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1.
DC resistivity, thermopower and optical absorption of xV2O5–(1 ? x) As2O3 (0.58  x  0.93) glasses have been studied as a function of composition. The transport mechanism in these glasses has been identified to be a combination of hopping of small polarons between V4+ and V5+ sites and small bipolarons between As3+ and As5+ sites respectively. Electrical conductivity is found to be more of a function of vanadium content than arsenic concentration in the glasses, indicating that the contribution of bipolarons to the conductivity is negligible. Thermopower has also been found to be sensitive to the composition of the glasses. At low vanadium concentrations, the thermopower is negative, which exhibits a sign reversal as vanadium concentration is increased (at x = 0.7). An important feature of these glasses is that the thermopower is not a function of [V5+]/[V4+] ratio, as is normally observed in vanadate glasses, and such a phenomenon suggests that the arsenic ions (bipolarons) in these glasses contribute to the thermal transport phenomena in a significant way.  相似文献   

2.
《Journal of Non》2006,352(21-22):2100-2108
Electrical and optical properties of phosphate glasses containing vanadium and manganese ions in the xP2O5–[(100  x)(V2O5 + MnO)] (PVM) system have been investigated. This is the last article of a III-part series devoted to the electronic properties of phosphate glasses containing a mixture of transition ions. The first article was devoted to the electrical conductivity of glasses having the general composition: xP2O5–[(100  x)(V2O5 + Fe2O3)] (PVF). Competitive transport of small polarons on V and Fe ion sites was found to contribute to a mixed transition-ion effect (MTE) in PVF glasses. Several features of MTE were found to be similar to the well known mixed alkali effect, observed in glasses containing two alkali ions. In the second article, optical absorption and electronic conduction of xP2O5–[(100  x)(Fe2O3 + MnO)] (PFM) glasses were reported. In the absence of competitive transport between the two transition ions (since Mn ions were determined not to contribute to dc conduction), MTE was not observed. The most important feature of PFM glasses was a sharp increase in resistivity at a critical concentration of iron ions, similar to ‘metal–insulator transition’ (MIT). In the present article, we report a resistivity transition in PVM glasses which is similar to that exhibited by the glasses of the PFM series. While Fe ions contributed the carriers in the PFM glasses, V ions serve the same purpose in the PVM compositions. As the concentration of vanadium ions, nV, is decreased in the composition range 0.82 > nV > 0.40, resistivity (ρ) increases marginally. For glasses with 0.2 < nV < 0.40, resistivity and the activation energy for dc conduction (W) increase sharply with decreasing nV, marking the incidence of an MIT-type transition. As in the PFM glasses, the observation of MIT coincides with the transformation of small polarons to small bipolarons, which is confirmed by the shifting of the small polaron optical absorption band to higher energies with decreasing V concentration.  相似文献   

3.
《Journal of Non》2005,351(40-42):3235-3245
The electrical and dielectrical properties of Bi2O3–Fe2O3–P2O5 glasses were measured by impedance spectroscopy in the frequency range from 0.01 Hz to 4 MHz and over the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe2O3 content and Fe(II)/Fetot ratio. With increasing Fe(II) ion content from 17% to 34% in the bismuth-free 39.4Fe2O3–59.6P2O5 and 9.8Bi2O3–31.7Fe2O3–58.5P2O5 glasses, the dc conductivity increases. On the other hand, the decrease in dc conductivity for the glasses with 18.9 mol% Bi2O3 is attributed to the decrease in Fe2O3 content from 31.7 to 23.5 mol%, which indicates that the conductivity for these glasses depends on Fe2O3 content. The conductivity for these glasses is independent of the Bi2O3 content and arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electronic conduction. The evolution of the complex permittivity as a function of frequency and temperature was investigated. At low frequency the dispersion was investigated in terms of dielectric loss. The thermal activated relaxation mechanism dominates the observed relaxation behavior. The relationship between relaxation parameters and electrical conductivity indicates the electronic conductivity controlled by polaron hopping between iron ions. The Raman spectra show that the addition of up to 18.9 mol% of Bi2O3 does not produce any changes in the glass structure which consists predominantly of pyrophosphate units.  相似文献   

