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1.
《Journal of Non》2007,353(52-54):4783-4791
Phosphate glasses have been prepared by melting batch materials in electric furnaces, induction furnaces, and in microwave ovens. In the present work mixtures of (NH4)2HPO4 and Fe3O4 or Fe2O3 were exposed to microwave energy, heated to 1200 °C, and cast to produce iron phosphate glasses. Glasses were also produced in electric furnaces for comparison. The material was analyzed by X-ray diffraction, Mössbauer spectroscopy, and differential thermal analysis. For magnetite-based glasses produced in an electric furnace, the Fe2+/(Fe2+ + Fe3+) ratio is compatible with the value in the batch material. The Fe2+/(Fe2+ + Fe3+) ratio is higher for glasses produced in a microwave oven. Glasses with nominal composition 55Fe3O4–45P2O5 (mol%) produced in an electric furnace present an arranged magnetic phase with hyperfine field that could be associated to hematite (estimated to be 21%). All the glasses submitted to heat treatments for crystallization present the following crystalline phases: FePO4, Fe3(PO4)2, Fe(PO3)3, Fe(PO3)2 and Fe7(PO4)6. The amount of these phases depends on the glass composition, and glass preparation procedure. Microwave heating allows to reach melting temperatures at high heating rates, making the procedure easy and economical, but care should be taken concerning the final Fe2+/(Fe2+ + Fe3+) ratio.  相似文献   

2.
《Journal of Non》2006,352(6-7):539-543
Iron commonly exists as an equilibrium mixture of ferrous ions, Fe2+, and ferric ions, Fe3+, in glass. Fe3+ is a strong absorber of ultraviolet light and imparts a yellow color to glass, while Fe2+ has an absorption band in the near-infrared, resulting in a blue coloration. This study synthesized soda-lime-silicate glasses with high iron contents (1–3 wt%) in which virtually all the iron was fully oxidized to the ferric redox state, resulting in a UV-absorbing, yellow glass. The effectiveness of three common oxidizing agents (cerium, manganese, and antimony) to react with Fe2+ in these high-iron glasses was determined as a function of the processing temperature (1200–1400 °C). Cerium was the best oxidizer at the highest iron contents (3 wt%), while manganese was more effective at the lowest iron contents (1 wt%).  相似文献   

3.
Glasses with composition 50GeO2–(50?x)PbO–5PbF2xLnF3 (Ln = Pr3+–Yb3+) were prepared from commercial raw materials. The content of PbF2 was constant and amounted to 5 mol% whereas the concentration of luminescent ions was diverse (0.2 and 2 mol%). Thermal stability of the glasses were monitored by differential thermal analysis (DTA). It has been found that increase of rare-earth fluoride content from 0.2 mol% to 2 mol% brings about a shift of the glass crystallization onset from 450 °C to 487 °C for Nd-doped samples and from 466 °C to 482 °C for Tm-doped samples. Optical absorption and emission spectra of Ln active ions in oxyfluoride glass have been investigated at room temperature in the ultraviolet (UV), visible (VIS) and near-infrared (NIR) region. Oscillator strengths, phenomenological Judd–Ofelt intensity parameters Ω2,4,6, radiative transition probabilities, branching ratios and radiative lifetimes of luminescent levels have been estimated. Analysis of decay curves of luminescence revealed that the increase of rare-earth fluoride content from 0.2 mol% to 2 mol% shortens the lifetime of the 4F3/2 level of Nd3+ from 224 μs to 90 μs.  相似文献   

4.
《Journal of Non》2006,352(21-22):2159-2165
The mechanism of crystallization from a B2O3-containing glass, with composition based in the CaO–MgO–Al2O3–SiO2 system, to a glass–ceramic glaze was studied by different techniques. Glass powder pellets were fast heated, simulating current industrial tile processing methods, at several temperatures from 700 to 1200 °C with a 5 min hold. Microstructural study by field emission scanning electron microscopy revealed that a phase separation phenomenon occurred in the glass, which promoted the onset of mullite crystallization at 900 °C. The amount of mullite in the glass heated between 1100 and 1200 °C was around 20 wt%, as determined by Rietveld refinement. The microstructure of the glass–ceramic glaze heated at 1160 °C consisted of interlocked, well-shaped, acicular mullite crystals longer than 4 μm, immersed in a residual glassy phase.  相似文献   

