Effects of OH− anion additive concentration in nitrate salt baths on chemical strengthening of Li2O–Al2O3–SiO2 (LAS) glass

Two ion-exchange processes of K⁺-Na⁺ and Na⁺-Li⁺ were used to strengthen LAS glass materials, and the effects of OH⁻ anion additive (introduced by hydroxide additive) in molten salt baths were investigated. The K⁺-Na⁺ ion-exchange was superior than Na⁺-Li⁺ ion-exchange in the strength enhancement, and with the hydroxide additive, the thickness of ion-exchange layer, the ion-exchange rate and the flexural strength of LAS glass specimens were enhanced remarkably. In detail, for two ion-exchange processes, the optimized ion-exchange time decreased from 24 h to 2 h and from 6 h to 1 h, and the thickness of ion-exchange layer increased from 16 μm to 22 μm and from 23 μm to 34 μm, respectively. Consequently, the corresponding optimized flexural strength increased from 360 MPa to 520 MPa and from 270 MPa to 460 MPa, attributing to the increased thickness of ion-exchange layer and the increased concentration of alkali ions. It is believed that the broken chemical bonds along with the depolymerized glass network induced by OH⁻ anion decreased the diffusion activation energy E_a and increased the diffusion coefficient D of alkali ions for ion-exchange, and thereby the chemical strengthening process of LAS glass materials was improved.     

Strengthening and toughening of a multi-component lithium disilicate glass-ceramic by ion-exchange

A multi-component lithium disilicate (LD) glass-ceramic with interlocking microstructure consisting of rod-like LD crystals and glassy matrix was ion-exchanged over wide temperature and time ranges in pure NaNO₃ or mixed NaNO₃ and KNO₃ baths below the glass transition temperature. Treatment temperature, time and salt bath dependences of surface characteristics and mechanical properties for the ion-exchanged glass-ceramic were investigated. It was found that the glass-ceramic with limited glassy matrix could be remarkably strengthened and toughened in NaNO₃ bath by adjusting the treatment temperature to a moderate level, at which Li⁺/Na⁺ exchange between the glassy matrix and the salt bath could form an ion-exchanged layer with larger depth and less stress relaxation. Furthermore, by using the mixed salt bath, the undesirable exchange of K⁺/Na⁺ in pure NaNO₃ bath could be limited; further enhanced strengthening effect was achieved. The results might renew the interest on strengthening LD glass-ceramics by traditional ion-exchange process.     

Effect of potassium and silver ion-exchange on the strengthening effect and properties of aluminosilicate glass

In this work, the aluminosilicate glass was subjected to ion-exchange using the KNO₃-AgCl mixed molten salt in order to strengthen the glass while imparting antimicrobial properties. The concentration distribution of K⁺ ions and Ag⁺ ions of the ion-exchanged glasses was characterized by EDS, the effects of ion-exchange temperature (460-500 °C), ion-exchange time (0.5-3 h) and AgCl concentration (0–2.5 wt%) in the mixed molten salt on the strengthening effect and properties of the glass were investigated. The results showed that Ag⁺-Na⁺ ion-exchange, K⁺-Na⁺ ion-exchange existed simultaneously, and Ag⁺-Na⁺ ion-exchange occurred preferentially. Due to the presence of metallic silver, the appearance of the Ag⁺ ion-exchanged glass was light yellow and its transmittance showed a decrease. The surface compressive stress trended up and then down with increasing temperature and time because of the stress relaxation effect. The Vickers hardness of ion-exchanged glass increased by 15%, and the densities and chemical stability were also increased. Ions leaching experiments showed that the Ag⁺ ions release concentration of silver-loaded glass in aqueous environment can reach the bactericidal level. It has been shown that ion-exchange of glass in KNO₃-AgCl mixed molten salts allowed the glass to be strengthened and incorporated with antimicrobial active ions, its chemical stability was improved, too.     

