Thermal properties of oxide glasses

A criterion based on the length of induction period of crystallization was used to study the effect of added CoO and NiO oxides on the thermal stability of Li₂O·2SiO₂ glass system against crystallization. It was found out that the thermal stability of studied glasses against crystallization is Li₂O·2SiO₂ < Li₂O·2SiO₂·0.1CoO < Li₂O·2SiO₂·0.1NiO. The addition of CoO and NiO oxides to Li₂O·2SiO₂ glass system increases its thermal stability. These results coincide with the order determined by stability criteria based on the characteristic temperatures.     

Thermal stability of Li2O-SiO2-CaO-P2O5-F glass

Two glasses, the first one with the composition of Li₂O·2SiO₂ and the second one with the addition of CaO, P₂O₅ and CaF₂ in the stoichiometric ratio corresponding to fluoroapatite were prepared and their tendency to crystallize has been studied by non-isothermal DTA analysis. The values of kinetic parameters calculated using the isoconversional integral method have been used to determine the temperature dependencies of both the length of isothermal induction period and the length of overall isothermal crystallization for both glasses. The estimated dependencies indicate that the glass containing CaO, P₂O₅ and CaF₂ has a lower thermal stability.     

Thermal properties of oxide

To evaluate the thermal stability of oxide glasses, various criteria have been used. Not only the simple parameters, as characteristic temperatures and values of activation energy and enthalpy changes, but also the combined criteria E/RTp and kf(T) have been taken into account. Three glasses with the composition of Li₂O·2SiO₂ (a), Li₂O_·2SiO₂·0.03TiO₂ (b) and Li₂O·2SiO₂·0.1TiO₂ (c) were prepared and the validity of the criteria was tested by applying them to these glasses. The results indicate that the sequence thermal stability of the studied glass system vs. crystallization depends not only on their composition but also on the used criteria. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal properties of oxide glasses

Glasses with the composition Li₂O·2SiO₂·nTiO₂ and Li₂O·2SiO₂·nZrO₂, where n=0, 0.03, 0.062, 0.1, were prepared and the onset and peak temperatures have been determined by DTA. From these characteristic temperatures, the kinetic parameters describing the nucleation and crystal growth have been obtained by isoconversional methods. The kinetic parameters have been used for the calculation of nucleation and crystal growth times for individual glasses so determining the order of glass stability at reheating. The stability of glasses increases with the content of TiO₂ or ZrO₂ where the increase is higher for ZrO₂. Within the concentration range under study, the increase of both times with the metal oxide concentration is quadratic. It has been discussed that the crystallization kinetics does not obey the Arrhenius law and, therefore, when using the evaluation methods based on this law, the results should not be extrapolated outside the temperature range of the measurements.     

Thermal stability of Li2O–SiO2–TiO2 gels evaluated by the induction period of crystallization

To evaluate the thermal stability of materials, various criteria have been used. Not only the simple parameters, as characteristic temperatures, but also the combined criteria E/RT _p , k _f (T) and criterion based on the length of induction period of crystallization have been taken into account. Four gels with the composition Li₂O–2SiO₂–nTiO₂ (n = 0.00, 0.03, 0.062, and 0.1) were prepared and the validity of the criteria was tested by applying them to these gels. The results indicate that thermal stability of the studied gels decrease with amount of TiO₂.     

Effect of molybdenum addition on the thermal properties of silicate–phosphate glasses

