Rheological behavior of the CaO-Al2O3-based mold fluxes with different Na2O contents

The CaO-Al₂O₃-based mold flux is expected during the casting of aluminum containing advanced high strength steels. In this study, the rheological behavior of the CaO-Al₂O₃-based mold fluxes with different Na₂O contents was investigated. The results show that the viscosity in the range of 1423–1573 K reduced sharply when the Na₂O content increased from 0 wt % to 10 wt %, but the tendency slowed down with further increasing Na₂O from 10 wt % to 15 wt %. The activation energy for viscous flow also decreased from 237.76 ± 4.88 kJ/mol to 180.37 ± 7.10 kJ/mol with increasing Na₂O. The structure analyses show that the melt networks were mainly constructed by [SiO₄]^4--tetrahedral, [AlO₄]⁵-tetrahedral and Si-O-Al structural units. These networks were depolymerized with the addition of Na₂O since the charge compensation effect from Na⁺ was relativity weaker comparing with the network breaking effect from O²⁻. In addition, the break temperature of the mold fluxes also decreased from 1406 K to 1198 K due to the more precipitation of low melting point Ca₂Al₂SiO₇, rather than MgAl₂O₄ in the mold flux, during the cooling cycle.     

Combustion synthesis of C/MgAl2O4 composite powders using magnesium oxalate as carbon source

In order to solve the bottleneck problems including uniform distribution, and oxidation resistance of nano carbons in oxide ceramics, C/MgAl₂O₄ composite powders were prepared with MgC₂O₄·2H₂O, MgO₂, Al₂O₃, and Al as raw materials via combustion method under argon atmosphere. The maximum adding amount of MgC₂O₄·2H₂O is 34.34 wt%. The phase compositions and microstructures of combustion products were characterized through X-ray diffraction (XRD), scanning electron microscope (SEM)/EDX, and Raman spectroscopy. The results showed that the phases of products are mainly composed of MgAl₂O₄ and carbon. The prepared MgAl₂O₄ has granular and rod-like morphologies, and the free carbon (1.172 wt%) exists between particles of MgAl₂O₄. Moreover, the addition of FeC₂O₄ as catalyst in raw materials ratio would be beneficial for improving crystallization of in situ carbon generated in the products. The oxidation activation energy of the prepared C/MgAl₂O₄ composite powders was calculated as 143.01 kJ/mol which was 22.17% higher than that of carbon black/MgAl₂O₄ powders (117.06 kJ/mol), suggesting that the C/MgAl₂O₄ composite powders prepared by combustion synthesis have excellent oxidation resistance.     

Effect of metastable phase on the crystallization and mechanical properties of MgO-Al2O3-SiO2 glass-ceramics without nucleating agents

Glass-ceramics without nucleating agents usually undergo surface crystallization, which deteriorates the overall performance of the products. In this paper, we evaluated the effects of the metastable MgAl₂Si₃O₁₀ crystalline phase on the crystallization behavior of a MgO–Al₂O₃–SiO₂ (MAS) glass without nucleating agents and mechanical properties of the glass-ceramics obtained. The results demonstrated that the precipitation of metastable MgAl₂Si₃O₁₀ crystallites promotes the crystallization mechanism transformed from surface crystallization into volume crystallization with two-dimensional crystal growth. Furthermore, the grain size of MgAl₂Si₃O₁₀ near the surface of the prepared glass-ceramics was larger than that of MgAl₂Si₃O₁₀ inside, which helps to generate compressive stress and improves its mechanical properties. The glass-ceramics containing metastable MgAl₂Si₃O₁₀ phase exhibited an enhanced hardness in the range of 7.6 GPa–9.5 GPa for indentation loads ranging from 2.94 N to 98 N, and indentation size effect behavior was observed in Vickers hardness tests of both MAS glass and glass-ceramics. The load-independent hardness values for MAS glass and glass-ceramics were reliably evaluated by the modified proportional specimen resistance (MPSR) model of 7.1 GPa and 7.6 GPa, respectively, with a high correlation coefficient of more than 0.9999. This work reveals the unexploited potential of the metastable phase in improving the crystallization ability and mechanical properties of glass-ceramics.     

