual glass phase. The concentration of crystal grains found to increase with increase in Nb2O5 content. The XRD studies have further revealed that the bulk samples are composed of columbite ZnNb2O6 crystal phases. Using generalized gradient approximation (GGA) quantitative information on these crystal phases viz., the lattice parameters, optical band gap and band structure were evaluated. The analysis of results of IR spectral studies have indicated that there is an increasing degree of polymerization of glass network with increase in Nb2O5 content due to the increased connectivity between various structural groups in the glass network. The optical absorption spectra indicated an increase in optical transmittance of the bulk samples with increase in Nb2O5 content. The dielectric parameters are observed to decrease, whereas the dielectric breakdown strength is observed to increase to a large extent due to the crystallization of the glass with the Nb2O5. The increase is attributed to the formation of ZnNb2O6 crystalline phases that contain intertwined ZnO6 and NbO6 structural units. As a whole, zinc borate glasses exhibited a significant increase in the electrical insulating strength due to the crystallization with Nb2O5 as the crystallizing agent. Further, the value of dielectric constant is also found to be the optimal with no dispersion with frequency up to 450 K. Overall, the studied glass‐ceramics meet the necessary physical conditions to be used as insulating layers in the display panels and hence may be considered for such applications.  相似文献   

7.
Lithium and sodium aluminosilicates are important glass‐forming systems for commercial glass‐ceramics, as well as being important model systems for ion transport in battery studies. In addition, uncontrolled crystallization of LiAlSiO4 (eucryptite) in high‐Li2O compositions, analogous to the more well‐known problem of NaAlSiO4 (nepheline) crystallization, can cause concerns for long‐term chemical durability in nuclear waste glasses. To study the relationships between glass structure and crystallization, nine glasses were synthesized in the LixNa1‐xAlSiO4 series, from x = 0 to x = 1. Raman spectra, nuclear magnetic resonance (NMR) spectroscopy (Li‐7, Na‐23, Al‐27, Si‐29), and X‐ray diffraction were used to study the quenched and heat‐treated glasses. It was found that different LiAlSiO4 and NaAlSiO4 crystal phases crystallize from the glass depending on the Li/Na ratio. Raman and NMR spectra of quenched glasses suggest similar structures regardless of alkali substitution. Li‐7 and Na‐23 NMR spectra of the glass‐ceramics near the endmember compositions show evidence of several differentiable sites distinct from known LixNa1‐xAlSiO4 crystalline phases, suggesting that these measurements can reveal subtle chemical environment differences in mixed‐alkali systems, similar to what has been observed for zeolites.  相似文献   

8.
Transparent and homogeneous tantalum phosphate glasses were prepared in the binary system (100-x)NaPO3-xTa2O5 with x varying from 10 to 50 mol%. Thermal, structural, and optical properties, as well as crystallization mechanisms, were investigated by thermal analysis, X-ray diffraction, Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopies, optical absorption, transmission electron microscopy in terms of Ta2O5 content. FTIR and Raman results support the tantalum insertion in the phosphate chains with [TaO6] polyhedra cross-linking the phosphate units. At higher Ta2O5 content, [TaO6] clusters are formed and connected to the phosphate network by P-O-Ta bonds. This structural evolution is in good agreement with the thermal features measured by differential scanning calorimetry (DSC) with a strong increase of the Tg temperatures up to 920°C, high thermal stability against crystallization for low Ta2O5 content and increasing of crystallization tendency for the most Ta-concentrated samples. Besides, due to the progressive insertion of [TaO6] units, the precipitation of Na2Ta8O21 perovskite-like phase was identified in the sample with 50 mol% of Ta2O5. The optimal heat treatment conditions were identified using DSC measurements and a transparent glass-ceramic from 50NaPO3 to 50Ta2O5 composition was prepared. The obtaines glass-ceramic has great potential for optical applications, such as host for rare-earth ions, nonlinear optical materials, and ferroelectric domain.  相似文献   