Aim of the study was analysis of two groups of glasses: silicate?Cphosphate (41?mol.% SiO₂?C6?mol.% P₂O₅) and with inverse phosphate?Csilicate matrix (41?mol.% P₂O₅?C6?mol.% SiO₂) modified by the addition of molybdenum ions. Their effect on glass forming ability, glass transition effect, crystallization process, and kind of crystallizing phases was examined using such methods as DSC, XRD, and SEM. It was found that the solubility limit of MoO₃ in silicate?Cphosphate glasses is 4.4?<?[MoO₃]?<?5.7?mol.%, whereas in phosphate?Csilicate glasses MoO₃ is fully dissolved. It was found that in the case of both matrixes addition of molybdenum ions decreases the glass transition temperature (T _g), as well as the value of specific heat change (?c _p ) accompanying the glass transformation. The presence of molybdenum caused reduced the thermal stability of the studied glasses and a multi-step crystallization of silicate?Cphosphate glasses. It was found that the crystallizing phases were silicates and phosphates in both groups of glasses. Only in the case of silicate?Cphosphate glasses containing MoO₃ in an amount ??3.3?mol.% one of the crystallization product was powellite (CaMoO₄). The nature of transitions taking place during heating of the analyzed glasses was in accordance with crystallochemical factors (strengths of bonds) and chemical affinity of the glass components (?G formation).     

Study of crystallization process of soda lead silicate glasses by thermal and spectroscopic methods

The crystallization process of some glasses in the ternary Na₂O–SiO₂–PbO system with good chemical stability that can be used for waste inertization was studied using X-ray diffraction (XRD), infrared spectroscopy (FT-IR), differential thermal analysis (DTA) and scanning electron microscopy. The parent glasses were characterized by XRD and FT-IR, and their vitreous state was determined. DTA measurements evidenced glass transition (T _g) and crystallization temperatures (T _c). The thermal treatments were conducted at vitreous transition temperature (400 °C) and at highest effect of crystallization (650 °C). XRD evidenced the lead and sodium silicate crystalline phases in samples treated at 650 °C for 12 h. Micrometer crystallites dispersed in the glass matrices have affected the transparence of glasses and made them opaque after treatment at 650 °C. The influence of oxide quantities in compositions on the crystallization tendency was revealed. A PbO higher content than that of SiO₂ as well as lower Na₂O content decreased the tendency of crystallization.     

Structure of Na2O–MgO–CaO–SiO2 glasses by combined Raman spectroscopy and thermodynamic modeling approach

The present contribution deals with the Raman spectra and structure of Na₂O–MgO–CaO–SiO₂ glasses. Six glasses with the trisilicate overall composition 15Na₂O·xMgO·(10–x)CaO·75SiO₂ (x = 0, 2, 4, 6, 8, 10) were studied. The structure of studied glasses was described by the thermodynamic model of Shakhmatkin and Vedishcheva. From the 27 components with the stoichiometry given by the composition of stable crystalline phases, only eight were found in significant abundance in the studied glasses—namely: SiO₂, 2MgO·SiO₂ (M2S), MgO·SiO₂ (MS), Na₂O·3CaO·6SiO₂ (NC3S6), Na₂O·CaO·5SiO₂ (NCS5), Na₂O·MgO·4SiO₂ (NMS4), Na₂O·SiO₂ (NS), and Na₂O·2SiO₂ (NS2). The correlation analysis points out that the strong positive correlations between the equilibrium molar amounts of: {M2S–MS–SiO₂}, {NC3S6–NCS5}, and {NMS4–NS–NS2}. From the components of significant abundance, only the content of MS and NC3S6 change significantly within the studied compositional series. These two components were identified with the result of the principal component analysis of Raman spectra that indicated the presence of two independent spectral components. Using the method of Malfait the partial Raman spectra of MS and NC3S6 components were found. The obtained results very well reproduce the experimental Raman spectra and confirmed in such way the thermodynamic model.     