5.
The redox behavior of various elements (Fe, Sb, Ce, Ti, Zn) was investigated in alkali–alkaline earth-silica CRT (Cathode ray tube: TV panel) model glass melts using the square-wave voltammetry (SWV). The current–potential curve, so called voltammogram, was produced at temperature range of 1000–1400 °C under the scanned potential between 0 and –800 mV at 100 Hz. The Fe, Ti and Zn doped melts exhibited one peak due to reduction reaction. In the case of the Sb doped melts, two traces doubted as peak were found in the voltammogram at low temperature while only one peak existed at high temperature. The peak potential was shifted to the negative direction with decrease of temperature, however, its temperature dependence showed linearity. On the other hand, no peak was found in voltammogram of the melts doped with Ce. Based on the temperature dependence of the peak potential, standard enthalpy (ΔH0) and standard entropy (ΔS0) for the reduction of Fe3+ to Fe2+, Sb3+ to Sb0 and Zn2+ to Zn0 in CRT model glass melts were calculated.  相似文献   

6.
Glass with composition of 51SiO2–24.5Al2O3–23MgO–1.5K2O doped with Co2+ ions was prepared by conventional melting method. The glass sample was heated at 900 °C for 360 min under atmosphere, and the powder XRD measurement showed that crystalline phase successfully precipitated in the sample. As is compared with standard JCPDS card, the crystalline phase identified as a mixture of zirconium titanate (ZrTiO4) and one of the compounds of magnesium aluminum oxide. The crystallite size was confirmed by transmission electron microscope (TEM) observation; it could be estimated as 30 nm in diameter from the TEM image. Based on the area ratio of crystalline phase and residual glass phase, the precipitated crystallite phase volume ratio can be estimated to be not higher than 30% in the Co2+ doped glass ceramic sample. The absorption coefficient at 1.54 μm for transparent glass ceramic sample is clearly higher than that in base glass, which can be explained by the fact that Co2+ ions entered into the precipitated nano-sized crystal phase and led to higher absorption coefficient at 1.54 μm for tetrahedral coordinated Co2+ ion. Consequently, the Co2+ doped transparent glass ceramic sample with thickness of 0.35 mm was used as a saturable absorber for 1.54 μm Er-glass laser oscillation, and Q switched pulses with pulse energy of 40 mJ, pulse width of 42 ns, and peak power of 0.95 mW were shown in the experiments.  相似文献   

7.
In order to crystallize a large quantity of the lithium?mica in glass?ceramics, 5.1 mass% MgF2 was added to the starting materials of the parent glasses having chemical compositions of Li(1+x)Mg3AlSi3(1+x)O10+6.5xF2 (x = 0.5 and 1.0). Transparent glass?ceramics, in which a large quantity of lithium?mica with particle size of <50 nm was separated, could be prepared from the MgF2-added parent glass with x = 0.5. While the parent glass, which had a binodal phase separation structure, did not exhibit electrical conductivity, the transparent glass–ceramic was given conductivity by the formation of an interlocking structure of mica. As the separated mica formed a tighter interlocking structure, the conductivity increased and reached a value of 2.0 × 10?3 S/cm at 600 °C. The MgF2-added parent glass with x = 1.0 was not transparent because of coarse spinodal phase separation. The conductivity was 4.3 × 10?4 S/cm at 600 °C but was significantly decreased by the separation of mica.  相似文献   

8.
《Journal of Non》2006,352(38-39):4069-4075
Glass melts with the basic compositions xLi2O · 15Al2O3 · (85  x)SiO2 (x = 8.5, 11, 13.5, 16 and 18.5) doped with 0.25 mol% Fe2O3 were studied by square-wave voltammetry and impedance spectroscopy at temperatures in the range from 1100 to 1600 °C. The square-wave voltammograms show a pronounced peak attributed to the reduction of Fe3+ to Fe2+. The attributed peak potentials which are equal to the standard potentials of the redox pair decrease linearly with the temperature. Impedance spectra measured could be simulated using an equivalent circuit attributed to a simple electron transfer reaction controlled by diffusion.  相似文献   

9.
《Journal of Non》2006,352(38-39):4101-4111
The structure of Li2O · 2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 °C, respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si–O–Si bond angle ∼7° lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa new high pressure form of lithium metasilicate crystallizes. This new phase, while having lithium metasilicate crystal symmetry, contains at least four different Si sites. NMR results for 6 GPa indicate the presence of Q4 species with (Q4)Si–O–Si(Q4) bond angles of ∼157°. This is the first reported occurrence of Q4 species with such large bond angles in alumina free alkali silicate glass. No five- or six-coordinated Si are found.  相似文献   