Transparent glazes with reduced concentration of B2O3

Na₂O?K₂O?CaO?B₂O₃?Al₂O₃?SiO₂ glasses low in B₂O₃ (14%) and highly resistant to crystallization and liquation under heating are synthesized. They are used for making transparent low-melting heat-resistant glazes with a low boron ion migration rate.     

Metastability in the MgAl2O4–Al2O3 System

Aluminum oxide must take a spinel form (γ‐Al₂O₃) at increased temperatures in order for extensive solid solution to form between MgAl₂O₄ and α‐Al₂O₃. The solvus line between MgAl₂O₄ and Al₂O₃ has been defined at 79.6 wt% Al₂O₃ at 1500°C, 83.0 wt% Al₂O₃ at 1600°C, and 86.5 wt% Al₂O₃ at 1700°C. A metastable region has been defined at temperatures up to 1700°C which could have significant implications for material processing and properties. Additionally, initial processing could have major implications on final chemistry.     

The Effects of Na2O and SiO2 on Liquid Phase Sintering of Bayer Al2O3

To determine how grain‐boundary composition affects the liquid phase sintering of MgO‐free Bayer process aluminas, samples were singly or co‐doped with up to 1029 ppm Na₂O and 603 ppm SiO₂ and heated at 1525°C up to 8 h. Na₂O retards densification of samples from the onset of sintering and up to hold times of 30 min at 1525°C compared to the undoped samples, but similar to the as‐received, MgO‐free Al₂O₃, Na₂O‐doped samples sinter to 98% density with average grain sizes of ~3 μm after 8 h. Increasing SiO₂ concentration significantly retards densification at all hold times up to 8 h. The estimated viscosities (20?400 Pa·s) of the 0.3 to 1.8 nm thick siliceous grain‐boundary films in this study indicate that diffusion greatly depends on the composition of the liquid grain‐boundary phase. For low Na₂O/SiO₂ ratios, densification of Bayer Al₂O₃ at 1525°C is controlled by diffusion of Al³⁺ through the grain‐boundary liquid, whereas for high Na₂O/SiO₂ ratios, densification can be governed by either the interface reaction (i.e., dissolution) of Al₂O₃ or diffusion of Al³⁺. Increasing Na₂O in SiO₂‐doped samples increases diffusion of Al³⁺ and Al₂O₃ solubility in the liquid, and thus densification increases by 1%. Based on these findings, we conclude that Bayer Al₂O₃ densification can be manipulated by adjusting the Na₂O to SiO₂ ratio.     

PRELIMINARY STUDY ON PORTIONS OF SYSTEMS Na2O-CaO-AI2O3-Fe2O3 AND Na2O-CaO-Fe2O3-SiO2*

Portions of the quaternary system Na₂O-CaO-Al₂O₃-Fe₂O₃ have been studied by the exploration of (1) the plane CaO-4CaO.Al₂O₃°Fe₂O₃-(Na₂O + 3Al₂O₃) and (2) planes above the base system CaO.5CaO.3Al₂O3–2CaO.Fe₂O₃ which contain successively increasing amounts of Na₂O up to 6%. A portion of the quaternary system Na₂O-CaO-Fe₂O₃-SiO₂ has been studied by the exploration of a plane containing 5% of Na₂O above the base system CaO-2CaO.SiO₂-CaO.Fe₂O₃. In the pseudosystem CaO-4CaO.Al₂O₃.Fe₂O₃-(Na₂O + 3A1₂O₃) the compound Na₂O.-8CaO.3A1₂O₈ was found to exist as a primary phase, and the area in which the plane cuts the Na₂O.8CaO.3A1₂O₃ primary-phase volume was established. Three points on uni-variant curves were located. The iron phase (4CaO.A1₂O₃.Fe₂O₃ solid solution) was observed to exist in a solid-solution series. In the system Na₂O-CaO-5CaO.3Al₂O_3--2CaO.Fe₂O₃ it was found that the compound Na₂O.8CaO.3Al₂O3 appears at an Na₂O concentration of 4.2%. As soda, however, is taken into solid solution by other phases, it was not feasible at this time to determine the invariant point for Na₂O.8CaO.3A1₂O₃, 3CaO.Al₂O₃, 5CaO.3A1₂O₃, and 4CaO.Al₂O₃.-Fe₂O_a solid solution. In the system Na₂O-CaO-2CaO.SiO₂-CaO.Fe₂O₃ no ternary compounds were observed up to the 5% limit of Na₂O employed. A soda-containing phase occurred in solid solution with α-2CaO.SiO₂, which may precipitate on cooling, forming inclusions in the ß-2CaO.SiO₂, or enter into reaction with the glassy phase.     

