Effects of alkali oxides and ion-exchange on the structure of zinc-alumino-silicate glasses and glass-ceramics

Types and contents of alkali metal ions play important role on crystallization and ion-exchange properties in glasses. In this work, effects of Na₂O/K₂O ratio on crystallization and ion-exchange properties of zinc-alumino-silicate glasses were investigated. The crystalline phases precipitated in glasses changes from ZnO to β-Zn₂SiO₄ with the progressive replacement of K₂O by Na₂O in parent glasses. Ion-exchange depth of layer (DOL) decreases gradually with the increase in Na₂O content in parent glasses. Precipitation of ZnO and β-Zn₂SiO₄ nanocrystals facilitated the ion-exchange and enlarged the DOL. Na⁺ and K⁺ ions were doped into ZnO and β-Zn₂SiO₄ nanocrystals during heat-treatment, and the extent of doping was facilitated by ion-exchange. Vickers hardness were improved significantly with the crystallization and ion-exchange. Results reported here are valuable for the controlled preparation and chemical strengthening of ZnO and β-Zn₂SiO₄ glass-ceramics.     

Sintering behavior and properties of lithium stabilized sodium β'' - alumina ceramics with YSZ addition

In this study, investigations of sintering behavior and properties were performed on lithium-stabilized Na-β''-alumina (LiSBA) ceramics with and without 15?wt% 8?mol% Y₂O₃ stabilized ZrO₂ (8YSZ) addition synthesized by solid phase reaction. Changes of phase composition, relative density, and grain size in the ceramics sintered at different temperature were analyzed. It was shown that phase transformation in sintering ceramics was controlled by relationship between the Na₂O evaporation and Li⁺ ions stabilization, while microstructure evolution was controlled by pore-boundary interaction. LiSBA with YSZ addition (Zr-LiSBA) showed more significant variation of β'' phase fractions, slower grain growth and faster densification with increasing sintering temperature, which were caused by enhanced Na₂O evaporation and gas transport by oxygen ion conductor ZrO₂ as well as the drag effect by second phase particles of YSZ in Zr-LiSBA ceramics. Zr-LiSBA specimens sintered at optimized condition achieved higher Vickers microhardness and intermediate Na⁺ ion conductivity.     

Crystallization mechanisms of cordierite glass-ceramics with “surface-center” crystallization behavior

Cordierite glass-ceramics usually begin to crystallize from the surface. As an efficient nucleating agent, TiO₂ can promote the rapid transformation of glass to bulk crystallization, but it is easy to cause the increase of dielectric constant and light absorption. High crystallinity cordierite glass-ceramics were prepared by optimizing the heat treatment process without or with different nucleating agents in stoichiometric cordierite glasses. The results show that the crystallization mechanisms of glasses without and with ZrO₂+P₂O₅ as nucleation agents are controlled by surface crystallization. While, the glass with TiO₂+ZrO₂+P₂O₅ as nucleation agents have the tendency to be bulk crystallization. The studied glasses are crystallized from surface and have different crystallization orientations with the inner glass. The thickness of crystalline layer increased with the increasing of heating temperatures, but the “surface-center” crystallization process cannot complete by further increasing heating temperatures because of softening deformation of glasses. At 1020 ℃, the glasses complete the “surface-center” crystallization for long durations. The glasses without nucleation agents and with ZrO₂+P₂O₅ require 10 h, but the glass with TiO₂+ZrO₂+P₂O₅ complete for 5 h. Although all the three glasses complete the “surface-center” crystallization, the glasses with nucleation agents show the higher crystallinity upon the same heat treatments. Finally, glass-ceramics with excellent performance were obtained, for example, the Z1# glass-ceramic have the high microhardness ∼7.4 GPa, low thermal expansion coefficient ∼1.4☓10⁻⁶ ℃⁻¹ at 20–300 ℃, and relatively high thermal conductivity ∼2.4 W/mK. It also exhibits low dielectric constant and loss, which was ∼4.5 and ∼1.2☓10⁻³ at 1 MHz, ∼ 4.9 and 2.3☓10⁻³ at 10.5 GHz..     