10.
Transparent glasses of composition 10BaO.20Bi2O3.(70 ? x)B2O3.xFe2O3 (wt.%) where 0  x  2.0, were characterized by XRD and SEM. Physical, spectroscopic and dielectric properties were investigated. At higher dopant of Fe2O3, EPR results revealed that, the number of Fe3+ ions participate in the resonance is decreased by forming a new signal at g  3.015 due to increase of antiferromagnetic interaction of Fe3+ ions and/or formation of low spin Fe3+ ions in the glass matrix. With initial 0.5 wt.% doping of Fe2O3, less dense glass is formed with colloids of metallic Bi0 atoms. The absorption bands at 604 and 712 nm in F5 glass are ascribed to Bi0 and Bi+ radicals respectively. No characteristic Fe3+ absorption bands (spin-forbidden) are found. Fe2+ ions are increased at higher concentration of Fe2O3. Higher concentration of Fe2O3 is favorable for BO2O?, BO3, BiO6 and FeO6 symmetry unit leads to low band gap and high Urbach energy. By doping of Fe2O3 the dielectric parameters like dielectric constant (ε′), loss (tanδ and ac electrical conductivity (σac) are found to increase.  相似文献   

11.
Sodium tracer diffusion coefficients, D*Na, have been measured using the radioactive isotope Na-22 in sodium boroaluminosilicate (NBAS) glasses containing either a small amount of As2O3 or Fe2O3. The chemical compositions of the first type of glasses are given by the formula [(Na2O)0.71(Fe2O3)0.05(B2O3)0.24]0.2[(SiO2)x(Al2O3)1 ? x]0.8 and those of the second type of glasses correspond to the formula [(Na2O)0.73(B2O3)0.24(As2O3)0.03]0.18[(SiO2)x(Al2O3)1 ? x]0.82. Tracer diffusion measurements were performed at different temperatures between 198 and 350 °C. Pre-annealing of the glass samples at their glass transition temperatures in common air was found to lead to changes in the values of sodium tracer diffusion coefficients. For the NBAS glasses containing Fe2O3, after pre-annealing for 5 h, the activation enthalpy derived for the sodium tracer diffusion increases almost linearly from 57.5 to 71.3 kJ/mol with a decrease in the alumina content while the pre-exponential factor of the sodium tracer diffusion coefficient increases from 2.1 · 10? 4 to 5.3 · 10? 4 cm2/s. For the iron-free NBAS glasses pre-annealed for 5 h, the activation enthalpy varies between 63.9 and 71.4 kJ/mol while the pre-exponential factor varies between 1.5 · 10? 4 and 1.2 · 10? 3 cm2/s. In addition, it was observed that the considered glasses take up water when annealed at 300 °C in wet air with PH2O = 474 mbar.  相似文献   

12.
《Journal of Non》2006,352(38-39):4082-4087
Liquids with the base compositions (16  x/2)Na2O · xNaF · 10CaO · 74SiO2 (x = 0, 1, 3, and 4) and (10  x/2) · Na2O · xNaF · 10CaO · yAl2O3 · (80  y)SiO2 (x = 0, 1, 3, 5 and y = 5 and 15) doped with 0.25 mol% Fe2O3 were studied by means of square-wave voltammetry in the temperature range from 1000 to 1500 °C. With increasing temperature, the redox equilibria were shifted to the reduced state. Also while increasing the alumina concentration, the Fe2+/Fe3+-redox equilibrium is shifted to the reduced state. In the soda-lime–silica melt the addition of fluoride shifts the equilibrium to the oxidized state, while in the aluminosilicate melts with 15 mol% Al2O3, the equilibrium is shifted to the reduced state. In the aluminosilicate melts with 5 mol% Al2O3, the equilibrium was not affected by the fluoride concentration. This is explained by the structure of the respective glass compositions.  相似文献   

