Glass forming,crystallization, and physical properties of MgO-Al2O3-SiO2-B2O3 glass-ceramics modified by ZnO replacing MgO

This study focused on the glass forming, crystallization, and physical properties of ZnO doped MgO-Al₂O₃-SiO₂-B₂O₃ glass-ceramics. The results show that the glass forming ability enhances first with ZnO increasing from 0 to 0.5 mol%, and then weakens with further addition of ZnO which acted as network modifier. No nucleating agent was used and the crystallization of studied glasses is controlled by a surface crystallization mechanism. The predominant phase in glass-ceramics changed from α-cordierite to spinel/gahnite as ZnO gradually replaced MgO. The phase type did not change; however, the crystallinity and grain size in glass-ceramics increased when the glasses were treated from 1030 °C to 1100 °C. The introduction of ZnO can improve the thermal, mechanical, and dielectric properties of the glass-ceramics. The results reveal a rational mechanism of glass formation, crystal precipitation, and evolution between structure and performance in the xZnO-(20-x)MgO-20Al₂O₃-57SiO₂-3B₂O₃ (0 ≤ x ≤ 20 mol%) system.     

Phase transformation and microstructure of MgO–Al2O3–SiO2 system glass–ceramics under different heat treatment conditions

Abstract

Effects of heat treatment conditions on phase transformation, microstructure and thermal expansion coefficient (TEC) in MgO–Al₂O₃–SiO₂ system glass–ceramics were investigated by means of differential thermal analysis, X-ray diffraction and scanning electron microscopy. The magnesium aluminium titanate (MAT) precipitated firstly at 850°C and β-quartz solutions (β-QSS) formed at 950°C. Further increasing temperature to 1000°C, MAT disappeared and β-QSS became master phase, following little amount of α-cordierite, MgTi₂O₅, rutile and sapphirine. When glass was treated at 1050°C, β-QSS content decreased and α-cordierite became master phase. As temperature reached higher than 1100°C, β-QSS and sapphirine disappeared, and α-cordierite became master phase accompany with rutile and MgTi₂O₅ as secondary phase. The microstructure transformed gradually from particle shape crystallites to slat shape network with the increase in heat treatment temperature. By controlling heat treatment condition, an ideal glass–ceramics with proper TEC for matching sealing to 4J29 alloy has been obtained.     

Mechanical properties of α-cordierite and β-spodumene glass-ceramics prepared by sintering and crystallization heat treatments

The α-cordierite and β-spodumene glass-ceramics containing B₂O₃, P₂O₅, and/or TiO₂ were produced in a bar shape by hot pressing and crystallization heat treatments of glass powders. Various physical properties of the glass-ceramics were examined. The α-cordierite glass-ceramics showed intrinsic high mechanical property values, whereas the β-spodumene glass-ceramics showed rather low ones. The relatively low density in β-spodumene glass-ceramics would lead to the low mechanical property values. This low density in the β-spodumene glass-ceramics would result from a possible premature crystallization which might hinder a completion of sintering of the matrix. The glass-ceramics without TiO₂ showed slightly higher mechanical properties than those with TiO₂. This difference would result from slightly higher density in the glass-ceramics without TiO₂.     

Crystallization of CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> glass prepared by float process

CaO–MgO–Al₂O₃–SiO₂ (CMAS) glass was prepared by float process. The effects of TiO₂ and heat-treatment on properties and crystallization behaviors of float glasses were investigated by atomic force microscope, differential scanning calorimeter, X-ray diffraction, electron probe microanalyzer, field emission scanning electron microscope and viscosity test. The results showed that CMAS parent glasses produced by float process had a high surface flatness (Ra is less than 80.1 ± 0.1 nm) and low tin penetration (14 μm). When the concentration of TiO₂ increased from 3.51 to 5.01 wt %, the glass transition temperature was decreased, and the crystallization temperature was shifted from 913 to 887°C using differential scanning calorimeter. Field emission scanning electron microscope images showed that phase separation was discovered in CMAS parent glass (containing 3.51 wt % TiO₂) treated at 670°C. Diopside as a major crystalline phase was precipitated in CMAS glass-ceramics nucleated at 700°C for 30 min and followed by crystallization at 910°C for 30 min.     