Thermal study of Mn-containing silicate–phosphate glasses

Silicate-phosphate glasses of SiO₂–P₂O₅–K₂O–MgO–CaO system containing manganese cations were investigated to obtain information about the influence of manganese ions on the thermal behavior of such glasses. Amorphous state of glasses and the course of phase transformation and crystallization taking place during their heating were investigated by DSC, XRD, and FTIR methods. It was shown that an increasing content of manganese replacing calcium and magnesium in the structure of analyzed glasses causes decrease of glass transition temperature (T _g) and heat capacity change (Δc _p) accompanying the glass transformation. Simultaneously, thermal stability of the glasses increased. Products of multistage crystallization of glasses containing up to 8 mol% of MnO₂ were: marokite (CaMn₂O₄), phosphate of Ca₉MgK(PO₄)₇ type, and diopside (CaMgSi₂O₆). Product of crystallization of glasses containing higher amount of manganese was braunite (Mn₇O₈SiO₄). This was accompanied by change of structure of magnesium calcium silicates from diopside-type structure to akermanite-type silicates (Ca₂MgSi₂O₇). The data interpretation was based on bonds and chemical interactions of the individual components forming the glass structure.     

Evaluation of the stability of substituted InF3 glasses by differential thermal analysis

The thermal properties and devitrification behaviour of substituted InF₃ glasses were studied by means of differential thermal analysis. A comparison of various simple quantitative methods to assess the level of stability of multicomponent fluoride glass systems was also made. Most of these methods are based on critical temperatures. In this paper, a new parameter,k _d(T), is introduced to the stability criteria. The stabilities of several substituted InF₃ glasses were evaluated experimentally and correlated with the activation energies of crystallization via this new kinetic criterion and compared with those evaluated by other criteria.     

57Fe-Mössbauer study of electrically conductive alkaline iron vanadate glasses

A relationship between local structure, thermal stability and electrical conductivity (σ) of xR₂O·10Fe₂O₃·(90 ? x)V₂O₅ glasses (abbreviated as xRFV glasses, where R = Li, Na, K; x = 20 and 40 in mol %) was investigated by ⁵⁷Fe-Mössbauer spectroscopy, X-ray diffractometry, differential thermal analysis (DTA) and DC two- and four-probe method. From DTA study, thermal stability of 20RFV glasses is lower than that of 40RFV glasses by evaluating Hruby parameter (K _gl). Constant activation energy for crystallization (E _a) of 2.5 eV obtained from both 20RFV and 40RFV glasses indicate that the crystallization proceeds with the cleavage of Fe–O bond having the energy of 2.6 eV. Isochronally annealed 20RFV glass at 400–450 °C resulted in the increase in electrical conductivity (σ) from the order of 10^?3 to 10^?1 S cm^?1, whereas slight decrease in σ was observed for 20RFV glass annealed above 460 °C. A paramagnetic doublet with an identical isomer shift (δ) of 0.39 mm s^?1 was observed in the ⁵⁷Fe-Mössbauer spectra of 20RFV glass after isothermal annealing conducted at 400–450 °C for 100 min, which caused a decrease of quadruple splitting (Δ) from 0.67 to 0.52 mm s^?1 for 20LiFV glass and from 0.66 to 0.53 mm s^?1 for 20NaFV glass. On the other hand, three paramagnetic doublets with δ and Δ of 0.40 and 0.25, 0.38 and 0.60, and 0.31 and 1.11 mm s^?1 respectively were observed for 20RFV glass annealed at 460–550 °C, reflecting precipitation of semiconducting FeVO₄ phase having σ of 6.0 × 10^?7 S cm^?1. It can be concluded that isochronal annealing of 20RFV glass below 450 °C resulted in increase in σ due to the structural relaxation, while annealing above 500 °C resulted in the decrease of σ due to the precipitation of FeVO₄ phase.     

Application of heating microscopy to the study of thermal behaviour of ZnO–P2O5–WO3 glasses

The effect of WO₃ on thermal behaviour and thermal stability of ZnO–P₂O₅–WO₃ glasses prepared in compositional series (100 ? x)[0.5ZnO–0.5P₂O₅] ? xWO₃ (x = 0–60) was investigated by heating microscopy and the results were correlated with the results determined by conventional thermodilatometry and differential thermal analysis. Thermoanalytical studies showed that the glass transformation temperature and dilatation softening temperature increase with increasing WO₃ content while thermal expansion coefficient decreases. The highest stability towards crystallization possess glasses containing 20–30 mol% WO₃. Major compounds formed by the crystallization of the glasses were Zn(PO₃)₂, WO₃ and W₁₈P₂O₅₉. The values of sphere temperature, hemisphere temperature and flow temperature obtained using heating microscopy were strongly influenced by the degree of crystallization process at the sintering.     

