The role of P2O5, TiO2 and ZrO2 as nucleating agents on microstructure and crystallization behaviour of lithium disilicate-based glass

The aim of this study was to investigate the effects of different nucleating agents (P₂O₅, TiO₂ and ZrO₂) on the crystallization behaviour and the properties of a parent glass with composition 23.7 Li₂O–2.63 K₂O–2.63 Al₂O₃–71.78 SiO₂ (mol%) and SiO₂/Li₂O molar ratio far beyond that of stoichiometric lithium disilicate (LD, Li₂Si₂O₅). The scanning electron microscopy examination of the as-cast non-annealed glasses revealed the occurrence of liquid–liquid phase separation for all the compositions. P₂O₅ revealed to be effective in promoting bulk crystallization of LD, while TiO₂ and ZrO₂ led to surface crystallization. Moreover, ZrO₂ enhances the glass polymerization and shifts T _p to higher temperatures, hindering crystallization. At 900 °C, TiO₂-containing glasses feature LD and lithium metasilicate (LMS, Li₂SiO₃), while P₂O₅- and ZrO₂-containing ones present monophasic LD and LMS glass–ceramics, respectively.     

Crystalline phase formation, microstructure and mechanical properties of a lithium disilicate glass–ceramic

In this work, crystalline phase formation, microstructure and mechanical properties of a lithium disilicate (LS2, Li₂Si₂O₅) glass–ceramic in the SiO₂–Li₂O–Al₂O₃–P₂O₅ system were investigated. A four-stage heat treatment process was used for crystallization of the glass. The effects of holding time and temperature at the final stage on the crystalline morphology of the glass–ceramic were studied. The experimental results revealed the two crystallization peaks at 672 and 839 °C. At a temperature lower than 770 °C and holding time of 20 min, the lithium metasilicate (Li₂SiO₃) phase dominates. On the other hand, when the glass was heated to a higher temperature or held for a longer time, the LS2 phase dominates and some other minor phases such as cristobalite and lithium phosphate emerge. Scanning electron microscopy and energy dispersive spectrometry revealed a large number of nanosized ZrO₂ particles when the crystallization temperature was above 790 °C. Vickers hardness of the LS2 glass–ceramic was about 8.1–8.4 GPa and flexural strength was in the range of 282–307 MPa. Crack deflection was observed along the LS2 cluster boundaries. The crystallization sequence was proposed to explain the observed microstructure and phases.     

Suppression of H2S gas generation from the 75Li2S·25P2S5 glass electrolyte by additives

Solid electrolytes in the system Li₂S–P₂S₅ are attractive for all-solid-state lithium batteries since the electrolytes have high lithium ion conductivities and wide electrochemical windows. In particular, the 75Li₂S·25P₂S₅ (mol%) glass showed the highest stability to moisture in the system Li₂S–P₂S₅ because the amount of H₂S gas generated from the glass was the smallest in the system Li₂S–P₂S₅. In this study, several additives such as metal sulfides and metal oxides (FeS, CuO, etc.) were mixed with the 75Li₂S·25P₂S₅ glass in order to suppress H₂S gas generation from the sulfide glasses in air. The addition of more than 30 mol% FeS greatly decreased H₂S gas generation from the sulfide glass in air. In the case of the FeS addition, sulfur crystal was precipitated and the 75Li₂S·25P₂S₅ glass changed to Li₃PO₄ crystal after a reaction with water. On the other hand, the addition of 30 mol% CuO dramatically decreased H₂S gas generation from the sulfide glass in air. In the case of the CuO addition, Cu₃PS₄ crystal was precipitated after the reaction with water. Furthermore, the 75Li₂S·25P₂S₅ glass added with 30 mol% FeS or CuO showed relatively high conductivities of more than 10^?4 S cm^?1 at room temperature. Therefore, the 75Li₂S·25P₂S₅ glass added with FeS or CuO was expected to be a suitable solid electrolyte material for all-solid-state batteries.     

Effects of P2O5 on sinterability, microstructures and properties of glass/alumina composites

We prepared the low-temperature fired glass/alumina composites and investigated the influence of P₂O₅ on the sinterability, microstructure, dielectric property, and mechanical strength. The result showed that although the nucleating agent P₂O₅ can promote the crystallization of CaO-B₂O₃-SiO₂ (CBS) glass, excessive P₂O₅ have negative effects on the sintering behavior of composites. Because the density decreases gradually with increasing P₂O₅ addition, the dielectric and mechanical properties deteriorate dramatically. The densification mechanism via P₂O₅ modification is revealed further. Due to the crystallization effect of P₂O₅, the increase in viscosity impedes the flowability and wettability of liquid glass, which partly inhibits the liquid-phase sintering. 2 mol% P₂O₅-added CBS glass/alumina composite achieves densification at 900 °C (2.79 g/cm³) and exhibits good performances: low dielectric constant (5.84), low dielectric loss (1.17 × 10^?3), and high flexural strength (166 MPa).     

