Role of MgO in lowering glass transition temperature and increasing hardness of lithium silicate glass and glass-ceramics

The effect of variation of MgO (1.5, 4.5 and 7.5 mol%) content on glass structure, crystallization behavior, microstructure and mechanical properties in a Li₂O–K₂O–Na₂O–CaO–MgO–ZrO₂–Al₂O₃–P₂O₅–SiO₂ glass system has been reported here. Increased amount of MgO enhanced the participation of Al₂O₃ as a glass network former along with [SiO₄] tetrahedra, reducing the amount of non-bridging oxygen (NBO) and increasing bridging oxygen (BO) amount in glass. The increased BO in glass resulted in a polymerized glass structure which suppressed the crystallization and subsequently increased the crystallization temperature, bulk density, nano hardness, elastic modulus in the glasses as well as the corresponding glass-ceramics. MgO addition caused phase separation in higher MgO (7.5 mol%) containing glass system which resulted in larger crystals. The nano hardness (～10 GPa) and elastic modulus (～127 GPa) values were found to be on a much higher side in 7.5 mol% MgO containing glass-ceramics as compared to lower MgO containing glass-ceramics.     

Fabrication of highly dense Si3N4 via record low-content additive system for low-temperature pressureless sintering

Dense Si₃N₄ ceramics were fabricated by pressureless sintering at a low temperature of 1650°C with a short holding period of 1 h under a nitrogen atmosphere. The role of ternary oxide additives (Y₂O₃–MgO–Al₂O₃, Y₂O₃–MgO–SiO₂, Y₂O₃–MgO–ZrO₂) on the phase, microstructure, and mechanical properties of Si₃N₄ was examined. Only 5 wt.% of Y₂O₃–MgO–Al₂O₃ additive was sufficient to achieve >98% of theoretical density with remarkably high biaxial strength (∼1200 MPa) and prominent hardness (∼15.5 GPa). Among the three additives used, Y₂O₃–MgO–Al₂O₃ displayed the finest grain diameter (0.54 μm), whereas Y₂O₃–MgO–ZrO₂ produced the largest average grain diameter (∼0.95 μm); the influence was seen on their mechanical properties. The low additive content Si₃N₄ system is expected to have superior high-temperature properties compared to the system with high additive content. This study shows a cost-effective fabrication of highly dense Si₃N₄ with excellent mechanical properties.     

A closer-look on Copper(II) oxide reinforced Calcium-Borate glasses: Fabrication and multiple experimental assessment on optical,structural, physical,and experimental neutron/gamma shielding properties

This study aimed to fabricate six different Copper(II) oxide reinforced Calcium-Borate glasses with different types of substitutions such as Al₂O₃/V2O₅, BaO₂/V₂O₅, and ZnO/V₂O_5. Accordingly, a depth characterization process has been performed for ACV, BCV and ZCV glasses with a nominal composition of 55B₂O₃–35CaO–9Al₂O₃-0.5CuO-0.5V₂O₅, 55B₂O₃–35CaO-8.5Al₂O₃-0.5CuO–1V₂O₅, 55B₂O₃–35CaO–9BaO₂-0.5CuO-0.5V₂O₅, 55B₂O₃–35CaO-8.5BaO₂-0.5CuO–1V2O5, 55B2O3–35CaO–9ZnO-0.5CuO-0.5V2O5, 55B2O3–35CaO-8.5ZnO-0.5CuO–1V₂O₅. Optical, structural, physical, and experimental neutron/gamma shielding properties of synthesized glasses were determined, respectively. Experiments measuring neutron exposure indicated how well glass samples attenuated fast neutrons. The RADACS software was used to record data from a BF3 gas proportional detector from the Canberra NP-100B series and a 241Am/Be neutron source with a 10 mCi activity. The absorption edge belonging to the samples are found between 420 nm and 480 nm. Our findings showed that the optical band gaps for the samples ranged from 1.179 to 2.022 eV. The wavenumber range of 400–1600 cm^-1 was evaluated for the resulting peaks. The region with the highest band formation was approximately 760–1170 cm^-1. While BCV0.5 and BCV1 glasses with 9% and 8.5% BaO₂ insertion have the largest MAC values ranging between 2.255–0.076 and 2.156–0.076 cm²/g, the lowest MAC values varying between 0.361–0.0761 and 0.366–0.076 cm²/g belong to ACV0.5 and ACV1 glasses with 9% and 8.5% Al₂O₃ addition. Our results showed that the BCV glass family has superior material properties among the fabricated glasses. It can be concluded that BaO₂/V₂O₅ glasses may be used in replacement of Copper(II) oxide glasses to provide monotonic behavior on crucial characteristics while maintaining the greatest density increase for large gamma ray shielding properties.     