9.
The structure, atomic packing density, calorimetric glass transition, and hardness of mixed sodium–lithium germanophosphate oxynitride glasses with varying Ge/P and N/P ratios were investigated. The combined influences of nitridation and mixed network former effect (MNFE) on the glass structure were analyzed using Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and 31P nuclear magnetic resonance (NMR) spectroscopy. Evidence for the existence of germanium in a higher coordination state, i.e., five‐ or sixfold coordination, was obtained by performing XPS analysis of the oxide glasses, with indication of conversion to tetrahedral coordination upon nitridation. Raman spectroscopy measurements implied that the germanate network was modified upon nitridation, including the removal of ring‐like germanate structures and P–O–Ge mixed linkages. The partial anionic N‐for‐O substitution gave rise to the linear dependence of the glass transition temperature (Tg) and hardness (HV) on nitrogen content (expressed as N/P ratio), especially for lower Ge/P ratio. However, nitridation also caused an unexpected increase in liquid fragility and decrease in density. This suggests that the governing structural parameter for property evolution in such LiNaGePON glasses is not only the increased degree of cross‐linking of the phosphate chains, but rather the short‐ and intermediate‐range structural modifications within the germanate component of the oxynitride glasses.  相似文献   

10.
《Ceramics International》2022,48(13):18433-18440
The addition of small amounts of niobia (Nb2O5) in borosilicate glasses was explored. By analysis on thermal and structural changes, we found evidences that niobium integrates the glass structure in octahedral NbO6 coordination. Adding up to 8.0 mol% of Nb2O5, the oxide partially ruptured the glass structure, interfering in the BO3/BO4 ratio, but the predominant network configuration was maintained. Thermally, there was an increase in the processing interval and the glasses became more resistant against crystallization, with the presence of niobia. Also, the oxide contributed to a notable decrease in the viscosity of the melts. The improvement of such properties were obtained by the controlled dispersion of the oxide in the glass network structure, avoiding large areas of phase-to-phase separation to preserve the desired ability of these glasses to incorporate a wide range of elements.  相似文献   

11.
This paper reports on the results of an investigation into the influence of the purity of the initial materials used for preparing vitreous lead metaphosphate, the acidity of the phosphate matrix, and the contents of additives of Group I–III and V elements and the second glass-former on the location of the UV transmission edge of simple binary and ternary lead phosphate glasses. It is shown that, even for a binary glass of the composition (mol %) 50PbO · 50P2O5, the location of the UV transmission edge can be shifted by ~50 nm on the wavelength scale depending on the purity of the initial reactants. The shift of the UV transmission edge toward the UV spectral range for ternary glasses containing no variable-valence elements other than lead is considerably larger than that for the high-lead phosphate glass of the previously proposed composition involving antimony, niobium, and cerium oxides. It is established that the addition of niobium oxide Nb2O5 to lead phosphate glasses brings about a red shift of the UV transmission edge and a change in the crystallization ability of the glasses. Niobium oxide at a content up to 1.5 mol % increases the crystallization ability of the glass, whereas a change in the niobium oxide content from 1.5 to 3.1 mol % results in a decrease in the crystallization ability. It is demonstrated that the crystallization ability of high-lead phosphate glasses increases at a boron oxide content higher than 5 mol %.  相似文献   

12.
The high refractive index La2O3–TiO2–Nb2O5 glasses were prepared by containerless processing, and the glass‐forming region was determined. The refractive index showed the range from 2.20 to 2.32, and the values were much higher than those of most optical glasses. The completely miscible 30LaO3/2–(70?x)TiO2xNbO5/2 (0 ≤ ≤70) system was fabricated to study the compositional dependence of refractive index and optical transmittance. The crucial determinants of the refractive index of oxide glasses, oxygen molar volume, and electronic polarizability of oxygen ions were calculated. The principle of additivity of glass properties was suitable for the calculation of refractive index between glass and compositional oxides. All the glasses were colorless and transparent in the visible to 6.5 μm middle infrared (MIR) region. These results are useful for designing new optical glasses with high refractive index and low wavelength dispersion in wide optical window.  相似文献   

