The state of magnesium in silicate glasses and melts

The properties of silicate glasses and melts containing magnesium are analyzed in comparison with the properties of glasses and melts in which magnesium is replaced by aluminum. In particular, the properties of the glass and the melt of the diopside composition CaMgSi₂O₆ are analyzed in comparison with the properties of the glass and the melt of the anorthite composition CaAl₂Si₂O₈. It is demonstrated that the properties of aluminosilicate and magnesium silicate glasses and melts differ not so strongly as should be expected upon replacement of modifier ions by network-former ions. By using the parameters γ _n characterizing the cation field strength, it is shown that Mg²⁺ cations can fulfill both the function of network formers like Al³⁺ cations and the function of modifiers like Ca²⁺ cations. The degree of depolymerization of the glass and the melt of the composition CaMgSi₂O₆ is estimated to be 0.4–0.5 from the dependences of the change in the relative density (d − d ₀)/d at different pressures on the degree of depolymerization NBO/T (the ratio of the number of nonbridging oxygen atoms to the number of network-former cations) for silicate glasses and the dependence of the isothermal bulk modulus K _t on the quantity NBO/T for silicate melts.     

Crystallization and Nonlinear Optical Properties of Potassium Niobium Silicate Glasses

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.     

Refractive index and compressibility of the KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glass at pressures up to 6.0 GPa

The refractive index of potassium aluminosilicate glass of the KAlSi₃O₈ composition in the pressure range up to 6.0 GPa has been measured using a polarizing interference microscope and an apparatus with diamond anvils. The changes in the relative density, which characterize the compressibility of the K₂O · Al₂O₃ · 6SiO₂ glass, have been estimated in the pressure range under investigation from the measured refractive indices within the framework of the theory of photoelasticity. The results have been compared with the data previously obtained for the Na₂O · Al₂O₃ · 6SiO₂ glass. Although the molar contents of Al₂O₃ and M ₂O (where M = K or Na) are identical in these glasses, the KAlSi₃O₈ glass exhibits a higher compressibility, which agrees with the lower degree of depolymerization of this glass as compared to that observed in the NaAlSi₃O₈ glass. The pressure derivative of the bulk modulus K′ _t , which is calculated from the Birch-Murnaghan equation for the KAlSi₃O₈ glass (K′ _t = 7–9), is higher than that for the NaAlSi₃O₈ glass (K′ _t = 5.5–6.0). An increase in the pressure derivative of the bulk modulus K′ _t upon replacement of the Na⁺ cations by the K⁺ cations is explained by the inhibition of compression of the large K⁺ cations, which are located in cavities and have a considerably larger orbital radius than the Na+ cations. This manifests itself in the fact that the curves describing the dependences of the change in the relative density (d − d0)/d (compressibility) on the pressure P for the KAlSi₃O₈ and NaAlSi₃O₈ glasses converge at pressures above 4.0 GPa.     

On the Possibility of Forming Complexes with the Participation of O2– Ions in Melts and Glasses of the Na2O–SiO2–Cu2O System

The structural role of copper ions in melts (glasses) of the Na₂O–SiO₂–Cu₂O–CuO system is analyzed in the framework of the acid–base concept with due regard for the geometric (the radius ratio for Cu²⁽¹⁾⁺ and O^2– ions) and energy (the mean enthalpies of the Cu²⁽¹⁾⁺–O bonds) factors. It is demonstrated that copper ions in the structure fulfill the function of modifier cations. In these melts, the Cu¹⁺–Cu²⁺ redox equilibrium can be described without regard for the formation of [Cu²⁽¹⁾⁺O_4/2]^2(3)– ionic complexes (which could be incorporated into the structure of silicon–oxygen anions) and [Cu²⁺O _b/k ]^{2 – b/k} polyhedra providing the interaction between Cu²⁺ ions and anions. The influence of the formation of these polyhedra on the redox equilibrium is considered within the formalism of chemical thermodynamics. The composition dependence of the oxygen ion exponent pO is measured by an electromotive force (emf) technique. The ratio between the numbers of copper atoms with different valences is determined by chemical analysis. The experimental data obtained are in agreement with the theoretical inferences.     