LAS微晶玻璃在离子交换后的去结晶相变化及机械性能表征

Li₂O-Al₂O₃-SiO₂(LAS)系微晶玻璃是一种高性能的实用微晶玻璃体系,以Li₂O、Al₂O₃和SiO₂作为主要原料,采用整体析晶法制备了以透锂长石(LiAlSi₄O₁₀)为主晶相的微晶玻璃,并采用低温离子交换单元盐浴的方法,对其进行化学强化。利用X射线衍射仪、扫描电子显微镜等设备研究了LAS系微晶玻璃化学强化后的表面形貌和机械性能。结果表明,化学强化后此体系微晶玻璃表面出现去结晶相,维氏硬度显著降低,但抗弯强度显著提高,强化10 h时,表面出现约740 nm的非晶相层,抗弯强度达到最大值472 MPa。     

Effect of ZrO2 crystallization on ion exchange properties in aluminosilicate glass

Ion exchange has the potential to improve the mechanical properties of glass ceramics. In this work, ZrO₂ nanocrystals embedded transparent glass ceramics were prepared and effect of the crystallization on ion-exchange properties was investigated. The crystallization of ZrO₂ did not affect the transmittance and Vickers hardness due to the small nanocrystal size and the low crystallinity, but significantly enhanced the ion exchange depth of layer (DOL). X-ray diffraction, high resolution transmission electron microscope, Raman spectra and nuclear magnetic resonance analysis demonstrated that with the crystallization of ZrO₂, the charge compensator (Na⁺) was released, which promoted the transformation of highly coordinated Al into [AlO₄]⁻ tetrahedral units and the formation of Na⁺ balanced non-bridging oxygens. These changes in structure of glass made the Na⁺ more mobile and increased the DOL upon the crystallization. Results reported here may be useful for the development of glass-ceramic materials suitable for chemical strengthening.     

The study of near-net shape lithium aluminosilicate glass-ceramics by direct ink writing

3D printing, a competitive manufacturing technology, has opened up new possibilities for fabricating complex structure ceramic components, but near-net forming is still difficult. This work presented a kind of near-net forming lithium aluminosilicate (LAS) glass-ceramics using direct ink writing (DIW) method by controlling thermal shrinkage. To achieve this goal, a high solid-loading ink was prepared using low thermal expansion LAS glass-ceramic powder containing β-spodumene as raw material. And we comprehensively evaluated the effects of the rheological properties of the slurry and sintering process on the thermal and mechanical performances. Attributed to the restricted sintering activity and thermal deformation of LAS glass-ceramic particles, the 3D-printed samples sintered at 1300 ^◦C for 2 h showed an average linear shrinkage of 0.84% with a flexural strength of 45.59 ± 2.82 MPa and a compressive strength of 65.58 ± 3.99 MPa, respectively. The results suggested that LAS glass-ceramics were excellent candidate materials for near-net forming 3D printing.     

Solid-state field-assisted ion exchange of Ag in lithium aluminum silicate glass-ceramics: A superfast processing route toward stronger materials with antimicrobial properties

Lithium-aluminum-silicate glass-ceramics (LAS) are of pivotal relevance in various applications as they combine excellent mechanical and functional properties. Due to their use in medical devices and cooking articles, antimicrobial properties are obviously of interest.Herein, we report the solid-state field-assisted (Ag→Li,Na) ion exchange in LAS glass-ceramics containing β-quartz and β-spodumene solid solutions. The ion-exchange is extremely rapid and deep silver penetration (>100 μm) can be achieved within a few minutes (<5 min), this being proportional to the treating time and applied current. The elemental profiles are characterized by a relatively complex shape which reflects the different alkali mobility in the different phases. The ion exchange initiates structural modifications involving: (i) β→α transition in spodumene; (ii) formation of lattice microstrain and quartz cell expansion; (iii) substantial changes in the IR absorption spectra. The obtained materials possess improved resistance to crack formation and antimicrobial activity against Staphylococcus aureus.     

Novel ion-exchangeable nepheline glass-ceramics for dental application

Ion exchange of a glass-ceramic system with a specific crystalline phase can lead to materials with superior chemical, physical and mechanical properties. The aim of this study is to characterize newly synthesised nepheline glass-ceramics for dental restorative applications. Four novel experimental glasses based on the nepheline composition were ground into fine powders and then sinter-crystallized into monolithic glass-ceramics. The developed glass-ceramics were characterized before and after ion exchange in a potassium nitrate bath using X-ray diffraction, EDX-SEM, and biaxial flexural strength, hardness and solubility testing in accordance with ISO-6872. The ion exchange process of nepheline containing glass-ceramic Al20 increased the characteristic strength by more than 163 % compared to the starting value. The experimental glass-ceramics increased in strength after ion exchange compared to their as-sintered values by 139 %, 24 % and 123 %. The strength scatter decreased after ion exchange for the nepheline-containing glass-ceramics by 10 %. The characterised glass-ceramics in this work require further investigation and have the potential to be developed into layered glass powders, which can be ion exchanged after sinter-crystallization to produce dental restorations with superior mechanical and chemical properties.     