13.
Modified iron phosphate glasses have been prepared with nominal molar compositions [(1?x)·(0.6P2O5–0.4Fe2O3)]·xRySO4, where x = 0–0.5 in increments of 0.1 and R = Li, Na, K, Mg, Ca, Ba, or Pb and y = 1 or 2. In most cases the vast majority or all of the sulfate volatalizes and quarternary P2O5–Fe2O3–FeO–RyOz glasses or partially crystalline materials are formed. Here we have characterized the structure, thermal properties, chemical durability and redox state of these materials. Raman spectroscopy indicates that increasing modifier oxide additions result in depolymerization of the phosphate network such that the average value of i, the number of bridging oxygens per –(PO4)– tetrahedron, and expressed as Qi, decreases. Differences have been observed between the structural effects of different modifier types but these are secondary to the amount of modifier added. Alkali additions have little effect on density; slightly increasing Tg and Td; increasing α and Tliq; and promoting bulk crystallization at temperatures of 600–700 °C. Additions of divalent cations increase density, α, Tg, Td, Tliq and promote bulk crystallization at temperatures of 700–800 °C. Overall the addition of divalent cations has a less deleterious effect on glass stability than alkali additions. 57Fe Mössbauer spectroscopy confirms that iron is present as Fe2+ and Fe3+ ions which primarily occupy distorted octahedral sites. This is consistent with accepted structural models for iron phosphate glasses. The iron redox ratio, Fe2+/ΣFe, has a value of 0.13–0.29 for the glasses studied. The base glass exhibits a very low aqueous leach rate when measured by Product Consistency Test B, a standard durability test for nuclear waste glasses. The addition of high quantities of alkali oxide (30–40 mol% R2O) to the base glass increases leach rates, but only to levels comparable with those measured for a commercial soda-lime-silica glass and for a surrogate nuclear waste-loaded borosilicate glass. Divalent cation additions decrease aqueous leach rates and large additions (30–50 mol% RO) provide exceptionally low leach rates that are 2–3 orders of magnitude lower than have been measured for the surrogate waste-loaded borosilicate glass. The P2O5–Fe2O3–FeO–BaO glasses reported here show particular promise as they are ultra-durable, thermally stable, low-melting glasses with a large glass-forming compositional range.  相似文献   

14.
《Journal of Non》2007,353(24-25):2383-2391
Thermal stability and crystallization kinetics of the glass 21% MgO, 21.36% Al2O3, 53.32% SiO2 and 4.11% TiO2 (mol%) has been studied using differential thermal analysis (DTA), dilatometry and X-ray diffraction (XRD). Glass in both bulk and frit forms were produced by melting in platinum crucible at 1600 °C for 1–2 h. From variation of DTA peak maximum temperature with heating rate, the activation energies of crystallization were calculated to be 340 kJ mol−1 and 498 kJ mol−1 for first and second crystallization exotherms, respectively. Crystallization of bulk glass was carried out at various temperatures and for different time durations in the range of 850–1000 °C. The influence of the addition of TiO2 on the crystallization sequence of the glass was experimentally determined and discussed.  相似文献   

15.
《Journal of Non》2006,352(38-39):4062-4068
Glasses with the base composition 16Na2O · 10CaO · 74SiO2 doped with copper and iron or copper and manganese were studied by high temperature UV–vis–NIR spectroscopy. The spectra exhibited distinct absorption bands attributed to the respective transition metal ions present (Cu2+, Fe2+, Fe3+, Mn3+). In glasses doped with only one polyvalent element, the absorption decreases linearly with increasing temperature, the absorption bands are shifted to smaller wave numbers and get broader. In glasses doped with two types of transition metals, the situation is the same up to a temperature of around 550 °C. At larger temperature, the Cu2+-absorption in glasses also co-doped with iron increases again, while in glasses doped with both copper and manganese the absorption is approximately the same as in glasses solely doped with copper. It is shown that this is due to redox reactions between polyvalent species. These reactions are frozen in at temperatures <550 °C.  相似文献   

16.
Li Chen  Chunlei Yu  Dongbing He  Lili Hu  Wei Chen 《Journal of Non》2011,357(11-13):2286-2289
Transparent glass-ceramics were synthesized by heat-treatment of glass with a composition of 5La2O3–13.2MgO–28.8Al2O3–46SiO2–4.5TiO2–2.5ZrO2–0.15CoO (LMAS) (wt.%). The activation energy of crystallization and the Avrami parameter for the LMAS glass were determined from the DTA curves at different heating rates. The most two intense bands of Raman spectrum of initial glass at ~ 810 cm?1 and ~ 900 cm?1 were connected with the presence of [SiO4] and [TiO4] tetrahedral, respectively. After heat-treated at 700 °C/10 h+820 °C/8 h, the intensity of the band for [TiO4] tetrahedral weakened, while an intensive band at ~ 800 cm?1 for the Ti–O bond appeared. Other bands were characteristics of high-silicate network and x(MgTi2O5y(Al2TiO5) polycrystals. The changes reflected phase separation after heat-treatment of the initial glass. The strong absorption band of glass-ceramics centered at 580 nm can be assigned to 4A2(4F)→4T1(4P) and the broad absorption band at 1100–1700 nm to 4A2(4F)→4T1(4F) transitions of tetrahedral coordinated Co2+ ion. Two broad emission bands, one was around 660 nm, the other was from 800 nm to 1050 nm, of glass-ceramics correspond to the 4T1(4P)→4A2(4F) and 4T1(4P)→4T2(4F) transitions of tetrahedral coordinated Co2+ ions. The absorption and emission features clearly demonstrated that Co2+ ions were incorporated into nanocrystals and located in tetrahedral sites.  相似文献   

