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1.
Niobium alkali germanate glasses were synthesized by the melt‐quenching technique. The ternary system (90‐x)GeO2xNb2O5–10K2O forms homogeneous glasses with x ranging from 0 to 20 mol%. Samples were investigated by DSC and XRD analysis, FTIR and Raman spectroscopy, and optical absorption. Structural and physical features are discussed in terms of Nb2O5 content. The niobium content increase in the glass network strongly modifies the thermal, structural and optical properties of alkali germanate glasses. DSC, Raman and FTIR analysis suggest niobium addition promotes NbO6 groups insertion close to GeO4 units of the glass network. XRD analysis also pointed out that samples containing high niobium oxide contents exhibit preferential niobium oxide‐rich phase after crystallization after heat treatment, which is similar to orthorhombic Nb2O5. Absorption spectra revealed high transmission range between 400 nm to 6.2 μm, added to a considerably decreased hydroxyl group content as the addition of niobium in the alkali germanate network. The niobium oxide‐rich phase crystallization process was studied and activation energy was determined, as well as nucleation and crystal growth temperatures and time for obtaining transparent glass‐ceramics.  相似文献   

2.
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   

3.
Gallium (Ga) helps solubilize rare‐earth ions in chalcogenide glasses, but has been found to form the dominant crystallizing selenide phase in bulk glass in our previous work. Here, the crystallization behavior is compared of as‐annealed 0–3000 ppmw Dy3+‐doped Ge–As–Ga–Se glasses with different Ga levels: Ge16.5As(19?x)GaxSe64.5 (at.%), for x = 3 and 10, named Ga3 and Ga10 glass series, respectively. X‐ray diffraction and high‐resolution transmission electron microscopy are employed to examine crystals in the bulk of the as‐prepared glasses, and the crystalline phase is proved to be the same: Ge‐modified, face centered cubic α‐Ga2Se3. Light scattering of polished glass samples is monitored using Fourier transform spectroscopy. When Ga is decreased from 10 to 3 at.%, the bulk crystallization is dramatically reduced and the optical scattering loss decreases. Surface defects, with a rough topology observed for both series of as‐prepared chalcogenide glasses, are demonstrated to comprise Dy, Si, and [O]. For the first time, evidence for the proposed nucleation agent Dy2O3 is found inside the bulk of as‐prepared glass. This is an important result because rare‐earth ions bound in a high phonon–energy oxide local environment are, as a consequence, inactive mid‐infrared fluorophores because they undergo preferential nonradiative decay of excited states.  相似文献   

4.
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   

5.
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   

6.
A series of regular shaped Pb(Zn1/3Nb2/3)O3‐based ternary ferroelectric single crystals (1 ? x)Pb(In1/2Nb1/2)O3–0.33Pb(Zn1/3Nb2/3)O3xPbTiO3 (PIN–PZN–PT) have been grown by means of the top‐seeded solution growth method that prevented pyrochlore phase and promoted [001] or [111] growth. The nucleation and crystallization behavior of the Pb(Zn1/3Nb2/3)O3‐based ferroelectric single crystals differed from other relaxor‐based ferroelectric single crystals was discovered. Di‐/piezo‐/ferro‐/pyroelectric properties were characterized systematically. The PIN–PZN–PT single crystals showed large coercive fields Ec, high Curie temperature TC and high pyroelectric coefficient P, presenting similar performance but better thermal stability compared with the PZN–PT single crystals, and making it a promising material for transducers and IR detectors in a wider temperature range.  相似文献   