Effect of BaO substitution for CaO on the structural and thermal properties of SiO2–B2O3–Al2O3–CaO–Na2O–P2O5 bioactive glass system used for implant coating applications

The present study replaced 3.30 and 9.00 mol.% BaO for CaO in a SiO₂–B₂O₃–Al₂O₃–CaO–Na₂O–P₂O₅ bioactive glass system used for implant coating applications. Variations of the glass structure, thermal properties, cytotoxicity, and radiopacity of glasses were studied. As demonstrated by the results, upon adding barium oxide to the glass structure, the weight density increased significantly, while a slight decrease in oxygen density was determined. Introducing barium oxide into glass composition did not cause any considerable change in the spectra of FTIR and Raman. It was demonstrated that the amount of bridging oxygen in the glass structure remained quite unaffected. The hot stage microscopy evaluations revealed further shrinkage of barium-containing frits due to lower viscosity and hence, higher viscous flow of these glasses. By substituting barium oxide for calcium oxide and increasing its concentration, the glass transition temperature (T_g) and the dilatometric softening temperature (T_d) decreased, while the thermal expansion coefficient increased. Moreover, upon substituting 9 mol.% barium oxide for calcium oxide, a 30 °C reduction in maximum sintering temperature (T_ms) of the glass was obtained, whereas the shrinkage rate was increased 1.7 times. It was indicated that the sintering process of barium-incorporated glasses would easily proceed without any phase crystallization. The barium-incorporated glasses exhibited more radiopacity. Additionally, no cytotoxic effect was caused by the substitution, and the Ba-containing glasses could be used for biomedical applications and implant coating as well.     

Thermal expansion and characteristic points of –Na2O–SiO2 glass with added oxides

A differential method with an optical lever system was used to determine the thermal expansion of the glasses based on Na₂O–SiO₂ and containing the following oxides: Al₂O₃, CaO, TiO₂, ZnO, Al₂O₃–TiO₂, CaO–TiO₂, or ZnO–TiO₂. The determination was carried out on both as-drawn and annealed rods. The influence of the thermal history as well as of the added oxide(s) on the thermal expansion of glasses is dealt with in this paper. The experimental results for the thermal expansion of annealed rods show that the addition of CaO–TiO₂ in the glass has the lowest value while the addition of CaO in the glass has the highest value for the coefficient of linear expansion. At the same time, the characteristic points of the annealed glasses, determined from the expansion-temperature curves, show that the addition of ZnO in the glass has the lowest values while the addition of TiO₂ in the glass has the highest values.     

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.     

Microscopic Origins of Compositional Trends in Aluminosilicate Glass Properties

Revealing and understanding the microscopic origins of the macroscopic properties of aluminosilicate glasses is important for the design of new glasses with optimized properties. In this work, we study the composition‐structure‐property relationships in 20 MgO/CaO sodium aluminosilicate glasses upon Al₂O₃‐for‐SiO₂ and MgO‐for‐CaO substitutions. We find that some properties (density, molar volume, Young's modulus, and shear modulus) are linear through the investigated range of Al₂O₃ compositions, while others (refractive index, coefficient of thermal expansion, Vickers hardness, isokom temperatures, and liquid fragility index) exhibit a change in the slope around the composition with [Al₂O₃] = [Na₂O], which is especially pronounced for the glasses containing MgO. We discuss these phenomena based on structural information obtained by NMR spectroscopy and topological considerations.     