13.
In this report, effect of enhanced rare earth (La2O3) concentration on substitution of TeO2 within ternary TeO2‐TiO2‐La2O3 (TTL) glass system has been studied with respect to its thermal, structural, mechanical, optical, and crystallization properties with an aim to achieve glass and glass‐ceramics having rare‐earth‐rich crystalline phase for nonlinear optical and infrared photonic applications. DSC analysis (10°C/min) demonstrates a progressive increase in glass‐transition temperature (Tg) from 359 to 452°C with the increase in La2O3 content. Continuous glass network modification with transformation of [TeO4] to [TeO3/TeO3+1] units is evidenced from Raman spectra which is corroborated with XPS studies. While mechanical properties demonstrate enhancement of cross‐linking density in the network. These glasses exhibit optical transmission window extended from 0.4 to 6 μm with calculated zero dispersion wavelength (λZDW) varying from 2.41 to 2.28 μm depending upon La2O3 content. Crystallization kinetics of TTL10 (80TeO2‐10TiO2‐10La2O3 in mol%) glass has been studied via established models. Activation energy (Ea) has been evaluated and dimensionality of crystal growth (m) suggests formation of surface crystals. Glass‐ceramic with crystalline phase of La2Te6O15 has been realized in heat‐treated TTL10 glass samples (at 450°C). As predicted from DSC analysis, FESEM study unveils the formation of surface crystallized glass‐ceramics.  相似文献   

14.
La2O3–Ga2O3M2O5 (M = Nb or Ta) ternary glasses were fabricated using an aerodynamic levitation technique, and their glass‐forming regions and thermal and optical properties were investigated. Incorporation of adequate amounts of Nb2O5 and Ta2O5 drastically improved the thermal stabilities of the glasses against crystallization. Optical transmittance measurements revealed that all the glasses were transparent over a wide wavelength range from the ultraviolet to the mid‐infrared. The refractive indices of the glasses increased and the Abbe number decreased upon substituting Ga2O3 with Nb2O5, and the decrease in the Abbe number was significantly suppressed when Ta2O5 was incorporated into the glass. As a result, excellent compatibility between high refractive index and lower wavelength dispersion was realized in La2O3–Ga2O3–Ta2O5 glasses. Analysis based on the single‐oscillator Drude–Voigt model provided more systematical information and revealed that this compatibility was due to an increase in the electron density of the glass.  相似文献   

15.
New magneto-optical vitreous materials were obtained by melting-quenching technique comprising wet route raw materials preparation. The glass has the following composition in oxide mol. %: 10 Li2O, 9 Al2O3, 5 ZnO, (35; 20; 50) B2O3, (35; 50; 20) P2O5, 3 Bi2O3, 3 PbO, phosphorus and boron oxide being the vitreous network formers. It was also prepared a similar reference glass composition but without Bi2O3 and PbO. Optical and structural characterization by ultraviolet-visible (UV–Vis), Fourier Transform Infrared (FTIR) and Raman Spectroscopy of the bulk glasses showed a transmission over 90%, metaphosphate structure of glass together with Q2 boron oxide units and P–O?B bonds. The mechanical parameters, hardness (H), Young's modulus (E) and fracture toughness (KIC) of boron phosphate glasses, evaluated by micro- and nanoindentation techniques, demonstrated mostly higher values in comparison with those for alumino-phosphate glasses due to mixed boro-phosphate network. Thermal behavior was investigated by Differential Scanning Calorimetry (DSC) putting in evidence the vitreous transition temperature which decreases with about 45 °C when Bi and Pb oxides were added and two crystallization effects. The diamagnetic character of a highly transparent Bi and Pb oxide co-doped boron phosphate glass was confirmed by ellipsometry, and the glass presented high magneto-optical properties at the top of the commercial bulk products.  相似文献   