4.
Glasses of the (20 ? x)CaO–xSrO–(20 ? y)Na2O–60B2O3 ? y (CSNB) system with (5  x  15) mol% and y = 0.1 mol% of V2O5 were characterized by X-ray diffraction (XRD), EPR (Electron Paramagnetic Resonance), Optical absorption Spectra and FT-IR (Fourier transform Infrared Spectroscopy) studies. EPR spectra of all the glass samples exhibit resonance signals characterstic of VO2+ ions. The values of spin-Hamiltonian parameters indicate that the VO2+ ions in CSNB glasses were present in octahedral sites with tetragonal compression and belong to C4v symmetry. Spin-Hamiltonian parameters ‘g’ and ‘A’ were evaluated. The Optical band energy (Eopt) and Urbach energy (ΔE) were calculated from their ultra violet edges. By correlating EPR and Optical data the molecular orbital coefficients have been evaluated. IR spectra of these glasses were analyzed in order to identify the contribution of each component to the local structure that determines the physical properties of these glasses.  相似文献   

5.
《Journal of Non》2007,353(13-15):1377-1382
Near infrared (NIR) to visible upconversions of a fluorophosphate glass of composition (mol%) 7Ba(PO3)2–32AlF3–30CaF2–18SrF2–13MgF2 doped with various concentrations (0.1, 0.3 and 1.0 mol%) of Ho2O3 have been investigated by exciting at 892 nm at room temperature. Three upconverted bands originated from the 5F3  5I8, (5S2, 5F4)  5I8 and 5F5  5I8 transitions have been found to center at 491 nm (blue), 543 nm (green) and 658 nm (red), respectively. These bands have been justified from the evaluation of the absorption, normal (down conversion) fluorescence and excitation spectra. The upconversion processes have been interpreted by the excited state absorption (ESA), energy transfer (ET) and cross relaxation (CR) mechanisms involving population of the metastable (storage) energy levels by multiphonon deexcitation effect. It is evident from the infrared reflection spectral (IRRS) analysis that the upconversion phenomena are expedited by the low multiphonon relaxation rate in fluorophophate glasses owing to their high intense low phonon energy of ∼600 cm−1 which is very close to that of fluoride glasses (500–600 cm−1).  相似文献   

6.
In earlier studies on phosphate and tellurite glasses containing vanadium and iron oxides, non-linear variation of physical properties as functions of the ratios of the transition ions (V/V + Fe) were observed. The most striking effect was observed with electrical conductivity, where a 3 orders of magnitude reduction in conductivity was observed at a V/V + Fe ratio of ~ 0.4. The effect was termed Mixed Transition-ion Effect or MTE. In phosphate glasses, however, MTE was not observed when one of the transition ions was manganese. It was concluded that Mn does not contribute to conduction in these glasses. In the present study, we demonstrate a mixed transition ion effect in tellurite glasses containing MnO and Fe2O3 (xFe2O3(0.2 ? x) MnO0.8TeO2 with x varying from 0 to 0.2). A maximum in the property at an intermediate composition (x = 8.5 mol%), was observed in DC resistivity, activation energy, molar volume etc. Mossbauer and optical absorption (UV–VIS–NIR) measurements were performed on these glasses and the transport mechanism has been identified to be hopping of small polarons between Fe3 + (Mn3 +) and Fe2 + (Mn2 +) sites.  相似文献   