Analysis of Regularities in Composition Dependence of the Viscosity for Glass-Forming Oxide Melts: II. Viscosity of Ternary Alkali Aluminosilicate Melts

The data available in the literature on the viscosity of alkali aluminosilicate melts are collected and analyzed using the SciGlass information system. It is established that there are two composition regions in which the composition dependences of the viscosity logarithm at a constant temperature (above 1000°C) are adequately described by linear equations. The largest amount of data is available for the composition region with an alkali oxide concentration exceeding the aluminum oxide concentration ([R ₂O] > [Al₂O₃]). In this region, the viscosity of melts is predominantly affected by two factors, namely, the concentration of alkali oxide uncombined into the alkali aluminate complex and the nature of alkali cations. At a constant concentration of unbound alkali oxide, the replacement of SiO₂ by AlRO₂ is accompanied by a noticeable decrease in the viscosity of lithium aluminosilicate melts, a very weak decrease in the viscosity of sodium aluminosilicate melts, and a considerable increase in the viscosity of potassium aluminosilicate melts. In the second composition region ([R ₂O] < [Al₂O₃]), the replacement of SiO₂ by AlO_1.5 at a constant alkali metal content is attended by a decrease in the viscosity. In this region, the viscosity increases when changing over from Li₂O to K₂O upon complete substitution of one alkali oxide for another. Different variants of structural interpretation of the regularities revealed are discussed.     

Cation field-strength effects on ion irradiation-induced mechanical property changes of borosilicate glass structures

We examine the impact of the glass network-modifier cation field strength (CFS) on ion irradiation-induced mechanical property changes in borosilicate (BS) glasses for the ternary M₂O–B₂O₃–SiO₂ systems with M = {Na, K, Rb} and the quaternary [0.5M₍₂₎O–0.5Na₂O]–B₂O₃–SiO₂ systems with M = {Li, Na, K, Rb Mg, Ca, Sr, Ba}. ¹¹B nuclear magnetic resonance (NMR) experiments on the as-prepared BS glasses yielded the fractional population of four-coordinated B species (B^[4]) out of all {B^[3], B^[4]} groups in the glass network, along with the fraction of B^[4]–O–Si linkages out of all B^[4]–O–Si/B bonds. Both parameters correlated linearly with the (average) CFS of the M⁺ and/or {M⁽²⁾⁺, Na⁺} cations. Both the nanoindentation-derived hardness and Young's modulus values of the glasses reduced upon their irradiation by Si²⁺ ions, with the property deterioration decreasing linearly with increasing M^z+ CFS, that is, for higher M^z+⋅⋅⋅O interaction strength. The irradiation damage of the glass network also increased linearly with the fraction of B^[4]–O–Si linkages, which are the second weakest in the structure after the M^z+⋅⋅⋅O bonds. Our results underscore the advantages of employing BS glasses with high-CFS cations for enhancing the radiation resistance for nuclear waste storage.     

The Viscosity of Molten Material in Pores and Capillary Channels of the Matrix Phase of High-Alumina Castables Employed in Thermal Power Units of Ferrous Metallurgy. 1. Viscosity Analysis of Melts in the CaO – Al2O3 –FeO – Fe2O3 – SiO2 System

A new approach to the viscosity analysis of high-alumina, low-calcium melts of the CaO – Al₂O₃ – FeO – Fe₂O₃ – SiO₂ system is used. A mathematical formalism for handling experimental viscosity data on the CaO – FeO – Fe₂O₃ – SiO₂ system is proposed that allows viscosity of the system to be evaluated within _av = 0.004 Pa · sec in the temperature range of 1500 – 1700°C at concentrations (mol.%) of CaO = 15.3 – 50.3, Fe_xO_y = 2.3 – 38.5, and SiO₂ = 17.7 – 57.7. An equation describing viscosity as a function of temperature is derived. Using this equation, the viscosity of model melts compositionally analogous to the products of interaction between molten slag and the glassy matrix phase of castables employed in thermal power units of ferrous metallurgy is considered.     

Elucidating the Effect of Iron Speciation (Fe2+/Fe3+) on Crystallization Kinetics of Sodium Aluminosilicate Glasses

We report on the influence of Fe₂O₃ on the crystallization kinetics of nepheline (Na₂O·Al₂O₃·2SiO₂)‐based sodium aluminosilicate glasses. A series of glasses with varying Al₂O₃/Fe₂O₃ content were synthesized in the system 25Na₂O–(25–x) Al₂O₃–xFe₂O₃–50SiO₂ (x varies between 0 and 5 mol%) through melt‐quench technique. A systematic set of experiments were performed to elucidate the influence of iron speciation (Fe²⁺/Fe³⁺) on the crystallization kinetics of these glasses including: (1) obtaining the details of nonisothermal crystallization kinetics by differential scanning calorimetry, (2) determining the influence of heat treatment on the structure and iron coordination in glasses by X‐ray photoelectron spectroscopy and wet chemistry, and (3) following the crystalline phase evolution in glasses in air and inert environments by X‐ray diffraction and scanning electron microscopy. The crystallization of two polymorphs of NaAlSiO₄—carnegieite (orthorhombic) and nepheline (hexagonal)—was observed in all the glasses, wherein the incorporation of iron promotes the formation of nepheline over carnegieite while shifting the crystallization mechanism from surface to volume. The influence of environment (air versus inert) and iron content on the crystallization kinetics of these glasses is contextualized from the perspective of the devitrification problem usually observed in sodium‐ and alumina‐rich high level nuclear waste glasses.     