Influence of acid‐treated talc and Na2CO3 flux on mineralogical phase composition and porosity in steatite ceramics

The work aimed with the effect of preceramic mixtures containing natural talc (Tc) or acid‐treated talc (Tc‐ac) supplemented by montmorillonite (Mt) or kaolinite (Ka), and the flux Na₂CO₃ on the mineral phase composition, porosity and pore size distribution in the steatite ceramics prepared using solid state sintering at 1300°C. The samples were analyzed using X‐ray diffraction and porometry techniques and scanning electron microscopy. Application of Mt or Ka in preceramic mixtures with provided comparable results. The acidification of talc using hydrochloric acid resulted in partial release of Mg²⁺ from the structure. The ratio of SiO₂:MgO in Tc was 35:65 (wt%) and 70:30 (wt%) in Tc‐ac. Tc, clay minerals, and flux Na₂CO₃ in the MgO–Al₂O₃–SiO₂–Na₂O glass system resulted to the separation of forsterite and protoenstatite, while Tc‐ac provided crystallization of protoenstatite at the expense of clinoenstatite in highly porous ceramics. The preceramic mixtures were precursors of bimodal pore size distribution at prepared steatite ceramics.     

Criterion for estimating the number of phases in phase-separated glass of the Na2O-K2O-B2O3-SiO2 system by dilatometric analysis

The data of dilatometry and electron microscopy of four series of xNa₂O-(8 ? x)K₂O-32B₂O₃-60SiO₂, xNa₂O-(8 ? x)K₂O-22B₂O₃-70SiO₂, xNa₂O-(6 ? x)K₂O-34B₂O₃-60SiO₂, and xNa₂O-xK₂O-(40 ? 2x)B₂O₃-60SiO₂ phase-separated glass heat-treated at 550°C for 144 h (for glass containing 70 mol % SiO₂) and 24 h (for glass containing 60 mol % SiO₂) for separation on phases are summarized. The comparison of dilatometric data and electron microscopy allow one to conclude that glass with a difference between the onset deformation temperature and a glass transition temperature of more than 100°C is phase-separated; and glass with a difference of less than 65°C is single-phase. Curves for the glass transition temperature as a function of the K₂O content reveal a mixed alkali effect, namely, minimums for glass containing 60% SiO₂, and maximums for glass containing 70% SiO₂.     

Structure of glasses in the Na2O - Fe2O3 - B2O3 - SiO2 system

The structure of glasses of a local area of the Na₂O - Fe₂O₃ -B₂O₃ - SiO₂ system is studied. The sequence of formation of oxygen-containing tetrahedral groups in the presence of nonbridge oxygen ions is established. Formation of groups of a six-coordinated into cation facilitates crystallization of sodium-boron-silicate glass melts in cooling. Translated from Steklo i Keramika, No. 1, pp. 11–13, January, 2000.     

Thermal Conductivity of Molten B2O3, B2O3–SiO2, Na2O–B2O3, and Na2O–SiO2 Systems

With the aid of the transient hot‐wire method, the thermal conductivity of molten B₂O₃, B₂O₃–SiO₂, Na₂O–SiO₂, and Na₂O–B₂O₃ systems was measured along with their temperature and composition. It was observed that the thermal conductivity of pure B₂O₃ increased with temperature, until about 1400 K, and then decreased subsequently. Using the MAS‐NMR, 3Q‐MAS, and Raman spectroscopy, the structure of B₂O₃ and SiO₂ in the B₂O₃–SiO₂ system was confirmed. Findings show that an addition of B₂O₃ into the pure SiO₂ system causes a significant decrease in thermal conductivity, due to the formation of boroxol rings. The thermal conductivity of the Na₂O–SiO₂ system was measured and its phonon mean free path was calculated. In addition, a positive linear relation between viscosity and thermal conductivity was observed. In the Na₂O–B₂O₃ system, it was found that a change in the relative fraction of 4‐coordinated boron has an influence on the thermal conductivity when the concentration of Na₂O is between 10 and 30 mol%, in which case the tetraborate unit is dominant.     

Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic

The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li₂O–MgO–Al₂O₃–SiO₂ glass-ceramic for the application of joining Si₃N₄ ceramics. We investigated the influence of the MgO/Al₂O₃ composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi₂O₆ and Mg₂SiO₄ were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg₂SiO₄. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10^?6/°C, which was very close to that of Si₃N₄ ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si₃N₄ ceramic surface was 32° and the interface was well bonded.     

Effect of Na2O on the High‐Temperature Thermal Conductivity and Structure of Na2O–B2O3 Melts

The effect of Na₂O and temperature on the thermal conductivity of the Na₂O–B₂O₃ binary system has been measured using the hot‐wire method to examine the relationship between the thermal conductivity and structure in high‐temperature melts. The thermal conductivity of the binary melt is measured from 1173 to 1473 K in the fully liquid state. The thermal conductivity slightly increases with Na₂O content up to 20 wt%. Above 20 wt% Na₂O, the thermal conductivity decreases with increasing Na₂O. The network structure of molten glass was analyzed using Fourier transform infrared (FTIR), Raman spectroscopy, and XPS. The FTIR analysis shows that 3‐D complex borate structures, such as tri‐, tetra‐, and pentaborate are made by [BO₄] tetrahedral units interconnected with 2‐D structure boroxol rings in the low Na₂O region. Above 20 wt% Na₂O content, nonbridged oxygen in [BO₂O^?] units and diborate groups increase with increase in Na₂O. The same tendency is shown by the Raman spectroscopy and XPS analyses. The Raman analysis shows that boroxol rings disappeared with large [BO₄] groups, such as tri‐, tetra‐, and pentaborate structures, which increase at low Na₂O content. Isolated diborate groups and nonbridged oxygen in [BO₂O^?] units increase at high Na₂O content. It can be inferred that single structure units, such as isolated diborate groups, interfere with conduction. The XPS analysis results show that free oxygen produced by the interconnection of Na₂O in the borate structure does not cause significant changes to O^2? in the low Na₂O region, but increases the O^o and decreases the O^?. Above 20 wt% Na₂O, O^? slightly increases and O^o shows a decreasing trend.     

Preparation of glass–ceramic glazes in the SiO2–Al2O3–CaO–MgO–K2O–Na2O–ZnO system by variable content of ZnO

This paper is focused on glass–ceramic glazes from the SiO₂–Al₂O₃–CaO–MgO–K₂O–Na₂O system with ZnO additions (2.5, 5, 10, 15, 15, 20 and 25 wt%). The compositions were designed based on constant molar ratio of SiO₂/Al₂O₃. In the resulting glazes diopside (CaMg[Si₂O₆]), willemite (Zn₂SiO₄) and vitreous phase were identified by X-ray diffraction. Morphological and structural date of these glazes were supplementary determined by EPMA, FTIR and Raman Spectroscopy. DSC analysis was carried out to characterize thermal properties of the materials.     

Volatilization of fluorine in a CaO–SiO2–CaF2-based system with the substitution of Na2O with K2O