7.
The changes observed in the IR and ESR spectra of the xV2O5(1 ? x)[0.8P2O5 ? 0.2BaO] glass system with 0  x  50 mol% show that vanadium oxide acts as a network modifier at low concentration (x  5 mol%) and as a network former for high content (x  10 mol%). Thus the IR bands belonging to the phosphate groups are strongly reduced except the specific bands of the short chain phosphate units due to the phosphate network depolymerization and the spectra are dominated by the vibrations characteristic for POP, POV and VOV linkages. At the same time the changes observed in the ESR spectra of these glasses are explained supposing the superposition of two signals, one with a well-resolved hyperfine structure typical for isolated V4+ ions and a broad line characteristic for clustered ions. The line width dependence versus V2O5 content shows that dipole–dipole interactions exist between vanadium ions until x = 5 mol% and the superexchange interactions prevail at high content (x > 10 mol%).  相似文献   

8.
J.Y. Hu  H.-W. Yang  Y.J. Chen  J.S. Lin  C.H. Lai  Y.M. Lee  T. Zhang 《Journal of Non》2011,357(11-13):2246-2250
This study explores a series of optical, thermal, and structural properties based on 60P2O5–30ZnO–10Al2O3 (60P) glasses that doped with varied rare earth (RE) elements Yb2O3 and P2O5 components replaced by SiO2. It was found that the glasses density decrease with SiO2 concentration added to replace P2O5, whereas they increase with increased concentration of Yb3+-doped. Moreover, the glasses transition temperature, softening temperature, and refractive index increase with Yb3+ concentrations added, whereas the thermal expansion coefficient decreases. For the 60P glasses, 7 mol% Yb2O3 doped has the maximum fluorescence which is suppressed when Yb2O3 is doped up to 9 mol%. In addition, maximum lifetime was found to be 2.68 ms at an optimal Yb3+-doping at 1 mol% for 53P2O5–7SiO2–30ZnO–10Al2O3 glass.  相似文献   

9.
《Journal of Non》2007,353(11-12):1070-1077
The structural properties of xCr2O3–(40  x)Fe2O3–60P2O5, 0  x  10 (mol%) glasses have been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The Raman spectra show that the addition of up to 5.3 mol% Cr2O3 does not produce any changes in the glass structure, which consists predominantly of pyrophosphate, Q1, units. This is in accordance with O/P  3.5 for these glasses. The increase in glass density and Tg that occurs with increasing Cr2O3 suggests the strengthening of glass network. The Mössbauer spectra indicate that the Fe2+/Fetot ratio increases from 0.13 to 0.28 with increasing Cr2O3 content up to 5.3 mol%, which can be related to an increase in the melting temperature from 1423 to 1473 K. After annealing, the 10Cr2O3–30Fe2O3–60P2O5 (mol%) sample was partially crystallized and contained crystalline β-CrPO4 and Fe3(P2O7)2. The SEM and AFM micrographs of the partially crystallized sample revealed randomly distributed crystals embedded in a homogeneous glass matrix. EDS analysis indicated that the glass matrix was rich in Fe2O3 (39.6 mol%) and P2O5 (54.9 mol%), but contained only 5.5 mol% of Cr2O3. These results suggest that the maximum solubility of chromium in these iron phosphate melts is 5.5 mol% Cr2O3.  相似文献   