Structure-property relations in crack-resistant alkaline-earth aluminoborosilicate glasses studied by solid state NMR

The effect of the average ionic potential ξ = Ze/r of the network modifier cations on crack initiation resistance (CR) and Young's modulus E has been measured for a series of alkaline-earth aluminoborosilicate glasses with the compositions 60SiO₂–10Al₂O₃–10B₂O₃–(20−x)M₍₂₎O–xM’O (0 ≤ x ≤ 20; M, M’ = Mg, Ca, Sr, Ba, Na). Systematic trends indicating an increase of CR with increasing ionic potential, ξ, have been correlated with structural properties deduced from the NMR interaction parameters in ²⁹Si, ²⁷Al, ²³Na, and ¹¹B solid state NMR. ²⁷Al NMR spectra indicate that the aluminum atoms in these glasses are essentially all four-coordinated, however, the average quadrupolar coupling constant <C_Q> extracted from lineshape analysis increases linearly with increasing average ion potential computed from the cation composition. A similar linear correlation is observed for the average ²⁹Si chemical shift, whereas the fraction of four-coordinate boron decreases linearly with increasing ξ. Altogether the results indicate that in pure alkaline-earth boroaluminosilicate glasses the crack resistance/E-modulus trade-off can be tailored by the alkaline-earth oxide inventory. In contrast, the situation looks more complicated in glasses containing both Na₂O and the alkaline-earth oxides MgO, CaO, SrO, and BaO. For 60SiO₂–10Al₂O₃–10B₂O₃–10MgO–10Na₂O glass, the NMR parameters, interpreted in the context of their correlations with ionic potentials, are consistent with a partial network former role of the MgO component, enhancing crack resistance. Altogether the presence of MgO in aluminoborosilicate glasses helps overcome the trade-off issue between high crack resistance and high elasticity modulus present in borosilicate glasses, thereby offering additional opportunities for the design of glasses that are both very rigid and very crack resistant.     

The mechanism of electrodeposition of acrylic resin on aluminium

A mechanism for the electrodeposition of acrylic resin on aluminium is proposed, based on experimental studies of acid value, anodic gas evaluation and anodic film resistance. The mechanism can be expressed as Alf Al³⁺ + 3e 2Al³⁺ + 3H₂Of Al₂O₃ + 6H⁺ 2Al³⁺ + 6H₂Of 2Al(OH)₃ + 6H⁺ H⁺ + RCOC^– f RCOOH. This is different from the mechanism for zinc and steel, where it is metal ions from anodic dissolution which neutralize the macro-ions and cause a deposit on the anode surface.     

A Study of the Acid–Base Properties of Melts in the Na2O–B2O3–SiO2 System: II. Composition Joins with Sodium Oxide Contents of 25, 30, and 35 mol %

The exponent of oxygen ion activity pO = for melts in the Na₂O–B₂O₃–SiO₂ system along the composition joins with constant sodium oxide contents of 25, 30, and 35 mol % is studied by an electromotive force (emf) technique at 950°C. Measurements are performed using two variants of the technique of determining pO, namely, in high-temperature salt solutions of oxide systems in KF and with a salt bridge between two oxide melts. It is shown that the basicity of melts increases with an increase in the Na₂O content at a constant concentration ratio of glass-forming oxides. The acid–base properties of sodium borosilicate melts are simulated under the assumption of acid–base interaction between the components. It is found that the basicity of the studied melts along the composition joins with constant sodium oxide contents of 30 and 35 mol % is governed primarily by the acid–base interaction in Na₂O–B₂O₃ and Na₂O–SiO₂ binary systems and, to a lesser extent as compared to low-alkali composition joins (below 20 mol % Na₂O), by the formation of Na₂O · B₂O₃ · 2SiO₂ and Na₂O · B₂O₃ · 6SiO₂ ternary compounds.     

Crystallization of Li2O-Al2O3-SiO2 amorphous chemical mixtures

Li₂O·Al₂O₃·(4-10)SiO₂ chemical mixtures, synthesized by sol-gel technology, are analyzed using quantitative x-ray phase and parametric unit cell techniques and compared with glasses of identical composition. Specific features involved in the crystallization of chemical mixtures and glasses are discussed.Translated from Steklo i Keramika, No. 11, pp. 8–10, November, 1996.     