Phase evolution and photoluminescence in Er3+ doped glass ceramics containing lutetium oxyfluoride nanocrystals

Crystalline phase evolution through merely adjusting composition was achieved in silicate glass ceramics containing Lu_nO_n-1F_n+2 (n = 5–10) nanocrystals. Orthorhombic or cubic phase nanocrystals were precipitated in the aluminosilicate glass matrix after thermal treatment together with varying the Na₂O/NaF ratio. Oxyfluoride nanocrystals with quasi-spherical shape show homogenous and dense distribution in glass matrix by transmission electron microscopy measurement. Intense upconversion and mid-infrared emissions were realized in these glass ceramics compared to the precursor glass, and the emission spectral shapes, relative emission intensity and fluorescence decay curves of Er³⁺ in cubic LuOF embedded samples exhibit remarkable differences due to the crystal phase dependent effect in glass ceramics. These results indicate that the crystallization and luminescence properties of oxyfluoride glass ceramics could be modified through the alteration of glass composition, which could be used for the development of novel glass ceramics and design of luminescent properties.     

Growth behavior,morphology and properties of lithium aluminosilicate glass ceramics with different amount of CaO,MgO and TiO2 additive

Li₂O–Al₂O₃–SiO₂ glass with CaO, MgO and TiO₂ additive were investigated. With more CaO + MgO addition, the crystallization temperature (T_p) and the value of Avrami constant (n) decreased, the activation energy (E) increased. The mechanism of crystallization of the glass ceramics changed from bulk crystallization to surface crystallization. With more TiO₂ addition, the crystallization temperature decreased, E and n had a little change. The crystallization of the glass ceramics changed from surface crystallization to two-dimensional crystallization. Plate-like, high mechanical properties spodumene-diopside glass ceramics were obtained. The mechanical properties related with crystallization and morphology of glass ceramics.     

Ion exchange properties of NASICON-type ceramics—Application to ion selective electrodes

The ion-exchange properties of NASICON type ceramics of composition Na₃Zr₂Si₂PO₁₂ were investigated in aqueous solutions of NaCl, LiCl and KCl. The solution analysis shows that the [Zr₂Si₂PO₁₂] framework strongly prefers Na⁺ ion relative to K⁺ and Li⁺. The exchange current density of the alkali-cations at the NASICON/solution interface determined by impedance measurements varies in the order Na⁺>Li⁺>K⁺. These results agree well with the selectivity coefficients of Na⁺ ion selective electrodes based on NASICON. The interference process to alkali-cations in the NASICON based electrode was shown to result from an ionic exchange. The selectivity was suggested to be governed by the mobility of the cation inside the NASICON framework.     

Influence of nucleation agents on crystallization and machinability of mica glass–ceramics

Effects of ZrO₂, La₂O₃, CeO₂, Yb₂O₃ and V₂O₅ on the crystallization kinetics, microstructure and mechanical properties of mica glass–ceramics were investigated by the differential scanning calorimetry (DSC), X-ray diffractometry (XRD), scanning electron microscopy (SEM) and microhardness tester. Results show that bulk crystallization can be obtained by introducing proper nucleation agents into the glass. Both Ozawa method and Kissinger method are suitable for analyzing the crystallization kinetics of mica glass–ceramic. The addition of nucleation agents has little influence on the value of n, keeping two-dimensional crystal growth mechanism. ZrO₂ and V₂O₅ are best nucleation agents in mica system. The increase of crystallization temperature is helpful for the increase of aspect ratio, and the microstructure of the glass–ceramics becomes interconnected, which contributes the improvement of the machinability of the glass–ceramics. Microhardness (H_v), cutting energy (μ¹) and machinability parameter (m) can be used for estimating the machinability of mica glass–ceramics.     