Surface strengthening of lithium disilicate glass-ceramic by ion-exchange using Rb,Cs nitrates

In order to further improve the flexural strength of lithium disilicate glass-ceramic, surface strengthening by ion exchange using Rb, Cs nitrates has been studied for the first time. The influences of ion exchange using rubidium and cesium salts on the flexural strength and corrosion resistance have been investigated. It was found that the mechanical properties of the lithium disilicate glass-ceramic could be increased greatly by the ion exchange in rubidium nitrate (RbNO₃) salt. After ion exchange for 4?h in RbNO₃ salt, the flexural strength and microhardness increased from 169?MPa and 587?kgf?mm^?2 (5.75?Gpa) of the original lithium disilicate glass-ceramic to 493?MPa and 654?kgf?mm^?2 (6.4?Gpa), respectively. Moreover, the corrosion resistance of the lithium disilicate glass-ceramic was further improved by ion exchange in rubidium and cesium nitrate salts. Furthermore, the maximum thickness of the ion exchange layer using RbNO₃ and CsNO₃ was only 4.3?µm and 0.45?µm respectively. Such a thin exchange layer, which will only require very low Rb⁺, Cs⁺ ions exchange amount, indicates that the molten salts of RbNO₃ and CsNO₃ can be reused for many times. So it is suggested that surface strengthening of lithium disilicate glass-ceramic by ion exchange using Rb, Cs nitrates is cost-efficient and very suitable for the actual production and applications.     

Chemical Strengthening of Glass-Ceramics in the System Li2O-Al2O3-SiO2

Fine-grained glass-ceramics containing a large proportion of β-spodumene solid-solution crystals were strengthened by immersion in molten sodium and potassium salt baths. An ion-exchange reaction placed sodium or potassium ions in lithium ion sites in the β-spodumene structure. The resultant "crowding" of the structure produced a surface compressive layer. In this system, strengths (modulus of rupture on abraded specimens) in excess of 100,000 psi were realized. In a similar manner, stuffed β-quartz solid-solution glass-ceramics derived from the crystallization of Li₂O-Al₂O₃-SiO₂ glasses containing an appropriate amount of nucleating agent were strengthened by K⁺-for-Li⁺ exchange. Stable β-quartz solid-solution glass-ceramics were strengthened by Na⁺-for-Li⁺ exchange, but no significant increase in strength was obtained in the metastable β-quartz materials.     

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.     

Effect of substitution of ZrO2 by SnO2 on crystallization and properties of environment-friendly Li2O–Al2O3–SiO2 system (LAS) glass-ceramics

In this study, a transparent and environmentally friendly Li₂O–Al₂O₃–SiO₂ (LAS) glass-ceramic was prepared by melt-quenching and two-step heat treatment. The influence of the substitution amount of ZrO₂ by SnO₂ on the crystallization, microstructure, transparency, and mechanical properties of LAS glass and glass-ceramics was investigated by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Ultraviolet–visible Spectrophotometer, three-point bending strength test, and microhardness test. The results indicate that the main crystalline phase of LAS glass ceramics was a β-quartz solid solution when heat treated at 780 °C for 2 h and 870 °C for 1.5 h. When the substitution amount of ZrO₂–SnO₂ increased from 0.4 mol% to 2.5 mol%, the grain size and thermal expansion coefficient of LAS glass-ceramics first decreased and then increased, and the crystallinity first increased and then decreased. When the substitution amount of ZrO₂–SnO₂ was 0.8 mol%, the transparency of the LAS glass-ceramics was maximum, the bending strength was 96 MPa, and the Vickers hardness was 10.9 GPa.     

Ion-Exchange Behavior of New and Novel Zirconium(IV)-Based Composite Cation-Exchangers

The synthesized polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers were characterized by Fourier transform infrared spectroscopy, UV spectra, X-ray diffraction, scanning electron microscope, thermogravimetric analysis, and conductivity studies. The ion-exchange capacities, effect of eluent concentration, elution time, elution behavior, and pH on ion-exchange capacity were also studied to exploit the ion-exchange capability of the composites. The study revealed that polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate ion exchangers are having excellent ion-exchange capacity values for K⁺ ion 1.36 and 1.44?meq?g^?1, respectively. The organic polymeric part of the composites provides mechanical and chemical stability, whereas the inorganic part supports the ion-exchange behavior and thermal stability. The increase in electrical conductivity is due to the inorganic and organic parts. A mechanism for the formation of the polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers is discussed, which may also be applied for the preparation of other composite ion exchangers. Sorption behavior of metal ions on the composites was studied in different solvent systems. On the basis of distribution coefficient values (K_d), it has been found that the cation-exchange materials are highly selective for Pb(II)-ions. Such modified composite materials can be applied as an electrochemically switchable ion exchanger for water treatment, especially water softening.     