Microstructure and properties of SiCf/SiC composite joints with CaO–Y2O3–Al2O3–SiO2 interlayer

Using CaO, Y₂O₃, Al₂O₃, and SiO₂ micron-powders as raw materials, CaO–Y₂O₃–Al₂O₃–SiO₂ (CYAS) glass was prepared using water cooling method. The coefficient of thermal expansion (CTE) of CYAS glass was found to be 4.3 × 10^?6/K, which was similar to that of SiC_f/SiC composites. The glass transition temperature of CYAS glass was determined to be 723.1 °C. With the increase of temperature, CYAS glass powder exhibited crystallization and sintering behaviors. Below 1300 °C, yttrium disilicate, mullite and cristobalite crystals gradually precipitated out. However, above 1300 °C, the crystals started diminishing, eventually disappearing after heat treatment at 1400 °C. CYAS glass powder was used to join SiC_f/SiC composites. The results showed that the joint gradually densified as brazing temperature increased, while the phase in the interlayer was consistent with that of glass powder heated at the same temperature. The holding time had little effect on phase composition of the joint, while longer holding time was more beneficial to the elimination of residual bubbles in the interlayer and promoted the infiltration of glass solder into SiC_f/SiC composites. The joint brazed at 1400 °C/30 min was dense and defect-free with the highest shear strength of about 57.1 MPa.     

Role of MgO on the HAp forming ability in phosphate based glasses

Phosphate-based glasses 45P₂O₅–30CaO–(25 ? x)Na₂O–xMgO for different compositions of x = 0, 1, 2.5, 5 and 10 mol% were prepared using the normal melt quench technique. To study the influence of MgO on phosphate glasses, a series of experimental analyses such as ultrasonic velocities, differential thermal analysis, X-ray diffraction, energy-dispersive X-ray spectroscopy, pH measurements, Fourier transform infrared spectroscopy, scanning electron microscopy and in vitro studies were carried out in all the prepared glasses. A maxima in ultrasonic parameters at x = 2.5 mol% of MgO content and a further decrease in the same with the addition of MgO content were observed in all glasses. The observed results indicate that structural compactness of glass network took place up to 2.5 mol% of MgO (PCNM2.5), beyond which a loose packing of atoms led to structural softening in glass network. The results obtained from X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy analyses in all glasses before and after in vitro studies revealed the existence of higher HAp-forming ability in PCNM2.5 glass.     

CaO–SiO2–Al2O3–Y2O3 glasses as model grain boundary phases for Si3N4 ceramics

The glasses with compositions derived from the eutectic composition [37.78 (Y₃Al₅O₁₂)·62.22 (SiO₂)] of the quasi-binary glass system (Y₃Al₅O₁₂)-(SiO₂) with addition of up to 20 mol.% CaO were investigated as model grain boundary phases for Si₃N₄ ceramics. The influence of CaO as model impurity on the physical properties of the glass (density, thermal expansion) and on the crystallisation behaviour was studied. Although the initial composition of the basic glass was that of yttrium-aluminium garnet (Y₃Al₅O₁₂–YAG), no crystalline YAG was detected. Apart from yttrium disilicate (Y₂Si₂O₇), anorthite (CaAl₂Si₂O₈), tricalcium aluminate (Ca₃Al₂O₆), and calcium yttrium oxide silicate (Ca₄Y₆O(SiO₄)₆), a new phase was detected, not found in the powder diffraction file (PDF) database. Cavities were formed within the devitrified glass due to the volume contraction after crystallisation. Possible implications for the mechanical properties of Si₃N₄ ceramics sintered with addition of Y₂O₃–Al₂O₃ are discussed in terms of the observed compositional dependences of the physical properties of CaO–Y₂O₃–Al₂O₃–SiO₂ glasses.     