17.
《Journal of Non》2007,353(24-25):2374-2382
Glass materials in the ZnO–Fe2O3–SiO2 system, containing zinc ferrite nanoparticles, were prepared by the sol–gel method and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer spectroscopy, AC- and DC-magnetization techniques. The gel samples, dried at 130 °C, were further heat treated in air at 500 and 800 °C. At 500 °C zinc ferrite and hematite nanoparticles, with an average size of approximately 24 nm, were precipitated in the brown and opaque 10ZnO–10Fe2O3–80SiO2 and in the ruby colored transparent 5ZnO–5Fe2O3–90SiO2 and 2.5ZnO–2.5Fe2O3–95SiO2 glass matrices. In the 5ZnO–5Fe2O3–90SiO2 sample the nanoparticles exhibited ferro or ferrimagnetic interactions combined with superparamagnetism with a blocking temperature of approximately 14 K. Heating at 800 °C seems to cause partial dissolution of the zinc ferrite and hematite particles in all the investigated compositions. Accordingly at 800 °C the 5ZnO–5Fe2O3–90SiO2 glass shows a paramagnetic behavior down to 2 K.  相似文献   

18.
In the present work, the solubility of tin dioxide is assessed as a function of time, temperature and basicity in simple ternary glasses: NC3S, NC4S, NC5S and NC6S (N: Na2O, C: CaO, S: SiO2). An increase of silica contents in the glass composition leads indeed to a decrease of the glass basicity. First, a kinetic study of the dissolution has been performed. Consequently, the solubility limits of tin dioxide have been determined after 2 h of heat treatment: this duration is long enough to reach the dissolution equilibrium, and short enough to limit the sodium oxide losses in the melt at high temperatures. Nevertheless the specific case of the most acid glass has been underlined, as its higher viscosity implies longer heating times. At equilibrium state, SnO2 solubility depends on the temperature (Arrhenius law) and on the glass basicity. In the 1200 °C–1400 °C temperature range, in these soda–lime glasses, the solubility of tin dioxide is between 1.3 and 2.1 at.% Sn and the temperature dependence of solubility exhibits a single mechanism of dissolution. Furthermore, the basicity dependence of the solubilization process is also discussed, and the presence of another oxidation state of tin (SnII) is thus proposed.  相似文献   

19.
《Journal of Non》2006,352(50-51):5309-5317
Three series of phosphate glasses were produced by melting together sodium phosphate salt (NaH2PO4) and the phosphate salts of either calcium (CaHPO4), magnesium (MgHPO4 · 3H2O) or iron (FePO4 · 2H2O) in a 5% gold/95% platinum crucible at 1200 °C. The glass compositions were confirmed by EDX and XRD analysis. Glass transition temperature (Tg), density and durability in water were determined for all the compositions. Maximum metal oxide contents before devitrification were between 55% and 59% for CaO + Na2O and 59% and 62% for MgO + Na2O. The normalized equivalent for Fe2O3 + Na2O was between 55% and 61%. Density values for the glasses lay between 2.49 and 2.75 g cm−3. Tgs lay between 295 °C and 470 °C. Degradation rates in deionized water at 37 °C lay between 0.03 g cm−2 h−1 for Na phosphate glasses and 9 × 10−6 g cm−2 h−1 for Ca phosphate glasses, 3 × 10−6 g cm−2 h−1 for Mg phosphate glasses and <3 × 10−6 g cm−2 h−1 for Fe phosphate glasses. The effect of metal addition on properties goes as Fe > Mg > Ca for degradation rates and Tg and Fe > Mg  Ca for density. The change in properties with metal addition was seen to be linear for Fe and Ca additions but not with Mg addition. This is in agreement with the anomalous behavior of magnesium phosphate glasses.  相似文献   

20.
《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   

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