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 composition and microstructure on transparency and diffusivity in ion-exchangeable spinel glass-ceramics

Ion-exchangeable, transparent spinel glass-ceramics are presented and discussed here for the first time. To retain transparency with increasing crystallinity, spinel glass-ceramics must have uniform crystallization of small (~9 nm) crystallites, not large spherulitic structures comprised of small crystallites. To obtain such a uniform microstructure, the amount of total nucleating agents (ZrO₂ + TiO₂) in the precursor glass composition must be greater than 5 mol%. With small changes in composition and significant differences in microstructure, the demarcation between transparent and opaque glass-ceramics is distinct as is the decrease in K diffusivity during ion-exchange from the transparent (14.7 microns²/h) to the opaque (11.2 microns²/h) compositions. Understanding how to retain transparency during ceramming and increase diffusivity during chemical strengthening is critical in designing materials for many real-world applications. Ion-exchangeable, transparent spinel glass-ceramics are presented and discussed here for the first time. To retain transparency with increasing crystallinity, spinel glass-ceramics must have uniform crystallization of small (~9 nm) crystallites, not large spherulitic structures comprised of small crystallites. To obtain such a uniform microstructure, the amount of total nucleating agents (ZrO₂ + TiO₂) in the precursor glass composition must be greater than 5 mol%. With small changes in composition and significant differences in microstructure, the demarcation between transparent and opaque glass-ceramics is distinct as is the decrease in K diffusivity during ion-exchange from the transparent (14.7 microns²/h) to the opaque (11.2 microns²/h) compositions. Understanding how to retain transparency during ceramming and increase diffusivity during chemical strengthening is critical in designing materials for many real-world applications.     

Eu2+-doped oxyfluoride glass-ceramic with nepheline as an efficient 400 nm UV-LED color converter

SiO₂-Na₂O-Al₂O₃-LaF₃ glass-ceramics doped with Eu²⁺ were synthesized as an efficient inorganic color converter for 400 nm UV-LED. When Eu²⁺ formed within the glass matrix, the obtained glass showed cyan emission under 400 nm excitation, but its emission peak drastically shifted to greenish yellow upon heat treatment. With heat treatment the glass-ceramic also showed highly increased emission intensity, and the color coordinate of the glass-ceramic shifted to yellow. When it was mounted on top of a 400 nm UV-LED, it demonstrated high color conversion efficiency and practical feasibility as an UV-LED color converter. To vary the color coordination the heat-treatment conditions and the thickness of the glass-ceramic were adjusted. The resulting ceramic showed a high quantum yield of up to 78%, which is comparable to conventional ceramic phosphors. The spectral change in the glass-ceramic is attributed to the formation of nepheline and LaF₃ crystalline phases. X-ray diffractometer (XRD), transmission electron microscope with energy dispervise spectroscopy (TEM-EDS) and cathode luminescence (CL) were used to investigate the mechanism of Eu²⁺-doped nepheline crystal formation, and its effect on the spectral change with heat treatment.     

Effect of ZnO on the structural,physio-mechanical properties and thermal shock resistance of Li2O–Al2O3–SiO2 glass-ceramics

The composition of lithium aluminosilicate (LAS) with different zinc oxide-magnesium oxide (ZnO–MgO) contents that ranged from 0 to 1.45 wt percent (wt%) was investigated to determine the thermal shock resistance properties of the glass-ceramics. The LAS glasses were melted in an alumina crucible at 1550 °C for 5 h, and the green compact samples were then heat-treated at 1100 °C for 3.5 h. The presence of zinc oxide (ZnO) in the compositions did not change the major crystal phase of β-spodumene. However, the addition of ZnO shifted the pronounced peak to a lower angle and increased the percentage of crystallinity from 55% to 59%. Additionally, the function of ZnO in LAS glass-ceramics as the network modifier was confirmed through Fourier Transform Infrared Spectroscopy (FTIR) analysis. The physio-mechanical properties were improved when 1.45 wt% ZnO was added to the LAS glass-ceramics. The results showed increased density (2.42 g/cm³), low porosity (0.85%), high flexural strength (125.23 MPa), and low coefficient of thermal expansion (25–800 °C) (CTE_{(25–800 °C)}) value of 1.73 × 10^?6 °C^?1. Meanwhile, the thermal shock resistance properties evaluation of the LAS glass-ceramics at different ZnO contents were conducted at different thermal shock temperatures of 200 °C, 500 °C, and 800 °C. The critical temperature of the LAS specimens with 1.45 wt% ZnO demonstrated the ability to withstand a thermal shock at 800 °C while preserving 87% of their initial strength of 108.40 MPa, exemplifying the best LAS glass-ceramics properties for rapid high-temperature change applications.     