Density and Young׳s Modulus of ternary glasses close to the eutectic composition in the CaO–Al2O3–SiO2-system

The elastic properties and the density of ternary glass forming systems within the CaO–SiO₂–Al₂O₃-system (CAS) were evaluated. Different glass compositions near the lowest eutectic (1170 °C) composition within the CaO–Al₂O₃–SiO₂-system have been melted from pure raw materials. Their target compositions differed not more than 4 wt% for each component. Exact chemical compositions were measured by x-ray fluorescence. The density, and acoustic properties were determined and the Young׳s Moduli were derived herefrom. It was of special interest to obtain information on these properties and their dependencies upon small variations in the composition. The density values were between 2.600 and 2.667 g cm⁻³ and the packing density factors V_p of the oxides glasses using the ionic radii of Pauling were in the range from 0.559 to 0.571. The determined data were compared to different model calculations. Density model calculations show relative deviations between 2 and 6%. The values calculated from the model for Young׳s Modulus by Makishima and Mackenzie (1973) [1] were somewhat smaller than the measured ones. The correction by Rocherulle et al. (1989) [3] of the Makishima model showed better agreement with the measured values.     

Tuning the interfacial reaction between CaO–SrO–Al2O3–B2O3–SiO2 sealing glass–ceramics and Cr-containing interconnect: Crystalline structure vs. glass structure

In this paper, Al₂O₃ was added to CaO–SrO–B₂O₃–SiO₂ sealing system to tailor the structure of sealing glass–ceramics and glass–ceramics/metal interfacial reaction. The addition of alumina in glasses contributes to increasing fraction of bridging oxygen in silica tetrahedral as well as the change in boron environment from three-fold to four-fold (BO₄ → BO₃). The devitrification tendency of glasses also decreases with increasing Al₂O₃ content. The condensed glass structure and increasing residual glass content play opposite roles on the interfacial reaction, consequently resulting in a maximum fraction of Cr⁶⁺ in reaction couples between Cr₂O₃ and glass containing 6 mole% Al₂O₃ at 700 °C. In addition, the good bonding can be observed at the interface between Cr-containing interconnect (Crofer 22APU) and glass containing 4 mole% Al₂O₃, held at 700 °C for 100 h. The reported results support the suitability of the prepared glass–ceramics as sealing materials for SOFC applications.     

Effect of boron oxide on the microstructure of mullite-based glass-ceramic glazes for floor-tiles in the CaO–MgO–Al2O3–SiO2 system

The effect of increasing replacement of Al₂O₃ by B₂O₃ in a parent glass on the sintering and further crystallization of mullite was investigated. The composition of the parent glass was chosen in the mullite primary phase field of the CaO–MgO–Al₂O₃–SiO₂ quaternary system. Glass powder pellets were heated under standard (10 °C/min and 2 h of hold time) and fast heatings (25 °C/min and 5 min of hold time) at different temperatures from 700 to 1190 °C. Sintering of B₂O₃-containing glasses took place in the range between 850 and 1050 °C. X-ray diffraction results showed that mullite formed as unique crystalline phase for glasses containing amounts of B₂O₃ larger than 6 wt%. For lower amounts of boron oxide cordierite was formed as secondary crystalline phase. Quantitative determination of mullite by Rietveld analysis indicated that the higher amount of mullite present in the glass-ceramic fast heated at 1160 °C was 19.5 wt% for the glass containing 9 wt% of B₂O₃. The final microstructure of the glass-ceramic glazes showed the presence of well shaped, long acicular mullite crystals dispersed within the residual glassy phase. Results of glass-ceramic glazes when applied as slurry and under industrial heating conditions pointed out promising mechanical properties.     