Effect of soluble Cr2O3 on the silicate network,crystallization kinetics,mineral phase,microstructure of CaO-MgO-SiO2-(Na2O) glass ceramics with different CaO/MgO ratio

Cr₂O₃ is often used as a glass additive to prepare glass ceramics. Chromium element exists mainly in two parts in the glass ceramics: chromium-containing spinel and soluble chromium in glass matrix. Herein, effect of soluble chromium on the CaO-MgO-SiO₂-(Na₂O) glass system is researched. Glass and glass ceramics were characterized by Raman spectrum, X-ray diffraction, scanning electron microscopy, energy dispersive spectrometry. It is found that the addition of Cr₂O₃ increased the Q²si structure unit in glass networks, especially in glass systems with high MgO content. The crystallization temperatures of the systems were increased with the addition of Cr₂O₃. Soluble chromium reduced the crystallization activation energy of the glass system slightly, but did not alter its crystallization behavior (surface crystallization). With the increase of MgO content, the mineral phases of the glass ceramics gradually changed from wollastonite to diopside. Cr₂O₃ reduced the lattice parameters of the mineral phases. The addition of Cr₂O₃ has a significant effect on grain refinement and structural compactness of the glass ceramics system with high MgO content.     

Properties and Crystallization Behavior of Sodium Iron Phosphate Glasses

Ternary Na₂O–Fe₂O₃–P₂O₅ (NFP) glasses with varying Na₂O/Fe₂O₃, Na₂O/P₂O₅, and Fe₂O₃/P₂O₅ ratios were prepared. The properties and crystallization tendencies were systemically investigated. It is shown that both density and chemical stability of the glass increase with Fe₂O₃. In contrast the Na₂O/P₂O₅ ratio has little effect on the glass properties for a fixed Fe₂O₃ content. The crystallization behavior of the glasses was analyzed by DTA and XRD. Unlike Li₂O–Fe₂O₃–P₂O₅ glasses NFP glasses were found to be stable against crystallization. 15Na₂O–27Fe₂O₃–58P₂O₅ glass was found to have the highest chemical stability among the studied NFP samples; the influence of TiO₂, ZrO₂ on crystallization in this composition was studied. It is found that addition of 3.4 mol% TiO₂ or 2.2 mol% ZrO₂ had little effect on the crystallization behavior of this glass. However, when the amounts of TiO₂ or ZrO₂ were increased to 8.4 or 5.5 mol% respectively the glass readily devitrified. Furthermore the addition of fluorine (introduced by replacing Na₂CO₃ with NaF in the glass batch) leads to amorphous glasses which could be crystallized to form NaFeP₂O₇ upon controlled thermal treatment. With increasing NaF additions the activation emergy for crystallization decreased from 428 to 381 kJ/mol.     

Phase formation during crystallization of a Li2O-Al2O3-SiO2 glass with ZrO2 as nucleating agent – An X-ray diffraction and (S)TEM-study

Glass ceramics based on the system Li₂O/Al₂O₃/SiO₂ (LAS) often show a coefficient of thermal expansion close to zero. Although these glass-ceramics are of high economic importance, the fundamentals of the crystallization process are still not fully understood. In this paper, the effect of ZrO₂ addition as a sole nucleation agent on the crystallization of the LAS glass is described predominantly using transmission electron microscopy and X-ray diffraction. The composition of the studied green glass was close to that of the commercially available Robax™ glass (Schott AG), which, however, contained both, ZrO₂ and TiO₂ as nucleating agents. It was found that during thermal treatment, in a first step, already at temperatures around 10–20 K below the glass transition temperature, T_g, ZrO₂ nanocrystals with sizes in the range from 5 to 15 nm were precipitated. The next crystalline phase that forms during the crystallization process was LAS with a structure similar to the hexagonal high temperature phase of quartz. These crystals were much larger than the ZrO₂ crystals. If thermal treatment was carried out at higher temperatures, a dense network of LAS crystals was formed. Differently shaped crystals in samples with different thermal history were visualized, and an enrichment of Ba and Sb in the residual glass phase in the late stages of thermal treatment was found. Also, an enrichment of aluminum around the ZrO₂ crystals was evident, which is a hint at a preceding droplet phase separation from which the ZrO₂ crystals were precipitated. The crystallization is notably different from that of mixed ZrO₂/TiO₂ nucleating agents used in commercial lithium alumosilicate glass ceramics.     