7.
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   

8.
The sequence of crystallization in a recrystallizable lithium silicate sealing glass‐ceramic Li2O–SiO2–Al2O3–K2O–B2O3–P2O5–ZnO was analyzed by in situ high‐temperature X‐ray diffraction (HTXRD). Glass‐ceramic specimens have been subjected to a two‐stage heat‐treatment schedule, including rapid cooling from sealing temperature to a first hold temperature 650°C, followed by heating to a second hold temperature of 810°C. Notable growth and saturation of Quartz was observed at 650°C (first hold). Cristobalite crystallized at the second hold temperature of 810°C, growing from the residual glass rather than converting from the Quartz. The coexistence of quartz and cristobalite resulted in a glass‐ceramic having a near‐linear thermal strain, as opposed to the highly nonlinear glass‐ceramic where the cristobalite is the dominant silica crystalline phase. HTXRD was also performed to analyze the inversion and phase stability of the two types of fully crystallized glass‐ceramics. While the inversion in cristobalite resembles the character of a first‐order displacive phase transformation, i.e., step changes in lattice parameters and thermal hysteresis in the transition temperature, the inversion in quartz appears more diffuse and occurs over a much broader temperature range. Localized tensile stresses on quartz and possible solid‐solution effects have been attributed to the transition behavior of quartz crystals embedded in the glass‐ceramics.  相似文献   

9.
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   

10.
Local structural rearrangements in lead‐based complex perovskites of the type (Ba1?xPbx)(In0.50Nb0.50)O3 responsible for transition from ferroelectric [Ba(In0.50Nb0.50)O3] to relaxor [Pb(In0.50Nb0.50)O3] are examined by careful analysis of their Raman spectra. Subtle changes in the bonding brought about by the differences in the chemical nature of A‐ and B‐site cations have been correlated with the dynamic A–O–B coupling. Deviations in the local structure as a result of such bonding preferences have been confirmed by studying the changes in the Raman spectra when Nb5+ is substituted by Sn4+ as the third B‐site cation.  相似文献   

11.
Although glass–ceramics have been widely explored for their thermal stability and mechanical properties, they also offer unique symmetry-dependent properties such as piezoelectricity and pyroelectricity through controlled crystallization of a polar phase. This work examines crystallization of LiNbO3 in a 35SiO2–30Nb2O5–35Li2O mol% composition and crystallization of LiNbO3 and NaNbO3 in a 35SiO2–30Nb2O5–25Li2O–10Na2O mol% composition. Crystallization kinetics are examined using the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory where the Avrami exponent, n, is calculated to be 1.0–1.5. Microscopical analysis shows dendritic morphology, which when combined with the JMAK analysis, suggests diffusion-controlled one-dimensional growth. Adding Na2O to the glass composition increases the inter-diffusivity of ions which causes LiNbO3 to crystallize faster and lowers the activation energy of transformation from 1054 ± 217 kJ/mol in the ternary composition to 882 ± 212 kJ/mol. Time-temperature-transformation diagrams are presented which show that the temperature for maximum rate of transformation for LiNbO3 is ∼650°C and for NaNbO3 is ∼715°C.  相似文献   

12.
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   

13.
《Ceramics International》2022,48(9):12699-12711
The effect of variation of MgO (1.5, 4.5 and 7.5 mol%) content on glass structure, crystallization behavior, microstructure and mechanical properties in a Li2O–K2O–Na2O–CaO–MgO–ZrO2–Al2O3–P2O5–SiO2 glass system has been reported here. Increased amount of MgO enhanced the participation of Al2O3 as a glass network former along with [SiO4] tetrahedra, reducing the amount of non-bridging oxygen (NBO) and increasing bridging oxygen (BO) amount in glass. The increased BO in glass resulted in a polymerized glass structure which suppressed the crystallization and subsequently increased the crystallization temperature, bulk density, nano hardness, elastic modulus in the glasses as well as the corresponding glass-ceramics. MgO addition caused phase separation in higher MgO (7.5 mol%) containing glass system which resulted in larger crystals. The nano hardness (~10 GPa) and elastic modulus (~127 GPa) values were found to be on a much higher side in 7.5 mol% MgO containing glass-ceramics as compared to lower MgO containing glass-ceramics.  相似文献   