All-solid-state batteries with Li2O-Li2S-P2S5 glass electrolytes synthesized by two-step mechanical milling

Sulfide solid electrolytes, which show high ion conductivity, are anticipated for use as electrolyte materials for all-solid-state batteries. One drawback of sulfide solid electrolytes is their low chemical stability in air. They are hydrolyzed by moisture and generate H₂S gas. Substituting oxygen atoms for sulfur atoms in sulfide solid electrolytes is effective for suppression of H₂S gas generation in air. Especially, the xLi₂O·(75-x)Li₂S·25P₂S₅ (mol%) glasses hardly generated H₂S gas in air. However, substituting oxygen atoms for sulfur atoms caused a decrease in conductivity. The x?=?7 glass showed high chemical stability in air and maintained high conductivity of 2.5?×?10^?4 S cm^?1 at room temperature. Performance of cells using the 7Li₂O·68Li₂S·25P₂S₅ and the 75Li₂S·25P₂S₅ glasses as solid electrolytes were compared. All-solid-state C/LiCoO₂ cell using the 7Li₂O·68Li₂S·25P₂S₅ glass produced performance as good as that obtained using the 75Li₂S·25P₂S₅ glass. Capacity retention and change of interfacial resistance of the former cell were superior to those of the latter cell after storage at 4.0 V and 60 °C. The diffusion of oxygen element into the 7Li₂O·68Li₂S·25P₂S₅ glass was less than that into the 75Li₂S·25P₂S₅ glass after storage at the voltage of 4.0 V at 60 °C. Improvement of the stability of sulfide solid electrolytes to moisture was related to cell performance as well as an increase in conductivity.     

Influence of thermal stability on dielectric properties of SiO<Subscript>2</Subscript>–K<Subscript>2</Subscript>O–CaO–MgO glasses

Compositions of 55SiO₂–10K₂O–(35–x)CaO–xMgO are prepared by melt and quench technique. Thermal parameters of the as-prepared glasses are studied using the differential thermal analyzer under non-isothermal conditions. Kissinger, Augis–Bennett and Lasocka models are employed to investigate the kinetics of crystallization and thermal stability of these glasses. Based on this, it is concluded that CM-15 glass exhibits highest thermal stability. Raman spectroscopy is used to reveal the structural units of the glasses. Dielectric properties are observed through impedance spectroscopy. All the glasses are phase separated. The ratio of CaO/MgO influences the thermal stability, which leads to affect the dielectric properties. The highest dielectric permittivity is observed ~22 at room temperature and 100 Hz for CM-15 glass, where CaO/MgO ratio is ~1.33.     

Kinetics of the pyrolysis and combustion of göynük oil shale

Thermal behaviour of the glass series (100–y)[0.5ZnO·0.1B₂O₃·0.4P₂O₅]·yTiO₂ (with y=0–39 mol% TiO₂) was investigated by DSC and TMA. The addition of TiO₂ results in a non-linear increase of glass transition temperature. The compositional dependences of thermal stability, evaluated by two criteria exhibit two maxima for the glasses doped with 10.7 and 35.9 mol% TiO₂. All the glasses crystallize on heating in the temperature range of 576–670°C. The crystallization mechanism was studied at the glasses with 19.4 and 35.9 mol% TiO₂ and the results showed that surface nucleation mechanism prevails in these glasses over the internal one.     