10.
Lithium yttrium silicate glasses mixed with different concentrations of Fe2O3 of the composition (40 ? x) Li2O–10Y2O3–50SiO2: x Fe2O3, with x = 0.3, 0.5, 0.8, 1.0, 1.2 and 1.5 (all in mol%) were synthesized. Electrical and dielectric properties including dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σac, impedance spectra as well as electric moduli, M(ω), over a wide continuous frequency range of 40 Hz to 106 Hz and in the low temperature range 100 to 360 K were measured as a function of the concentration of Fe2O3. The dc conductivity is also evaluated in the temperature range 100 … 360 K. The temperature and frequency dispersions of dielectric constant as well as dielectric loss have been analyzed using space charge polarization model. The ac and dc conductivities have exhibited increasing trend with increasing Fe2O3 content beyond 0.5 mol%, whereas the activation energy for the conductivity demonstrated decreasing tendency in this dopant concentration range. Both quantum mechanical tunneling (QMT) and correlated barrier hopping models (CBH) were used for clarification of ac conductivity origin and the corresponding analysis has indicated that CBH model is more appropriate for this glass system. For the better understanding of relaxation dynamics of the electrical properties we have drawn the scaling plots for ac conductivity and also electric moduli. The plots indicated that the relaxation dynamics is independent on temperature but depends on concentration of Fe2O3. The dc conductivity is analyzed using small polaron hoping model. The increase of conductivity with the concentration of Fe2O3 beyond 0.5 mol% is explained in terms of variations in the redox ratio of iron ions in the glass network. The results were further analyzed quantitatively with the support of experimental data from IR, optical absorption and ESR spectral studies. The overall analysis has indicated that Li2O–Y2O3–SiO2 glasses containing more than 0.5 mol% of Fe2O3 are more suitable for achieving good electrical conductivity in these glasses.  相似文献   

11.
The 70Li2S · (30 ? x)P2S5 · xP2O5 (mol%) oxysulfide glasses were prepared by the melt quenching method. The glasses were prepared in the composition range 0  x 10. The glass–ceramics were prepared by heating the glasses over crystallization temperatures. The POnS3?n (n = 1–3) oxysulfide units were produced in the glasses and glass–ceramics by partial substituting P2O5 for P2S5. In particular, the P2OS64? unit would be produced by substituting a small amount of P2O5 for P2S5. The oxygen atoms were incorporated into the Li7P3S11 crystal structure because the diffraction peaks of the oxysulfide glass–ceramic shifted to the higher angle side. The glass–ceramic with 3 mol% of P2O5 exhibited the highest conductivity of 3.0 × 10?3 S cm?1 and the lowest activation energy for conduction of 16 kJ mol?1. The P2OS64? dimer units in the oxygen-incorporated Li7P3S11 crystal would improve conductive behavior of the Li2S–P2S5 glass–ceramics.  相似文献   

12.
《Journal of Non》2003,315(1-2):77-88
The crystallisation of CaO–ZrO2–SiO2 glasses doped with V2O5 (0.1–5 mol%) has been investigated in terms of microstructure and thermal parameters. Results indicate that crystallisation is predominantly controlled by a surface nucleation mechanism, even though a partial bulk nucleation has been encountered in compositions containing more than 2 mol% of doping oxide. As detected from differential thermal analysis curves, glass transition temperature and crystallisation temperature, are strongly dependent upon V2O5 content varying from 0.0 to 2.0 mol%, while the crystallisation activation energy values decrease with a parabolic trend from B-glass (0.0 mol% V2O5 content, 495±7) to V-0.7 (0.7 mol% V2O5 content, 420±6) composition, increasing again to 442±5 kJ/mol K with higher amount of V2O5. The microstructure of the glass-ceramic materials clearly showed a marked dependence upon the amount of V2O5, also due to the presence of phase separation for content higher than 0.7 mol%. Wollastonite, CaO·SiO2, and a calcia–zirconia–silicate, 2CaO·4SiO2·ZrO2, are the main crystalline phases whose ratio slightly varies with vanadium oxide content. The glass ceramics obtained from the studied materials are greenish and bluish coloured, so it is possible to use the studied glasses as coloured frits for tile glazes.  相似文献   

13.
A series of borophosphate glasses in the composition (B2O3)0.10–(P2O5)0.40–(CuO)0.50?x–(MoO3)x; 0.05 ? x ? 0.50 have been investigated for room temperature density and dc conductivity over the temperature range from 350 to 650 K. The density decreased with increase in MoO3 over the composition range studied except a slight increase around 0.35 mole fraction. The observed initial decrease in conductivity with the addition of MoO3 has been attributed to the hindrance offered by the Mo+ ions to the electronic motions. The observed peak-like behavior in conductivity in the composition range 0.20 – 0.50 mol% of MoO3 is ascribed to the mixed transition metal ion effect (MTE). Mott’s small polaron hopping model has been used to analyze the high temperature conductivity data and the activation energy for conduction has been determined. The low temperature conductivity has been analyzed in view of Mott’s and Greaves variable range hopping models. It is for the first time that conduction mechanisms have been explored and MTE detected in mixed transition metal ions doped borophosphate glasses.  相似文献   