Powellite‐Rich Glass‐Ceramics: A Spectroscopic Study by EPR and Raman Spectroscopy

The aim of this study was to better understand the incorporation of rare‐earth elements in glass‐ceramics of nuclear interest. We synthesized glass‐ceramics from glasses in the system SiO₂–B₂O₃–Na₂O–CaO–Al₂O₃–MoO₃–Gd₂O₃ by various heat treatments. Gadolinium is used both as a spectroscopic probe and as a minor actinide surrogate. Glass‐ceramics contain only one crystalline phase in the bulk: powellite (CaMoO₄). This phase can incorporate Gd³⁺ and Na⁺ ions by substitutions on the Ca site. We demonstrated that the charge compensation by Na⁺ favors the incorporation of rare‐earth elements. Moreover, the incorporated elements do not seem to be randomly distributed into the powellite structure.     

Understanding the structural origin of crystalline phase transformations in nepheline (NaAlSiO4)‐based glass‐ceramics

Nepheline (Na₆K₂Al₈Si₈O₃₂) is a rock‐forming tectosilicate mineral which is by far the most abundant of the feldspathoids. The crystallization in nepheline‐based glass‐ceramics proceeds through several polymorphic transformations — mainly orthorhombic, hexagonal, cubic — depending on their thermochemistry. However, the fundamental science governing these transformations is poorly understood. In this article, an attempt has been made to elucidate the structural drivers controlling these polymorphic transformations in nepheline‐based glass‐ceramics. Accordingly, two different sets of glasses (meta‐aluminous and per‐alkaline) have been designed in the system Na₂O–CaO–Al₂O₃–SiO₂ in the crystallization field of nepheline and synthesized by the melt‐quench technique. The detailed structural analysis of glasses has been performed by ²⁹Si, ²⁷Al, and ²³Na magic‐angle spinning — nuclear magnetic resonance (MAS NMR), and multiple‐quantum MAS NMR spectroscopy, while the crystalline phase transformations in these glasses have been studied under isothermal and non‐isothermal conditions using differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and MQMAS NMR. Results indicate that the sequence of polymorphic phase transformations in these glass‐ceramics is dictated by the compositional chemistry of the parent glasses and the local environments of different species in the glass structure; for example, the sodium environment in glasses became highly ordered with decreasing Na₂O/CaO ratio, thus favoring the formation of hexagonal nepheline, while the cubic polymorph was the stable phase in SiO₂–poor glass‐ceramics with (Na₂O+CaO)/Al₂O₃ > 1. The structural origins of these crystalline phase transformations have been discussed in the paper.     

Effects of Al/Na and heat treatment on the structure and properties of glass ceramics from molten blast furnace slag

Glass ceramics with different Al/Na molar ratio from blast furnace slag were prepared using conventional melting-casting method. The structure and properties of glasses or glass ceramics were investigated by DSC, Raman, MAS NMR, XRD, and SEM. The DSC results indicated that the thermal stability (ΔT = T_c-T_g) and crystallization temperature (T_c) of the parent glass firstly increased and then decreased when Al/Na exceeded 1.21. The Raman and ²⁷Al MAS NMR spectra analysis revealed that [AlO₆] increased positively with Al₂O₃/Na₂O. The calculation of Qⁿ ([SiO₄] units with bridging oxygen atoms number of n) suggested an obvious decline of (Q⁰+Q²)/(Q¹+Q³) and that [SiO₄] mainly existed in the form of Q¹ when Al/Na exceeded 1.21, which accorded closely with T_c variation. The crystallization results determined by XRD showed that as Al/Na increased, the main crystal phase was transformed from akermanite to gehlenite and nepheline disappeared. Glass ceramics with Al/Na of 1.48 nucleated at 780 °C for 2 h and crystallized at 880 °C for 3 h exhibited the maximum value of flexural strength. Orthogonal experiment (L9(3⁴)) were carried out to investigated the optimum heat treatment of glass ceramics with a Al/Na of 1.48. The analyses indicated that nucleation time variation has little influence on the flexural strength, and the optimum heat treatment was determined as 760 °C – 1 h–900 °C – 1 h and the flexural strength was characterized as 81.310 MPa.     