Cuspidine-based systems are used to control the crystallization in mold fluxes, which is enabled by CaF₂ additions. However, excess CaF₂ increases the corrosion of casting machines. Therefore, Na₂O and K₂O are added to the mold flux system to ensure an optimized crystallization and lubrication ability of the flux with the CaF₂ content. This study investigated the effect of substituting Na₂O with K₂O on the volatilization of fluorine in a CaO–SiO₂–CaF₂-based slag system at high temperatures. The substitution of Na₂O with K₂O was performed at 5 mol% intervals. The volatilization was observed by thermogravimetric analysis under several isothermal conditions. The mass loss was measured at a heating rate of 5, 10, and 20 K/min. As the temperature increased, the volatilization of the mixed samples increased. The activation energy was calculated using the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods. A kinetic analysis of the volatilization of fluorine was conducted using the calculated parameters and several known kinetic models. Consequently, the volatilization of the Na-rich sample was controlled by chemical reactions and that of the K-rich sample was identified to be controlled by a phase-boundary-controlled reaction. These results suggest that the addition of mixed alkali oxide promote the volatilization during the early stages of the reaction. From the post-experimental composition analyses, the remaining Na and K in the samples suggested a different mechanism for the Na and K volatilization. The volatilization of Na increased with time, whereas K volatilized easily during the beginning of the reaction.     

Tuning energy storage and light transmittance properties in ZrO2-modified Na2O–K2O–Nb2O5–SiO2 glass-ceramics

Crystallization kinetics in ZrO₂-modified glass-ceramics, (35-x)Na₂O–5K₂O–40Nb₂O₅–20SiO₂-xZrO₂ (x = 0, 1, 3, 5, 10 mol%), is analyzed by crystallization activation energy E_c and kinetic parameter k. A large kinetic parameter k of 1.657 × 10²⁵ is found for the sample with x = 1, which indicates a high tendency toward crystallization. NaNbO₃ is formed as the major phase, and its crystallinity changes significantly by the addition of ZrO₂. It is found that the dielectric permittivity and maximum polarization are affected by crystallinity. Large domains are formed, and a relaxation process appears at high frequencies. In addition, the breakdown strength (BDS) is affected by the strong electric field distortion rather than the resistance in this system. Complex impedance analysis shows that resistance decreases with the addition of ZrO₂. The electric field distortion of the glass-ceramics is simulated by COMSOL. A low interfacial polarization activation energy E_a of 0.821 eV is achieved by the addition of ZrO₂. The maximum pulse power density reaches 90 MW/cc at 350 kV/cm for the sample with x = 10, and the pulse energy density attains 0.91 J/cm³ at 300 kV/cm for the sample with x = 1. Light transmittance is achieved because of the low crystallinity and the disappearance of cristobalite SiO₂ in the Na₂O–K₂O–Nb₂O₅–SiO₂ glass-ceramics.     

Investigating the effect of WO3 on the crystallization behavior of SiO2–B2O3 – Al2O3–Na2O – CaO–ZnO high VIS-NIR reflecting glazes

White glass enamels with high solar reflectance and containing different WO₃ concentrations have been prepared and characterized with regard to their optical, mechanical and microstructural characteristics. Upon addition of WO₃ to a glass containing SiO₂, B₂O₃, Al₂O₃, Na₂O, CaO, and ZnO, the crystallization of scheelite follows a crystallization mechanism of bulk type where scheelite grows in one-dimension in a patterned morphology dominated by the heating rate and the concentration of WO₃. Octahedral bipyramids and arrow-like crystals appeared in enamels containing WO₃ concentration above 6%. The presence of scheelite crystals with different orientations also leads to slight variations in hardness and Young modulus thus obtaining Hv values between 8 and 8.8 GPa and E values between 72 and 83 GPa. Similarly, the optical properties such as whiteness, brightness and solar reflectance increase with the presence of scheelite, and the highest solar reflectance occurs for the enamel containing arrow-like and bipyramidal crystals.     

Degradation of Al2O3f/SiO2 composites exposed to Na2SO4 environment and MMH/N2O4 bipropellants test