Equilibrium Studies of Sodium-Ammonium,Potassium-Ammonium,and Calcium-Ammonium Exchanges on Clinoptilolite Zeolite

Abstract

Forward and reverse ion-exchange isotherms for the binary sodium-ammonium, potassium-ammonium, and calcium-ammonium systems on clinoptilolite have been measured in aqueous solutions at a total concentration of 0.1 equiv/dm³ and at 298 K. Prior to exchange experiments it was attempted to prepare homoionic forms of the zeolite by exhaustive treatments with appropriate salt solutions of cations. With no binary exchanges, full replacement of the cation by the ammonium ion is observed, which conflicts with some earlier work on clinoptilolite. Despite the observed partial exchange levels, clinoptilolite shows a very high preference for ammonium ion over sodium and calcium but not over potassium. Thermodynamic values for the exchanges were calculated and compared with data in the literature. Both the selectivity and thermodynamic affinity sequence, in agreement with previous work reported in the literature, are K⁺ > NH⁺ ₄ > Na⁺ > Ca²⁺.     

Crystallization,structure and properties of MgO-Al2O3-SiO2 highly crystalline transparent glass-ceramics nucleated by multiple nucleating agents

Generally, highly crystalline transparent glass-ceramics possess excellent physical and chemical properties compared to organic and other inorganic optical materials. We have successfully prepared highly crystalline transparent glass-ceramics in the MgO-Al₂O₃-SiO₂ system by "extreme-time" nucleation & "finite-time" crystallization processes using P₂O₅, ZrO₂ and TiO₂ as multiple nucleating agents. The results revealed that the crystallization of glass is controlled by a three-dimensional interfacial crystal growth process. These glass-ceramics mainly consisted of cordierite crystals with a residual glassy phase, and crystallinity increased with crystallization time, but light transmittance decreased with crystallization time due to enlarged grain sizes. EDS mapping revealed a uniform distribution of elements within the glass-ceramic. In the optimal preparation condition (825?°C/96?h?+?990?°C/3?h), these glass-ceramics exhibited a high crystallinity (87.3?vol. %), high transmittance (78%), and excellent mechanical properties. This work provides a roadmap for preparing highly crystalline transparent glass-ceramics for applications in optical engineering.     

Low Li2O content study in Li2O-Al2O3-SiO2 glass-ceramics

The price of lithium-containing minerals and other chemical materials continues to increase, resulting in an increase in the production cost of Li₂O-Al₂O₃-SiO₂ (LAS) system glass-ceramics. In the LAS glass-ceramics component, the reduction in the amount of Li₂O used can reduce the cost of the product. It is worthwhile to study whether it is possible to prepare glass-ceramics with low expansion properties under low Li₂O content. The effect of Li₂O content on the glass-ceramics of LAS system was studied. In this paper, spodumene was used as the main raw material, and TiO₂ and ZrO₂ were added as crystal nucleating agents to prepare transparent glass-ceramics with low expansion coefficient. The effects of the change of Li₂O content on the crystal phase and microstructure of glass-ceramics were investigated by XRD, DSC, FTIR and SEM. The results show that the main crystalline phase of the low expansion transparent glass-ceramics is β-quartz solid solution. When Li₂O content is in the range of 2.99 wt% to 4.13 wt%, low expansion glass ceramics can be prepared by an appropriate method. With the increase of Li₂O content, the average coefficient of thermal expansion (CTE) in the temperature range of 30 °C–300 °C shows a decreasing trend. When Li₂O content is in the range of 3.51 wt% to 4.13 wt%, the thermal expansion coefficient of the glass ceramics is extremely small, and even a negative expansion coefficient occurs.