Investigation of the Electrode Properties of Glasses as a Method for Elucidating the Structural Role of Their Components: The 25Na2O–15TiO2–6ZrO2–4RxOy–50SiO2 System (R = Ca, Ba, Sr, La, Nb, and Ta)

Glass electrodes are fabricated from the title glasses, and the emf–pH curves are measured at room temperature. The structural role played by the glass components is elucidated from an analysis of the curves. The TiO₂, ZrO₂, Nb₂O₅, and Ta₂O₅ oxides are network-formers, and their effect on the electrode properties of glasses upon simultaneous introduction is summarized within the limits of the studied compositions, whereas the total acidity of the glass increases. The oxides of modifiers La, Ba, Sr, and Ca neutralize the acidic groups of the network-former (supposedly [ZrO_6/2]^2–). The tendency to neutralization decreases in the above order. The ionic electrode selectivity of glasses with an increased content of ZrO₂, which contain Nb₂O₅ and Ta₂O₅, is expressed by the series H⁺ Na⁺ > Li⁺ > K⁺.     

Crystallization and luminescence properties of Eu<Superscript>2+</Superscript> doped diopside glass ceramics

Eu²⁺ doped glass ceramics have been prepared and characterized. The crystallization and optical properties of the glass ceramics were studied by XRD, SEM, and fluorescence spectra. The precipitated crystalline phase in the glass ceramics was prismatic diopside (CaMgSi₂O₆) and plate-like cristobalite (β-SiO₂). As the heat treatment time increases, the content of crystals increases gradually. Fluorescence measurements showed that Eu²⁺ ions entered into the diopside crystalline phase and induced a much stronger emission in the glass ceramics than that in the corresponding glass. With increase of Eu²⁺ content, concentration quenching was observed.     

Effect of ZrO2 on the bioactivity properties of gel-derived CaO-P2O5-SiO2-SrO glasses

Zr-incorporated CaO-P₂O₅-SiO₂-SrO-ZrO₂ (BG-Zr) bioactive glasses were prepared through the sol-gel process by adding zirconium oxychloride to the synthesis batch as the zirconia precursor. The added amount of ZrO₂ was 5, 8 and 11 wt%, respectively, to replace the same amount of CaO. The effect of ZrO₂ on the solubility, bioactivity and structural properties of BG-Zr were investigated. The differential thermal analysis (TG/DTA) and X-ray diffraction (XRD) indicated that the addition of ZrO₂ to the base glass composition increased its crystallization temperature as well as weakened its crystallization tendency. Zr⁴⁺ ion substituted for Ca²⁺ favors covalent O-Zr-O bonding formation, making the glass network stronger, and thus BG-Zr glasses exhibit enhanced bending strength. Immersion tests in hydroxymethylaminomethane (Tris) buffer and simulated body fluid (SBF) show BG-Zr glasses to exhibit slower dissolution rate and lower rate of apatite formation with increasing ZrO₂ content compared to the base glass, which is likely associated with their structure stabilization and lower solubility.     

Controllable competitive nanocrystallization of La3+-based fluorides in aluminosilicate glasses and optical spectroscopy

Glass ceramic has been regarded as an alternative to traditional bulk materials such as single crystal and transparent ceramic. The nucleation/growth behavior of glass ceramic via crystallization is an important topic but is seldom studied so far. In the present work, a series of La³⁺-based oxyfluoride aluminosilicate glasses are designed to understand their nanocrystallization processes upon heating. Impressively, controllable LaF₃, α-NaLaF₄ and β-NaLaF₄ phase-competitive crystallization in glasses is achieved and structural/spectroscopic characterizations confirm the key role of Al/Si ratio to determine the release of Na⁺ ions from glass network to participate in crystallization and phase transformation. Furthermore, the developed glass ceramics are evidenced to be ideal hosts for lanthanide dopants (such as Eu³⁺ and Yb³⁺/Er³⁺), which can effectively incorporate into the precipitated fluoride crystal lattices by substituting La³⁺ ions. As a consequence, incoherent LED-excitable upconverting devices are constructed to demonstrate their promising application as emitting media in display.     