Preparation and structural studies in the (70 − x)TeO2–20WO3–10Li2O–xLn2O3 glasses

Quaternary tellurite glass systems (70 ? x)TeO₂–20WO₃–10Li₂O–xLn₂O₃ where x = 0, 1, 3 and 5 mol% and Ln are La, Pr, Nd, Sm, Er and Yb, respectively, have been prepared by the melt quenching technique. Densities of the obtained glasses were measured and the molar volume was calculated. IR absorption spectra of the present glass systems were determined at room temperature over the range of wavenumbers from 400–1,600 cm^?1. Raman spectra of the present glass samples were measured in the range of 30–1,030 cm^?1. Density, molar volume, IR and Raman spectra of the glasses were discussed by calculating average cross-link density, packing density, theoretically calculated Poisson’s ratio and number of bonds per unit volume of the studied glasses. Also, the quantitative interpretations were based on concentration of ions per unit volume of Te, Ln and O, short distance in nanometre between ions for (Te–O) of TeO₄ and TeO₃ groups, (W–O) of WO₄, WO₆ groups and calculated wavenumber, $ \bar{\upsilon } $ , for TeO₄ and TeO₃, respectively. The average stretching force constant that present in these quaternary glasses has been calculated in order to interpret the data obtained.     

Subsolidus phase relations of Li2O–FeO–P2O5 system and the solid solubility of Li1+x Fe1−x PO4 compounds under Ar/H2 atmosphere

The phase relation of Li₂O–FeO–P₂O₅ ternary system under the 95 %Ar + 5 %H₂ atmosphere has been systematically investigated by X-ray diffraction (XRD), and there exist 8 binary compounds, 4 ternary compounds, 2 two-phase regions, and 17 three-phase regions. No other new lithium ferrous phosphates can be existed in the Li₂O–FeO–P₂O₅ ternary system under the 95 %Ar + 5 %H₂ atmosphere. In this system, the Li_1+x Fe_1?x PO₄ solid solution phase with the homogeneous range of ?0.15 ≤ x ≤ 0.06 is determined. Their corresponding lattice parameters are obtained by the refinement results, and the results show that the lattice parameters (a, b, c, V) vary linearly with the increasing amount of excess Li-ion (x > 0) or with the increasing amount of excess Fe-ion (x < 0). The phase diagram determined in this paper can provide more information about the phase relation of Li₂O–FeO–P₂O₅ ternary system and serve as a guide for the future investigation of lithium iron phosphates in this system.     

Formation of Li<Superscript>+</Superscript> superionic crystals from the Li<Subscript>2</Subscript>S–P<Subscript>2</Subscript>S<Subscript>5</Subscript> melt-quenched glasses

The 70Li₂S·30P₂S₅ (mol%) glass was prepared by the melt quenching method and the glass–ceramic electrolytes were obtained by heating the prepared glass over crystallization temperatures. The superionic metastable Li₇P₃S₁₁ crystal was formed by heating the glass in the temperature range from 280 and 360 °C. The conductivity of the glass–ceramics was enhanced by the precipitation and growth of the Li₇P₃S₁₁ crystal, and the highest conductivity of 4.1 × 10⁻³ S cm⁻¹ at room temperature was achieved in the glass–ceramic heated at 360 °C for 1 h. The Li₇P₃S₁₁ crystal changed into the thermodynamically stable phase such as the Li₄P₂S₆ crystal with further increasing heat treatment temperature and holding time, resulting in lowering conductivities of the glass–ceramics.     