Structure–property relationship amphoteric oxide systems via phase stability and ionic structural analysis

The effects of basicity and amphoteric oxides (Al₂O₃ and Fe_tO) on the structure–property relationships of CaO–SiO₂–(Al₂O₃ and Fe_tO) and CaO–SiO₂–Al₂O₃–Fe_tO slags were investigated to determine the constitutional effects on the structure of high-temperature ionic melts. The proportion of Qⁿ species, which is determined by Raman spectroscopy, and the viscosity measured by the rotating cylinder method are both correlated and shown together with the slag structure index (NBO/T) concept. The NBO/T of CaO-SiO₂ binary slags showed a linear relationship with basicity (CaO/SiO₂), including an inflection point at CaO/SiO₂ = 1.0 resulting from the stability and Qⁿ-dominant unit of the melt, which changes close to the wollastonite (CaSiO₃) congruent point. This inflection point changes with the increasing amphoteric oxide content (Al₂O₃ and Fe_tO) because of the change in the dominant polymeric unit (Si⁴⁺–O–Si⁴⁺→M⁴⁺–O–Si⁴⁺; M: Al and Fe), in accordance with the equilibrated primary phases. As the Al₂O₃ content increased, the viscosity and activation energy of slags both drastically increased owing to the change in the flow unit (Si–O–Si, Al–O–Si, and Al–O–Al). In contrast, as Fe_tO increased, the viscosity and activation energy (E_η) of slags decreased because of the change in the flow unit (Si–O–Si, Fe–O–Si, and Fe–O–Fe). Ultimately, the flow unit (T–O–T; T = Si, Al, and Fe) and activation energy of the slags were found to be closely related to the solid primary phase on the phase diagram, and the physical-property–structure relationship was determined from the phase stability.     

Kinetics and Mechanism of the Interaction of Alkali Calcium Silicate Glasses with Salt Melts in the KNO3–Pb(NO3)2 System

The interaction of alkali calcium silicate glasses with salt melts in the KNO₃–Pb(NO₃)₂ system is investigated at temperatures of 420–520°C. The chemical composition of crystalline coatings formed upon treatment contains both components of the initial glass (SiO₂, 9–12 wt %; CaO, 0.8–1.2 wt %) and components of the salt melt (PbO, 82–89 wt %). The treatment temperature is the main factor affecting the structure of the modified surface layer. The mechanism of the interaction of alkali calcium silicate glasses with salt melts is analyzed. According to this mechanism, the interaction involves the ion exchange (with the participation of Na⁺, K⁺, Ca²⁺, and Pb²⁺ ions), crystallization of modified surface layers, and incorporation of Pb _x O _y nanoparticles (formed in the salt melt) into the coating structure.     

Influence of CuO on the formation and coexistence of 3CaO·SiO2 and 3CaO·3Al2O3·CaSO4 minerals

The influence of CuO on the formation and coexistence of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals in Portland cement containing 3CaO·3Al₂O₃·CaSO₄ mineral is reported in this paper. The results show that a suitable amount of CuO can lower the clinkering temperature and improve the burn-ability of clinkers. It can also promote the formation of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals and facilitate the coexistence of the two minerals in the clinkers. But adding 1% CuO to the raw material can cause the decomposition of 3CaO·3Al₂O₃·CaSO₄.     

Impact of the cation field strength on physical properties and structures of alkali and alkaline-earth borosilicate glasses

The impact of the cation field strength (CFS) of the glass network-modifier cations on the structure and properties of borosilicate glasses (BS) were examined for a large ensemble of mixed-cation (R/2)M₍₂₎O–(R/2)Na₂O–B₂O₃–KSiO₂ glasses with M⁺ ={Li⁺, Na⁺, K⁺, Rb⁺} and M²⁺ ={Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺} from four series of {K, R} combinations of K = n(SiO₂)/n(B₂O₃) = {2.0, 4.0} and R =[n(M₍₂₎O) ?+ ?n(Na₂O)]/n(B₂O₃) = {0.75, 2.1}. Combined with results from La³⁺ bearing glasses enabled the probing of physical-property variations across a wide CFS range, encompassing the glass transition temperature (T_g), density, molar volume and compactness, as well as the hardness (H) and Young's modulus (E). We discuss the inferred composition–structure/CFS–property relationships. Each of T_g, H, and E revealed a non-linear dependence against the CFS and a strong T_g/H correlation, where each property is maximized for the largest alkaline-earth metal cations, i.e., Sr²⁺ and Ba²⁺, along with the high-CFS La³⁺ species. The ¹¹B MAS NMR-derived fractional BO₄ populations decreased linearly with the average M^z+/Na⁺ CFS within both K–0.75 glass branches, whereas the NBO-rich K–2.1 glasses manifested more complex trends. Comparisons with results from RM₂O–B₂O₃–KSiO₂ glasses suggested no significant “mixed alkali effect”.     