Structural and thermal characterization of CaO–MgO–SiO2–P2O5–CaF2 glasses

The influence of varying the CaO/MgO ratio on the structure and thermal properties of CaO–MgO–SiO₂–P₂O₅–CaF₂ glasses was studied in a series of eight glass compositions in the glass forming region of diopside (CaMgSi₂O₆)–fluorapatite [Ca₅(PO₄)₃F]–wollastonite (CaSiO₃) ternary system. The melt-quenched glasses were characterized for their structure by infrared spectroscopy (FTIR) and magic angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy. Silicon is predominantly present as Q² (Si) species, while phosphorus tends to coordinate in orthophosphate environment. The sintering and crystallization parameters of the glasses were obtained from differential thermal analysis (DTA) while crystalline phase fractions in the sintered glass–ceramics were analyzed by X-ray diffraction adjoined with Rietveld refinement. Diopside, fluorapatite, wollastonite and pseudowollastonite crystallized as the main crystalline phases in all the glass–ceramics with their content varying with respect to variation in CaO/MgO ratio in glasses. The implications of structure and sintering behaviour of glasses on their bioactivity were discussed.     

Thermal properties of ecological phosphate and silicate glasses

The present work deals with ecological phosphate and silicate glasses that belong to the oxide systems: Li₂O-MgO-P₂O₅, Li₂O-CaO-P₂O₅, Li₂O-MgO-P₂O₅-Fe₂O₃; Li₂O-CaO-P₂O₅-Fe₂O₃ and SiO₂-R₂O-R′O (R = Na, K; R′ = Mg, Ca), the last system contains certain amounts of ZrO₂, ZnO, TiO₂. These ecological glasses do not contain toxic substances as BaO, PbO, As₂O₃, As₂O₅, fluorine, CdS, CdSe and they have applications as regards the retention and counteracting action of the harmful compounds resulted from the nuclear plants. The replacement of MgO by CaO leads to an insignificant increasing of the thermal expansion index and a slight decreasing of the characteristic temperatures, except the softening point where the effect is opposite. Adding of iron oxide in the phosphate glass composition causes the increasing of characteristic temperatures and the decreasing of thermal expansion index, both in MgO and CaO-containing phosphate glasses. The ecological silicate glasses are used as opal glasses free of fluorine as well as for lead-free crystal glass (CFP) where BaO and PbO are replaced by non-toxic oxides as K₂O, MgO, ZrO₂, and TiO₂. The paper presents different glass compositions and the technological parameters to prepare the ecological glass samples. Both ecological phosphate and silicate glasses have been characterized as regards the characteristic temperatures (vitreous transition point, low and high annealing points, softening point) and the thermal expansion coefficient. This study presents the changes of the thermal parameters when CaO replaces MgO in phosphate glass samples and the role of iron oxide in the vitreous network. In the case of silicate glasses, the viscosity and wetting angle dependency of temperature are presented. The elemental analysis of the ecological glasses was made by XPS (X-ray photoelectron spectroscopy) which also put in evidence the iron species from the vitreous network.     

Effect of Ta2O5 Substituting on Thermal and Optical Properties of High Refractive Index La2O3–Nb2O5 Glass System Prepared by Aerodynamic Levitation Method

High refractive index glasses with nominal composition of 0.35La₂O₃–(0.65?x)Nb₂O₅–xTa₂O₅ (x ≤ 0.35) were prepared by aerodynamic levitation method. The effect of Ta₂O₅ substituting on their thermal and optical properties was investigated. All the glasses obtained were colorless and transparent. Differential thermal analyzer results show that as the content of Ta₂O₅ increased, the thermal stability of the glasses increased but the glass‐forming ability decreased. The transmittance spectra of all the obtained glasses exhibited a wide transmittance window ranging from 380 to 5500 nm. As the content of Ta₂O₅ increased, the refractive index of the glasses was enhanced from 2.15 to 2.21 and the dispersion was reduced with the Abbe number increasing from 20 to 27.     