14.
The performance of phosphate glasses as a catalyst for water decomposition and a proton conductor was investigated. Glasses with a composition of 30Na2O–10BaO–30P2O5–(30?x)WO3xNb2O5 (5 < x < 25) decompose water vapor and generate hydrogen at 500 °C. The best decomposition performance was observed on a specimen with the Nb2O5 composition of x = 15. A part of hydrogen produced on the glass surface changes to protons by reducing W6+ ions and penetrates into the glass. The electron is the dominant charge carrier in the electric conduction of W-rich glasses, whereas proton conduction is predominant in Nb-rich glasses in hydrogen atmosphere. A Raman scattering experiment revealed that Nb contributes to depolymerize the –P–O–P– chains in the phosphate glass producing non-bridging oxygen. A possible model was proposed for the water decomposition and proton conduction processes.  相似文献   

15.
Thermal properties, water durability and structure of Nb2O5–SrO–P2O5 glasses containing 0–25 mol% Nb2O5 and 35–60 mol% SrO were explored aiming to develop high refractive index optical glasses. Structure studied using Raman and NMR spectra reveals that by increasing Nb2O5 content, niobium plays the role as intermediate. Nb5+ tends to break P–O–P and O–P–O bonds forming [NbO6] structure. Thus fractions of Q3 and Q2 decrease, while Q1 fraction increases. Furthermore the Q0 fraction replaces the lessened Q3 fraction. As P2O5 content is reduced to 30 mol%, partial [NbO6]octa turns into [NbO4]tetra and partial (Nb–O)short-octa becomes (Nb–O)short-tetra bond to stabilize the glass structure. Glass-transition and softening-temperatures of the glasses increase by increasing SrO and Nb2O5 contents. Thermal expansion coefficient increases by increasing SrO while decreases with Nb2O5 content. Water durability is enhanced as increasing Nb2O5 and SrO contents. Properties of the glasses correlate well with the worked out structure.  相似文献   

16.
《Journal of Non》2006,352(28-29):3088-3094
Bulk binary ZnO–P2O5 glasses with 50–70 mol% ZnO were immersed in distilled water at 30–90 °C for up to 72 h. The immersed samples were characterized by weight loss, the change in solution pH, X-ray diffraction (XRD) analysis, scanning electron microscopy and Raman spectroscopy. Weight loss decreased with ZnO concentration for all immersion temperatures. Dissolution behavior was classified into two types in terms of weight loss and macroscopic appearance. Type I was primarily recognized in 50–60 mol% ZnO glasses. In type I, the weight loss for 72 h was relatively large (>1.0 × 10−7 kg mm−2, >10% of initial sample weight). Raman spectra of the type I glasses indicated that the depolymerization of phosphate glass network occurred during the dissolution process. Crystalline Zn2P2O7 · 3H2O was precipitated in the water solution after immersion. Type II dissolution behavior was recognized in the 65 and 70 mol% ZnO glasses except for the 65ZnO–35P2O5 glass immersed at 90 °C. In the type II behavior, the weight loss for 72 h was relatively-small (<1.0 × 10−8 kg mm−2, <1% of initial sample weight). The microstructure of the type II glass indicated selective dissolution. The dissolution process of the type II glass is discussed.  相似文献   