Low temperature cofirable Li2Zn3Ti4O12 microwave dielectric ceramic with Li2O–ZnO–B2O3 glass additive

The effects of Li₂O–ZnO–B₂O₃ (LZB) glass additive on the sintering behavior, phase composition, microstructure and microwave dielectric properties of Li₂Zn₃Ti₄O₁₂ ceramics were investigated. The addition of a small amount of LZB glass can reduce the sintering temperature of Li₂Zn₃Ti₄O₁₂ ceramics from 1,075 to 900 °C without much degradation of the microwave dielectric properties. Only a single-phase Li₂Zn₃Ti₄O₁₂ is formed in Li₂Zn₃Ti₄O₁₂ ceramic with LZB addition. Typically, the 1.5 wt% LZB glass-added Li₂Zn₃Ti₄O₁₂ ceramic sintered at 900 °C for 2 h can reach a high relative density of 97.5 % and exhibits good microwave dielectric properties, i.e., relative dielectric constant (ε _r ) = 19.1, quality factor (Q) = 7083.5 at 9 GHz, and temperature coefficient of resonant frequency (τ _f ) = ? 48.9 ppm/°C. In addition, the ceramic could be co-fired well with an Ag electrode, which is made it as a promising dielectric ceramic for low temperature co-fired ceramics technology application.     

Domaine vitreux,structure et conductivite electrique des verres du systeme LiCl /1b Li2O /1b P2O5

The glass forming region in the LiCl /1b Li₂O /1b P₂O₅ system was determined. Glass transition temperature was obtained from differential thermal analysis studies. The determination of the electrical conductivity as a function of the temperature and the composition in Li₂O and LiCl was carried out. The conductivity reaches a maximum value of the order of 5·10^?7 (ohm^?1·cm^?1) at 25° C. Raman spectra are examined in order to show the influence of the composition on the vitreous structure.     

Ionic conductivity of Li4GeO4, Li2GeO3 and Li2Ge7O15

The ionic conductivity of polycrystalline samples of three lithium germanates: Li₄GeO₄, Li₂GeO₃, and Li₂Ge₇O₁₅, has been determined using a c techniques and complex plane analysis. Conductivities at 400°C are 8.7 × 10^?5, 1.5 × 10^?5, and $\text{1.4 × 10}{}^{\mathrm{?7}}\text{(Ω·}\text{cm}\text{)}{}^{\mathrm{?1}}$ respectively. The conductivity of Li₄GeO₄ rises appreciably in the range 700–750°C.     

Anisotropy of acousto–optic figure of merit in lithium tetraborate crystals

We analyse anisotropy of acousto–optic figure of merit (AOFM) for Li₂B₄O₇ crystals in order to estimate the prospects of these crystals in acousto–optics. We find that the maximal AOFM, 3.44 × 10^?15 s³/kg, is peculiar for the isotropic acousto–optic interaction of the incident ordinary optical wave with the quasi-longitudinal acoustic wave. For the case of anisotropic diffraction in Li₂B₄O₇, the maximum 1.87 × 10^?15 s³/kg can be reached using the interaction of the extraordinary optical wave with the quasi-longitudinal acoustic wave. The case of collinear diffraction is characterized by small AOFMs, with the largest value 0.26 × 10^?15 s³/kg.     

Sintering, densification and crystallization of Ca–Al–B–Si–O glass/Al2O3 composites for LTCC application

Ca–Al–B–Si–O glass/Al₂O₃ composites were prepared based on the borosilicate glass powders (D₅₀ = 2.84) and Al₂O₃ ceramic powders (D₅₀ = 3.26), and the sintering, densification, crystallization of samples were investigated. The shrinkage of sample starts to have a sharp increase at 600 °C. The shrinkage of sample starts to have a further rapid increase after the glass softening temperature of about 713 °C. Glass/Al₂O₃ composites can be sintered at 875 °C/15 min and exhibit better properties of a relative density of 98.4 %, a λ value of 2.89 W/mK, a ε _r value of 7.82 and a tan δ value of 5.3 × 10^?4. The interface between glass and Al₂O₃ grains and the interface between anorthite and glass phase depicts a good compatibility according to transmission electron microcopy test. It is the low sintering temperature, high density and good compatibility with Ag electrodes that, guarantee borosilicate glass/Al₂O₃ composites suitable for low temperature co-fired ceramic materials.     

Effect of annealing pressure on structure and properties of ferroelectric Bi3.25La0.75Ti3O12 thin films prepared by sol�Cgel method

The effect of annealing pressure was investigated for Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films prepared on Pt/TiO₂/SiO₂/p-Si(100) substrates by sol?Cgel method. The amorphous films were annealed at 750 °C for 30 min under different oxygen pressures varying from 10^?4 to 3 atm. The largest P _r of 17.8 ??C/cm² with the E _c of 73.6 kV/cm was obtained for the film annealed under 0.1 atm P_O2. Then the structure, crystallization degree, and morphology were characterized by X-ray diffraction (XRD), Raman spectroscopy, and field-emission scanning electron microscope (FSEM) to clarify the effect of annealing pressure on the ferroelectric properties. The XRD and Raman spectroscopy results indicated a clear decreasing of the crystallization degree of the films annealed under 10^?4 and 3 atm P_O2. FSEM results showed the different growth orientation of grains under different oxygen pressures. This study indicated some important effects of annealing pressure on the physical properties of BLT thin films.     