Barium Borosilicate Sealing Glasses Synthesized by a Sol–Gel Process: Chemical Interactions with a Stainless Steel and Gas‐Tightness of a SOFC

Several glasses synthesized by sol–gel route and based on the BaO–B₂O₃–X–Al₂O₃–SiO₂ (X = CaO, MgO) glass system have been investigated to evaluate their applicability as sealant for solid oxide fuel cell (SOFC). Chemical interactions with K41X stainless steel and hydrogen‐tightness of these materials were evaluated after operations at high temperatures over 1,000 h in air atmosphere. Formation of a new phase at the steel–glass interface and formation of porosity in the glass were observed and determined as critical problems over mid‐term operations. The role of MgO is important to obtain a gas‐tight sealing. Application of the glass paste without binder addition was performed in order to avoid possible residual porosity related problems. The best glass was finally used as sealant between anodic and cathodic compartments in complete SOFCs operated at 760 and at 800 °C. Open circuit voltages and power densities of the cells were recorded during the first hours of operation.     

Effect of Ta2O5 addition on the structure,crystallization mechanism,and properties of CaO–B2O3–SiO2 glasses for LTCC applications

CaO–B₂O₃–SiO₂–Ta₂O₅ (CBST) glass-ceramics, with different Ta₂O₅ content, (up to 6 mol%), have been prepared by using glass melt quenching followed by heat treatment between 800 and 880 °C. The Fourier Transform Infrared (FTIR) results showed that the stronger the attraction of Ta⁵⁺ to the oxygens in the BO₃^3? and SiO₃^2? structures, the more easily the B–O and Si–O bonds will be destroyed. The underlying reason is most probably the high field strength of Ta⁵⁺, which results in a weakening of the vibration intensities of the [BO₃] and [SiO₄] units. Moreover, the Differential Scanning Calorimetry (DSC) results showed that the softening point (T_g), crystallization starting temperature (T_c1), and exothermic crystallization peak temperature (T_p1), of the CaSiO₃ phase, shifted to higher values with the addition of Ta₂O₅. Also, the crystallization activation energy (E_a) and the glass stability factor (ΔT) of the CaSiO₃ phase increased, which indicated that the CaSiO₃ phase of the glass became inhibited by the addition of Ta₂O_5. It was, thus, obvious that there was a need of glass characterization. The results of the crystallization kinetics showed that the critical cooling rate decreased with the addition of Ta₂O₅, which indicated that the viscosity of the system had increased. The CBST glass-ceramics, containing 1 mol% Ta₂O_5, that were sintered at 875 °C for 15 min showed excellent dielectric properties: ε_r = 6.22 and tanδ = 1.19 × 10^?3 (1 MHz). To sum up, CaO–B₂O₃–SiO₂–Ta₂O₅ glass-ceramics are potential low temperature co-fired ceramic substrate materials.     

The role of PbO/Bi2O3 insertion on the shielding characteristics of novel borate glasses

Impacts of lead and bismuth oxides insertion on a novel glass system of P₂O₅, B₂O₃, Li₂O, Al₂O₃ according the formula 25B₂O₃–25P₂O₅–10Li₂O–5Al₂O₃–5ZnO-xPbO+ (30-x)Bi₂O₃, x = 5,10, 15, 20, 25 mol%. The mass attenuation coefficient (μ_m = μ/ρ) simulated between 0.015 and 15 MeV using MCNP and calculated theoretically using Phy-X/PSD program. Based on the simulated μ_m, other significant parameters such as linear attenuation coefficient (LAC), half and tenth value layer (HVL, TVL), mean free path (MFP), and effective atomic number (Z_eff) were calculated for fabricated glasses. The G-P fitting methods were used to calculate the exposure and energy absorption buildup factors (EBF and EABF) for fabricated glasses. Furthermore, fast neutron removal cross sections (Σ_R) were calculated theoretically for fabricated glasses. The prepared glasses were effective shielding material which can reduce fast neutrons as well as gamma rays.