14.
The effects of adding Nb2O5 on the physical properties and glass structure of two glass series derived from the 45S5 Bioglass® have been studied. The multinuclear 29Si, 31P, and 23Na solid‐state MAS NMR spectra of the glasses, Raman spectroscopy and the determination of some physical properties have generated insight into the structure of the glasses. The 29Si MAS NMR spectra suggest that Nb5+ ions create cross‐links between several oxygen sites, breaking Si–O–Si bonds to form a range of polyhedra [Nb(OM)6?y(OSi)y], where 1 ≤ y ≤ 5 and M = Na, Ca, or P. The Raman spectra show that the Nb–O–P bonds would occur in the terminal sites. Adding Nb2O5 significantly increases the density and the stability against devitrification, as indicated by ΔT(Tx ? Tg). Bioglass particle dispersions prepared by incorporating up to 1.3 mol% Nb2O5 by replacing P2O5 or up to 1.0 mol% Nb2O5 by replacing SiO2 in 45S5 Bioglass® using deionized water or solutions buffered with HEPES showed a significant increase in the pH during the early steps of the reaction, compared using the rate and magnitude during the earliest stages of BG45S5 dissolution.  相似文献   

15.
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   

16.
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   

17.
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   

18.
In this work, the effect of gradual addition of Al2O3 substituting SiO2 on the structural, thermal, and mechanical properties of SiO2–BaF2–K2O–GdF3–Sb2O3‐based oxyfluoride glasses have been studied. The X‐ray diffraction (XRD) patterns and differential scanning calorimetric (DSC) curves indicate that there is a distinct primary crystallization corresponding to BaGdF5 phase formation in the samples without (0AlG) and with 5 mol% substitution of Al2O3 (5AlG) while the sample with 10 mol% of Al2O3 (10AlG) does not show such crystallization event. Further, the activation energy (Ea) for fluoride crystal formation is higher for the 5AlG in comparison to the 0AlG glass as determined by Kissinger, Augis‐Bennett and Ozawa models. Fourier transform infrared (FTIR) and Raman spectroscopy analysis confirmed the structural modification with the gradual addition of Al2O3 in the glass matrix revealing dominant presence of AlO4 tetrahedral units in 10AlG sample unlike in 5AlG sample which exhibited the manifestation of AlO6 units. Such structural variation has further been substantiated from the estimated elastic properties like Young's modulus (E), shear modulus (G), bulk modulus (K), longitudinal modulus (L), and mean ultrasonic velocity (Um) by showing a decrease for 5AlG sample in comparison with 0AlG sample followed by subsequent increase for 10AlG sample.  相似文献   

19.
《Ceramics International》2020,46(8):11492-11498
(1-x) (K2O–Na2O–2Nb2O5)-x (2BaO–Nb2O5–2SiO2) glass-ceramics with x = 0.10, 0.15, 0.20, 0.25 have been successfully prepared by traditional melting method. XRD and microstructure analysis demonstrate that all glass-ceramics are crystallized into uniform Na0.9K0.1NbO3 and K2(NbO)2(Si4O12) ferroelectric crystalline phase. Increasing x promotes the formation of Ba2NaNb5O15 phase with a tungsten bronze structure. Raman and complex impedance data confirmed that Ba2+ is introduced to repair the disruption of the glass network and make carrier migration difficult when x = 0.15. Thus, the x = 0.15 glass-ceramic sample possesses a maximum calculated energy storage density of 2.32 J/cm3 under 820 kV/cm because of a high degree of polymerization (DOP) glass network structure. Moreover, the pulsed discharge-charge tests are carried out to evaluate actual energy storage performance.  相似文献   

20.
A series of glasses composed of xB2O3–8Al2O3‐(90?x)Na2O–R2O3 (x = 65, 70, 75, 80, 85; R = Dy3+, Tb3+, Sm3+) were prepared through melt‐quenching. Structural evolution was induced by varying the glass composition. Increasing the glass network former B2O3 enhanced the luminescence of rare‐earth ions, as observed in the emission spectra. The mechanism of the glass structural evolution was investigated by the NMR spectra analysis. The dispersant effect of the glass structure was believed to promote the better distribution of the rare‐earth ions in the matrix and reduced the concentration quenching between them. The relationship between the glass structure and its optical properties was established.  相似文献   

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