Structural relaxation and electrical conductivity of molybdovanadate glass

⁵⁷Fe Mössbauer spectrum of conductive barium iron vanadate glass with a composition of 20BaO·10Fe₂O₃·70V₂O₅ (in mol%) showed paramagnetic doublet peak due to distorted Fe^IIIO₄ tetrahedra with isomer shift (δ) value of 0.37 (±?0.01) mm s^?1. Mössbauer spectra of 20BaO·10Fe₂O₃·xMoO₃·(70???x)V₂O₅ glasses (x?=?20–50) showed paramagnetic doublet peaks due to distorted Fe^IIIO₆ octahedra with δ’s of 0.40–0.41 (±?0.01) mm s^?1. These results evidently show a composition-dependent change of the 3D-skeleton structure from “vanadate glass” phase, composed of distorted VO₄ tetrahedra and VO₅ pyramids, to “molybdate glass” composed of distorted MoO₆ octahedra. After isothermal annealing at 500 °C for 60 min, Mössbauer spectra also showed a marked decrease in the quadrupole splitting (Δ) of Fe^III from 0.70 to 0.77 to 0.58–0.62 (±?0.02) mm s^?1, which proved “structural relaxation” of distorted VO₄ tetrahedra which were randomly connected to FeO₄, VO₅, MoO₆, FeO₆ and MoO₄ units by sharing corner oxygen atoms or edges. DC-conductivity (σ) of barium iron vanadate glass (x?=?0) measured at room temperature was 3.2?×?10^?6 S cm^?1, which increased to 3.4?×?10^?1 S cm^?1 after the annealing at 500 °C for 60 min. The σ’s of as-cast molybdovanadate glasses with x’s of 20–50 were ca. 1.1?×?10^?7 or 1.2?×?10^?7S cm^?1, which increased to 2.1?×?10^?2 (x?=?20), 6.7?×?10^?3 (x?=?35) and 1.9?×?10^?4 S cm^?1 (x?=?50) after the annealing at 500 °C for 60 min. It was concluded that the structural relaxation of distorted VO₄ tetrahedra was directly related to the marked increase in the σ, as generally observed in several vanadate glasses.     

Effect of borosilicate glasses on the microwave dielectric properties of ZnO–Nb2O5–Ta2O5 system

(1 ? y)[0.5ZnNb₂O₆–0.5Zn₃Nb₂O₈]–yZnTa₂O₆ with y = 0.91 (ZNT) ceramic have been prepared by conventional solid state ceramic route. The effect of glass additives on the microstructure, densification, and microwave dielectric properties of the ZNT ceramic for low temperature co-fired ceramic applications was investigated. Different weight percentages of quenched glass such as ZnO–B₂O₃–SiO₂, BaO–B₂O₃–SiO₂, LiO–B₂O₃–SiO₂ and MgO–B₂O₃–SiO₂ were added to ZNT powder. The crystal structure of the ceramic–glass composites was studied by X-ray diffraction and microstructure by scanning electron microscopy. The microwave dielectric properties such as relative permittivity (ε_r), quality factor (Q_uxf) and co-efficient of temperature variation of resonant frequency (τ_f) of the ceramics have been measured in the frequency range 4–6 GHz. The 5 wt% ZnO–B₂O₃–SiO₂ added ZNT ceramic sintered at 900 °C showed: ε_r = 28.1, Q_uxf = 32820 GHz (at 4.92 GHz), and τ_f = ?7.7 ppm/^oC respectively.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Microwave dielectric properties and low temperature firing of (1 − x)Li2Zn3Ti4O12 –xLi2TiO3 (0.2 ≤ x ≤ 0.8) ceramics with B2O3–CuO addition

In the present work, the (1 ? x)Li₂Zn₃Ti₄O₁₂–xLi₂TiO₃ (0.2 ≤ x ≤0.8) ceramics were prepared via the solid state reaction method. The 0.8Li₂Zn₃Ti₄O₁₂–0.2Li₂TiO₃ ceramic sample sintered at 1,160 °C for 2 h demonstrated high microwave dielectric property with a relative permittivity of 18.0, a high quality factor (Q × f) ~ 100,000 GHz (at 7.2 GHz), and a temperature coefficient of resonant frequency about ?47.8 ppm/°C. With 2.0 wt% 0.4B₂O₃–0.6CuO addition, a relative permittivity of 17.5, a Q × f value of 71,000 GHz and a temperature coefficient of resonant frequency of ?44.4 ppm/^oC can be obtained in 0.8Li₂Zn₃Ti₄O₁₂–0.2Li₂TiO₃ ceramic sintered at 925 °C for 5 h and the chemical compatibility with silver electrode indicates that the ceramics may be a suitable candidate for the low temperature co-fired ceramic technology application.     