IR spectroscopic investigations on the determination of the water content in glasses

The IR spectra of glasses of the composition 16 Cs₂O?·?10 CaO?·?74 SiO₂ with different water contents were measured and quantitatively analyzed with regard to the water content. Nuclear reaction analysis (NRA) was used for calibration. The practical extinction coefficients were determined for the OH vibrational bands at 3500 and 2800 cm^–1. The two-band method of Scholze was applied to IR spectra of three different alkali lime silica glasses containing Na⁺, K⁺, or Cs⁺ as network modifier cations. After correcting the extinction coefficients, this method is very suitable for determination of total water concentrations in glasses.     

The vitrification of alkali borate and alkali silicate melts

Glasses and crystals of compositions corresponding to the congruently melting compounds M₂O·2SiO₂ (M = Na. Rb, and Cs) and M₂O·4SiO₂ (M = K, Rb, and Cs) were studied by differential scanning calorimetry. The structure temperatures (T _f) and excess entropies at T _f of glasses were measured depending on the rate of cooling of the corresponding melts. The activation energies of glass formation (ΔE) and scale of cooperative motion in the transition region (ξ_a) were estimated. The totality of the data obtained were used to compare the thermodynamic (the ratio between the excess (with respect to the corresponding crystals) entropy of glass at T _f and the entropy of crystal melting), kinetic (fragility m = f(ΔE, T _f)), and microscopic (ξ_a) parameters of the vitrification of alkali silicate melts. The behaviors of alkali silicate and alkali borate melts were shown to be similar.     

Thermal behaviour and excess entropy of bioactive glasses and Zn-doped glasses

Bioactive glasses prepared in SiO₂–CaO–Na₂O and P₂O₅ system are used as biomaterials in orthopaedic and maxillofacial surgery. Zn presents high physiological interest. It enhances physiological effects of implanted biomaterials. In this work, the thermal characteristics (T _g, T _c and T _f) of pure bioactive glass elaborated with different amounts of CaO, Na₂O in pure glass and with different amounts of introduced Zn in glass (ranging from 0.1 to 10 in mass%), were studied. The excess entropy was calculated for different compounds. Glasses were prepared by the melting process. The thermal behaviour of obtained bioactive glasses was determined using differential thermal analysis. Therefore, the glass transition (T _g), the crystallization (T _c) and the melting temperatures (T _f) were revealed. Moreover, according to Dietzel formula, the thermal stability (TS) of the studied bioactive glasses has been calculated. The first results concerning the impact of different oxides, revealed a decrease of the TS, T _g, T _c and T _f when the SiO₂/CaO increases and revealed an increase of these thermal characteristics when the SiO₂/Na₂O and CaO/Na₂O ratios increase. Introducing Zn into the bioactive glasses induces a decrease of T _f and an increase of TS. Contrary to crystals, prepared glasses have entropy different to zero at T = 0 K and vary versus T _f. The excess entropy of pure glasses and Zn-doped glasses were calculated. The significant variations were registered.     

Direct crystallization of silicate–phosphate glasses of NaCaPO4–SiO2 system

The subject of the study was silicate–phosphate glasses of NaCaPO₄–SiO₂ system which are precursors of glass–crystalline materials. Glass–crystalline materials of NaCaPO₄–SiO₂ system obtained via crystallization of glasses belong to a group of the so-called bioactive materials. In order to obtain glass–crystalline materials with pre-established parameters, it is necessary to conduct crystallization of glasses at specific conditions. In order to design direct crystallization process properly, it is necessary to know the structure and microstructure of the glassy precursor. Microscopic investigation showed that liquation takes place in all the studied glasses. Based on DSC examinations, it has been found out that crystallization of the glasses of NaCaPO₄–SiO₂ system is a multistep process. The presence of several clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the separated phase with the matrix remaining amorphous or vice versa. Conducted detailed X-ray and spectroscopic studies of the materials obtained by heating in a gradient furnace (in the temperature specified on the basis of DSC) showed that separated phase and matrix crystallizes separately. Therefore, bioactive glass–crystalline materials can be obtained due to the existence of the phase separation phenomenon and pre-established sizes of the crystalline phase.