A modified B2O3 containing Li2O-Al2O3-SiO2 glass with ZrO2 as nucleating agent - Crystallization and microstructure studied by XRD and (S)TEM-EDX

Glass-ceramics based on lithium-alumo-silicate glasses are commercially important for a wide range of applications, due to their special properties, like a vanishing thermal expansion. In order to tailor these properties, the composition of the glass and the temperature/time schedule are crucial factors. For the industrial production of most lithium-alumo-silicate glasses, high melting temperatures are required due to the high viscosities of the respective melt compositions. In this study, a simplified lithium-alumo-silicate glass composition with ZrO₂ as nucleating agent, on the basis of the commercially available Robax^® composition, is studied. Adding boron oxide leads to lower viscosities of the glass melt and notably lower melting temperatures may be supplied. The resulting glass is investigated using X-ray diffraction and transmission electron microscopy. During the crystallization process, phases such as ZrO₂ and β-quartz types are formed. The microstructure of the glass ceramics is notably coarser than that of glass-ceramics which are obtained from lithium-alumo-silicate glasses of standard compositions. EDX-analyses indicate a considerable enrichment of chemical elements in comparatively small areas of the microstructure. Especially boron oxide is found to be enriched in the residual glass of the investigated glass-ceramics.     

Highly translucent and strong ZrO2-SiO2 nanocrystalline glass ceramic prepared by sol-gel method and spark plasma sintering with fine 3D microstructure for dental restoration

Balance of better mechanical strength and good translucency for dental restorative materials is always a challenge. A translucent glass ceramic/ceramic with improved mechanical properties or a strong glass ceramic/ceramic with good translucency would therefore be interesting for dental application. Nanocrystalline glass ceramics (NCGC) attract a lot attention because of their superior optical and mechanical properties. This study aims to obtain ZrO₂-SiO₂ nanocrystalline glass-ceramic that possesses high mechanical strength as well as excellent translucency by controlling the content, size, and connection of nanocrystalline ZrO₂ in a ZrO₂-SiO₂ glass-ceramic material. Toward this end, well-homogenized nano-powders with three different compositions, 45%ZrO₂-55%SiO₂ (molar ratio, 45Zr), 55%ZrO₂-45%SiO₂ (55Zr), and 65%ZrO₂-35%SiO₂ (65Zr)_, were synthesized, followed by a fast sintering process. Highly-translucent nanocrystalline glass ceramics composed of tetragonal ZrO₂ were obtained. Samples with high zirconia content showed that the structure of the skeleton was predominately built by nano-sized ellipsoidal ZrO₂ particles bonded by grain boundaries, with amorphous SiO₂ filling the voids between the ZrO₂ particles. The achieved flexural strength measured by piston-on-three-ball test was as high as 1014 MPa. To our knowledge, this is one of the highest flexural strength values of glass ceramics ever reported, which is higher than transparent zirconia and alumina ceramics. The 3D structure of nanocrystalline zirconia in silica matrix did enhance the flexural strength of the NCGC. The results of this study suggest that the new ZrO₂-SiO₂ NCGC has great potential of using as dental restoration.     

Influence of dopants on the crystallization of borosilicate glass

The effects of TiO₂ nucleating agent and CeO₂, ZrO₂, La₂O₃ and Y₂O₃ network modifiers on crystallization and structure of borosilicate glasses were systematically investigated. It was found that the nucleating Ti⁴⁺ ions entered [TiO₆] octahedron, participated in network formation and promoted glass crystallization, while the network modifiers induced α-quartz formation, favoring its crystallization as major crystal phase, which positively affected thermal expansion coefficient of the glass–ceramics. Network modifiers allowed strengthening glass network and conduced α-quartz-like structure, which was helpful for α-quartz crystallization.