Low-temperature sintering and microwave dielectric properties of Li2TiO3 based ceramics

New low sintering temperature and temperature-stable low-loss ceramics based on Li₂TiO₃ with lithium zinc borate (LZB) glass and LiZnNbO₄ doping have been prepared by the conventional solid-state reaction route. The effect of LZB glass addition on the sinterability, phase purity, microstructure, and microwave dielectric properties of Li₂TiO₃ ceramics has been investigated. The XRD results suggest the presence of single Li₂TiO₃ phases for LZB glass-added Li₂TiO₃ ceramics. The addition of LZB glass can effectively lower the sintering temperature to 900 °C, and does not induce much degradation of the microwave dielectric properties. Typically, the 2.0 wt% LZB glass-added ceramic sintered at 900 °C has better microwave dielectric properties of ε_r = 23.2, Q × f = 38,909 GHz, and τ _f  = 30.1 ppm/°C. Meanwhile, LiZnNbO₄ compound is selected to tune the temperature coefficient of resonant frequency (τ _f ) to near zero. It is found that the 2.0 wt% LZB glass-added Li₂TiO₃ ceramics with 35 wt% LiZnNbO₄ sintered at 925 °C have good microwave dielectric properties of ε_r = 20.7, Q × f = 19,366 GHz, τ _f  = ?0.5 ppm/°C, which can find applications in microwave devices that require low sintering temperature.     

Non-isothermal crystallization kinetics of niobium-doped BGO70 glasses

Niobium-doped BGO glass of composition 85[3Bi₂O₃–7GeO₂ (BGO70)]–Nb15 was investigated for its kinetic parameters n and activation energies E _i : i = 1, 2, g of transformations via available models. Two crystallization exothermal peaks were observed for all heating histograms exploiting 5, 10, 15, and 20 K/min heating rates following the glass transition in non-isothermal DTA curves. An exothermal shoulder prior to first crystallization peak P₁ was identified as thermally favorable crystallizing metastable phase Bi₂GeO₅. P₁ was assigned to thermally stable crystal phase Bi₄Ge₃O₁₂. T _g lied between 729 and 731 K ± 4 K; T _p1 varied from 835–855 K ± 2 K, and T _p2 had values 965–986 K ± 2 K. Independent of the model exploited, activation energies E _g, E _p1, and E _p2 were 32.89 ± 3.1, 47.33 ± 0.72, and 62.74 ± 0.72 kcal/mol, respectively. P₁ corresponds to crystalline disks of Bi₄Ge₃O₁₂, and P₂ identified stable phase BGO crystal rods growing inward from the surface imbedded in glass matrix. Niobium doping modified the transformation kinetic parameters n and E _a of the composition by providing a control on growth mechanism for BGO platelets or rods.     

Microstructure and thermoelectric properties of tungsten trioxide ceramics doped with a low amount of terbium dioxide

The effect of the nonstoichiometric compound terbium dioxide (Tb₄O₇) on the thermoelectric properties of tungsten trioxide (WO₃) ceramics was investigated. Among the sintered ceramics, the sample doped with 0.1 mol% Tb₄O₇ showed the maximum grain size and density. Doping with Tb₄O₇ also increased the electrical conductivity (σ) of the ceramics by about two orders of magnitude, and the sample doped with 0.1 mol% Tb₄O₇ showed the highest electrical conductivity. The absolute value of Seebeck coefficient (|S|) of the doped samples increased as well. Consequently, the power factor (σs ²) markedly increased. The sample doped with 2.0 mol% Tb₄O₇ demonstrated the maximum σs ² of 2.88 μW m^?1 K^?2 at 973 K, which was larger than the highest recorded σs ² for WO₃ ceramics (2.71 μW m^?1 K^?2 at 1,023 K). In addition, the low-doped sample (0.1 mol%) exhibited excellent thermoelectric properties.