Y3Al5O12–SiO2 Glasses: Structure and Polyamorphism

Aerodynamic levitation and CO₂ laser melting have been used to synthesize the yttrium aluminosilicate glasses zY₂O₃–yAl₂O₃–xSiO₂ with z/y = 3/5 corresponding to the YAG (Y₃Al₅O₁₂) composition and x between ~5 and ~45 mol%. The low‐ and high‐density (LDA inclusion and HDA matrix) polyamorphic phases in glasses with less than ~14 mol% SiO₂ were identified with backscattering electron imaging. Polarized and depolarized Raman spectra show the formation of various Qⁿ SiO₄ species whose relative populations change smoothly as the SiO₂ content is altered. The AlOs (s = 4–6) and YOz (z = 6–9) polyhedra formed in the YAG glass are preserved upon silica additions while the terminal oxygens of the Q²AlO₄ tetrahedra are gradually bridged to the Qⁿ‐SiO₄ species. The low‐frequency Boson Peak overlaps with the vibrational spectrum and its maximum is redshifted with increasing silica content. Micro‐Raman spectra measured for the LDA and HDA amorphous phases are found to be similar to the spectra of the bulk glass indicating common structural characteristics. The stability of the LDA phase against crystallization appears to be lower than that of the HDA phase. The crystallinity on certain inclusions consisted of YAG microcrystals and a new unidentified microcrystalline phase within Y₄Al_2(1?x)Si_2xO_(9+x) solid solution.     

Enhanced photoluminescence quantum yield of Ce3+-doped aluminum–silicate glasses for scintillation application

Ce³⁺-doped 20Gd₂O₃–20Al₂O₃–60SiO₂ (GAS:xCe³⁺) glasses (x = 0.3, 0.7, 1.1, 1.5, 1.9 mol%) with Si₃N₄ as a reducing agent were prepared. The density of the glasses is around 4.2 g/cm³. With the increase in the Ce³⁺ concentration, both the photoluminescence (PL) and PL excitation peaks of GAS:xCe³⁺ glasses show a redshift because the 4f–5d energy levels of Ce³⁺ ions are narrowed. PL quantum yield and PL decay time of GAS:xCe³⁺ glasses are 28.32–50.59% and 43–64 ns, respectively. In addition, they both first increases and then decreases with the Ce³⁺ concentration increasing, reached the maximum when x = 1.1 mol%. The integrated X-ray excited luminescence (XEL) intensity of the GAS:1.1Ce³⁺ glass is 23.86% of that of Bi₄Ge₃O₁₂ (BGO) crystal, and the light yield reaches 1200 ph/MeV with an energy resolution of 22.98% at 662 keV when exposed to γ-rays. The PL and XEL thermal activation energies of GAS:xCe³⁺ glasses are independent of Ce³⁺ ions concentration. Scintillating decay time of the glasses exhibits two components consisting of nanosecond and microsecond levels, and the scintillating decay time gradually decreases with the Ce³⁺ concentration increasing. The difference between PL and scintillating decay time is discussed regarding the different luminescent mechanisms.     

Pulsed Cathodoluminescence and Vibrational Structure of Localized Electronic States in Alkali Silicate Glasses

The cathodoluminescence of localized electronic states (L intrinsic centers) in glasses of the composition (mol %) 22Me ₂O · 3CaO · 75SiO₂ and Me ₂O · 3SiO₂ (Me = Li, Na, K) is investigated upon excitation with a pulsed electron beam (180 keV, 700 A/cm², 2 ns). The luminescence spectra recorded in a pulsed periodic mode contain bands of L centers of two types whose occurrence reflects the formation of fragments with different degrees of atomic ordering in the microstructure of glasses. The line spectra with separations between the lines ₀ = 820 cm^-1 and ₁ = 520-640 cm^-1 are measured in a single-pulse mode. The effect revealed is attributed to the manifestation of the vibronic interactions during radiative relaxation of the triplet state of L centers. It is demonstrated that, according to the mechanism of cathodoluminescence, electronic excitations interact with local vibrations of nonbridging oxygen atoms and phonon modes of the glass network. The corresponding interactions are classified as vibronic(₀) and electron-phonon (₁) interactions.