17.
The atomic structures of two V2O5–P2O5 glasses and vitreous (v-) V2O5 were investigated by X-ray and neutron diffraction. The V=O double bond is a common characteristic of the VOn units that constitute the structures of the glasses. VO5 square pyramids with elongated bonds of ~ 0.190 nm to the pyramidal base are found for the 50V2O5–50P2O5 glass. These weaker V–O bonds are balanced in V–O–P bridges by overbonded P–O bonds. The V(IV) sites, which account for 19.7% and 35.2% of the total V sites in the 73V2O5–27P2O5 and 50V2O5–50P2O5 glasses, respectively, form similar pyramids in agreement with the structure of crystalline (VO)2P2O7. The short-range structure of v-V2O5 and the 73V2O5-27P2O5 glass is formed of mixtures of VO5 and VO4 pyramids. A significant amount of V···O distances > 0.22 nm found for all glasses belong either to linkages V=O···V or to three-coordinated O sites.  相似文献   

18.
High resolution O 1s, K 2p and Si 2p XPS Spectra were collected for a series of potassium silicate glasses ranging in composition from 10 mol% to 35 mol% K2O. The mole fraction of bridging oxygen (BO) has been accurately evaluated from the O 1s spectra. BO mole fractions of K-silicate glasses were calculated from Q-species distributions previously reported by 29Si MAS NMR data. The mole fractions of BO are identical for the two techniques (within experimental error) in glasses containing 13 mol% to 25 mol% K2O but in the compositional range between 25 mol% and 35 mol% BO mole fractions obtained by XPS are slightly greater than values derived from NMR data. The slight discrepancies between the two techniques at higher K2O content have not been resolved. The experimental data between 13 mol% and 25 mol% K2O indicate the presence of a third type of oxygen, O2?, in these glasses. A thermodynamic analysis indicates O2? is present at a few mol% in the glasses of low K2O content, but increases monotonically with increased K2O content.The O 1s XPS line widths for the BO peaks are highly variable. The variation in line widths may result from two types of BO contributing to the BO peak. As in the Na2O–SiO2 glass system, one type probably bridges two Si atoms (SiOSi) and the second type is O bonded to two Si atoms and one K atom.The Si 2p XPS spectra are distinctly non-symmetric, with low binding energy shoulders commonly present on the major peak, suggesting two contributions to the Si 2p signal. There is a strong correlation of Si 2p XPS peak and shoulder intensities with the abundances of the Q4 and Q3 species in glasses of the same composition suggesting that, with additional resolution, XPS may be capable of resolving individual Q-species in this system.  相似文献   

19.
This work presents a study on the structure, microstructure and properties of 50Li2xB2O3·(50 ? x)P2O5 glasses. The structure has been studied through NMR spectroscopy and the microstructure by TEM. The properties of the glasses are discussed according to their structure and microstructural features. The introduction of boron produces new linkages between phosphate chains through P–O–B bonds, whose amount increases with boron incorporation; at the same time, a depolymerisation of the phosphate chains into Q1-type phosphate units takes place. The introduction of boron produces an increase in Tg together with a decrease in the molar volume. The room temperature electrical conductivity increases with boron content as well. However, B2O3 contents higher than 20 mol% lead to crystallisation of lithium orthophosphate which contributed to hinder ionic conduction of the glasses.  相似文献   

20.
In an effort to design low-melting, durable, transparent glasses, two series of glasses have been prepared in the NaPO3–ZnO–Nb2O5–Al2O3 system with ZnO/Nb2O5 ratio of 2 and 1. The addition of ZnO and Nb2O5 to the sodium aluminophosphate matrix yields a linear increase of properties such as glass transition temperature, density, refractive index and elastic moduli. The chemical durability is also significantly, but nonlinearly, improved. The glass with the highest niobium concentration, 55NaPO3–20ZnO–20Nb2O5–5Al2O3 was found to have a dissolution rate of 4.5 × 10? 8 g cm? 2 min? 1, comparable to window glass. Structural models of the glasses were developed using Raman spectroscopy and nuclear magnetic resonance spectroscopy, and the models were correlated with the compositional dependence of the properties.  相似文献   

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