Al₂O_3f/SiO₂ composites were fabricated efficiently using sol-gel process. The degradation behavior exposed to Na₂SO₄ environment at 1100℃ and MMH/N₂O₄ bipropellants test were investigated and compared. The results showed that the strength of Al₂O_3f/SiO₂ composites gradually decreased as the ratio of Na₂SO₄:water increased; the strength of the composites was only 23.56 MPa at 20% (Na₂SO₄:water), which suggested that the composites maintained lower strength. Cracks began to appear in SiO₂ matrix, and the structure of Al₂O₃f/SiO₂ composites could be corroded which would corrode the SiO₂ matrix, leaving naked fibers. Developing a protective layer with higher stability for Al₂O_3f/SiO₂ composites would be considered for long time use. The composites showed higher ablation resistance to MMH/N₂O₄ bipropellant test; the flexural strength was (77.15 ± 4.56) MPa and the retention ratio was 98.7%. The degradation of Al₂O_3f/SiO₂ composites was promoted owing to the thermal-mechanical and chemical factors. SiO₂ matrix became weak and fragile at elevated temperature; some SiO₂ matrix became loosened and porous after being washed away through the shearing of MMH/N₂O₄ bipropellants, which prevented cracks from penetrating Al₂O₃ fibers. With ongoing test, the fibers were worsened by thermal-mechanical corrosion.     

Effect of Al2O3 and K2O content on structure,properties and devitrification of glasses in the Li2O–SiO2 system

The effect of Al₂O₃ and K₂O content on structure, sintering and devitrification behaviour of glasses in the Li₂O–SiO₂ system along with the properties of the resultant glass–ceramics (GCs) was investigated. Glasses containing Al₂O₃ and K₂O and featuring SiO₂/Li₂O molar ratios (3.13–4.88) far beyond that of lithium disilicate (Li₂Si₂O₅) stoichiometry were produced by conventional melt-quenching technique along with a bicomponent glass with a composition 23Li₂O–77SiO₂ (mol.%) (L₂₃S₇₇). The GCs were produced through two different methods: (a) nucleation and crystallization of monolithic bulk glass, (b) sintering and crystallization of glass powder compacts.Scanning electron microscopy (SEM) examination of as cast non-annealed monolithic glasses revealed precipitation of nanosize droplet phase in glassy matrices suggesting the occurrence of phase separation in all investigated compositions. The extent of segregation, as judged from the mean droplet diameter and the packing density of droplet phase, decreased with increasing Al₂O₃ and K₂O content in the glasses. The crystallization of glasses richer in Al₂O₃ and K₂O was dominated by surface nucleation leading to crystallization of lithium metasilicate (Li₂SiO₃) within the temperature range of 550–900 °C. On the other hand, the glass with lowest amount of Al₂O₃ and K₂O and glass L₂₃S₇₇ were prone to volume nucleation and crystallization, resulting in formation of Li₂Si₂O₅ within the temperature interval of 650–800 °C.Sintering and crystallization behaviour of glass powders was followed by hot stage microscopy (HSM) and differential thermal analysis (DTA), respectively. GCs from composition L₂₃S₇₇ demonstrated high fragility along with low flexural strength and density. The addition of Al₂O₃ and K₂O to Li₂O–SiO₂ system resulted in improved densification and mechanical strength.     

Experimental investigation on high temperature wettability and structural behaviour of SAW fluxes using MgO–TiO2–SiO2 and Al2O3–MgO–SiO2 flux system

To establish the relationship between wettability and structure with the change in SAW flux composition, the contact angle measurement study was performed at 1700 K. For MgO–TiO₂–SiO₂ and Al₂O₃–MgO–SiO₂ flux system the wetting behaviour was studied by evaluating the contact angle as well as surface tension properties. Sessile drop method was used to determine the wetting properties of SAW fluxes. Twenty-one SAW fluxes were designed & developed by applying mixture design approach of design of experiments. Chemical, phase and structural properties of SAW fluxes were measured using modern techniques such as X-ray fluorescence (XRF), X-ray diffraction (XRD) & Fourier Transform Infra-red spectroscopy (FTIR). As per the calculated contact angle value, different surface tension values for MgO–TiO₂–SiO₂ and Al₂O₃–MgO–SiO₂ flux system was calculated using Young's & Boni's equations. Using Dupre's equation the adhesion energy for twenty-one basic fluxes was also calculated. Measured contact angle value increased with increase in the TiO₂/MgO & TiO₂/Al₂O₃ flux ratio. Lower contact angle gives higher wettability between the flux and the heating substrate. With increase of TiO₂/SiO₂ ratio up to 1.5 to 2.0 the calculated surface tension value is decreasing while after that it is increased with increase in TiO₂/SiO₂ ratio.