16.
The amorphous silica (a‐SiO2) and germania (a‐GeO2) have a wide range of applications in glass industry. Based on a previously constructed near‐perfect continuous random network model with 1296 atoms and periodic boundary conditions, we extend our study to amorphous Si1?xGexO2 models of homogeneous random substitution of Si by Ge with x ranging from 0 to 1. We have calculated the structural, electronic, mechanical, and optical properties for the series by using the first‐principles density functional theory methods. The x‐dependence of the variations in the properties is analyzed and critically compared with available experimental data. The mass density, volume, total bond order density, bulk mechanical properties, and refractive index are found to vary linearly as a function of x. For x = 0.5, we have also constructed six different kinds of particle immersion models to test the effect of inclusion of spherical particles of one glass of different sizes in the medium of the other glass on their physical properties. It is shown that particle sizes do affect the properties of particle immersion. Our calculations provide deep insight on the properties of mixture and nanocomposites of a‐SiO2 and a‐GeO2 glasses.  相似文献   

17.
We study the structure, crystallization, and performances of the sealing glasses with the composition (mol.%) of 12Al2O3·8B2O3·40SiO2·40RO (R = Mg, Ca, Sr) for solid oxide fuel cells (SOFCs) before and after isothermal treatment at 700°C, which is within the operation temperature range (600-800°C) of SOFCs. The crystallization behavior has been investigated by differential scanning calorimetry and X-ray diffraction under both dynamic and isothermal conditions. The structural evolution is probed using the Raman and nuclear magnetic resonance spectroscopies. The performances of the sealing glasses are characterized in terms of the coefficient of thermal expansion, the crystallization-induced stress at glass–steel interface. We find that strong crystallization occurs at the operation temperature (700°C) far below the crystallization onset temperature measured by DSC. The structure origin of this anomalous crystallization is discussed in terms of structural heterogeneity of the three studied glasses. We determine the residual stress at the interface between the Ca-containing glass and the steel after isothermal treatment at 700°C for 48 h, but this stress does not lead to falling off the glass layer from the steel. This indicates that this glass is a good candidate to be applied in SOFCs.  相似文献   

18.
Transparent (Sr0.5Ba0.5)Nb2O6 (SBN50) nanocrystallite‐precipitated phosphate glass‐ceramics were prepared by a conventional glass‐ceramic process. x(SrO–BaO–2Nb2O5) ? (100–4x)P2O5 (xSBNP) glasses with a refractive index of 1.9–2.0 exhibited high water resistance owing to the presence of Q0 and Q1 phosphate units. Both bulk and surface crystallization of the SBN50 phase were observed in 20SBNP and 21SBNP glass‐ceramics. Although the nominal content of SBN50 crystals in the 21SBNP glass was larger than that in the 20SBNP glass, the latter exhibited better crystallinity of SBN50 and a higher number density of precipitated SBN nanocrystallites. By tuning the two‐step heat‐treatment and the chemical composition, transparent SBN50‐precipitated glass‐ceramics were successfully obtained. Given that no remarkable increase of the relative dielectric constants was observed after crystallization of the SBN50 nanocrystallites, it is postulated that the relative dielectric constant of the bulk is mainly governed by the amorphous phosphate region, and that the contribution of precipitation of the SBN50 nanocrystallites to the dielectric constant is not very significant in this system.  相似文献   

19.
Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P2O5 – 20RO – 5TiO2xEu2O3 (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (Tg) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (5D07F2) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P2O5 – 20BaO – 5TiO2xEu2O3 (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu2O3. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu2O3. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.  相似文献   

20.
The crystallization of the xK2O · xNb2O5· (1 – 2x)SiO2(x= 0.167–0.250) glasses and glasses close in composition to K2O · Nb2O5· 4SiO2at the ratio K2O : Nb2O5 1 is investigated. In high-silica glasses, the metastable phase separation followed by the bulk multiphase crystallization are observed at temperatures close to the glass transition point T g. The nanostructured transparent glasses that exhibit the optical second harmonic generation (SHG) effect are formed at the early stages of phase separation. The surface crystallization of glasses with the precipitation of the KNbSi2O7noncentrosymmetric phase occurs at higher temperatures.  相似文献   

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