珍珠岩制备单一α-堇青石微晶玻璃及其性能

以珍珠岩为主要原料制备了单相α-堇青石微晶玻璃.采用DSC、XRD及FESEM分别研究了微晶玻璃的烧结和晶化行为、晶相组成及显微结构.探讨了烧结温度和SiO2含量对微晶玻璃晶相、显微结构及性能的影响.结果表明,随着烧结温度升高,微晶玻璃中μ-堇青石逐渐减少并转变成α-堇青石,微晶玻璃的孔隙率减少.随着SiO2含量升高,α-堇青石晶相析出温度先降低后增高,微晶玻璃的密度及抗折强度先增大后减小,介电性能变差.当Mg∶Al∶Si=2∶2∶5.95时经900 ℃烧结6 h制得单一α-堇青石微晶玻璃,并具有高抗折强度(116 MPa),低介电常数(5.72,10 MHz),低介电损耗(0.0059,10 MHz),与Si相匹配的热膨胀系数(2.91×10-6 K-1),可以用作低温共烧陶瓷材料.     

Effect of different nucleating agent ratios on the crystallization and properties of MAS glass ceramics

The effects of different kinds of nucleating agents on crystallization, microstructure and performances of Magnesium Aluminosilicate (MgO-Al₂O₃-SiO₂, MAS) glass-ceramics which were fabricated by melting method in this study. Also, this paper systematically investigated the mechanism of glass stability, crystallization kinetics and element distribution of MAS glass-ceramics. Herein, we used three kinds of nucleating agents, which was TiO₂, ZrO₂ and composite nucleating agent (TiO₂/ZrO₂). The results showed after the doping of nucleating agent, the content of α-cordierite was increased, the stability and crystallization kinetics of glass was changed, the precipitated crystal phase was finer and more compact. Wherein, the sample with composite nucleating agents (TiO₂, ZrO₂) has the best performance due to the highest contents of α - cordierite, uniform distribution of elements without agglomeration in the crystal phase and the most compact structure, whose Vickers hardness and bending strength can reach 9.70 GPa and 312 MPa, respectively.     

Effect of ZnO on the crystallization behavior and properties of SiO2–CaO–Al2O3–Fe2O3 glass-ceramics prepared from simulated secondary slag after reduction of copper slag

The feasibility of preparing low-cost glass-ceramics from Zn-containing dust and secondary molten slag generated during the carbothermal reduction of copper slag was investigated. Analytical-grade agents, such as ZnO, Fe₂O₃, SiO₂, CaO, and Al₂O₃, were used to simulate the dust and secondary slag. The effect of ZnO content on the crystallization behavior, structure, and mechanical properties of the glass-ceramics was investigated through X-ray diffraction analysis, scanning electron microscopy-energy dispersive spectrometry, differential scanning calorimetry, Fourier transform infrared spectroscopy, and Raman spectroscopy. The results showed that with increased ZnO content from 0 to 6 wt%, the crystallization activation energy of base glass increased from 386.05 to 425.89 kJ/mol. Meanwhile, the average value of the crystal growth index increased from 1.91 to 4.10, and the highest crystallization rate of the glass-ceramics increased from about 1.44 to 23.11 mm³/min. The increased ZnO in glass-ceramics promoted the precipitation of gehlenite, but inhibit the crystallization of anorthite. When the ZnO content was 6 wt%, the comprehensive properties of the glass-ceramics were better; the flexural strength, microhardness, volume density, water absorption rate, and open porosity were 58.67 MPa, 738.35 HV, 2.92 g/cm³, 0.44% and 1.27%, respectively.     

Structural and Textural Modifications of Ternary Phosphate Glasses by Thermal Treatment

Phosphate-based glasses of composition xNa₂O−(45+(10−x))CaO−45P₂O₅ with different Na₂O, CaO (x = 1, 5, 10, 15, and 20 mol%), and invariable P₂O₅ (45 mol%) contents were prepared using the rapid melt quench technique. The obtained thermal data from differential thermal analysis revealed a decline in glass transition (T_g) and crystallization (T_c) temperatures of glasses against the compositional changes. The inclusion of Na₂O at the cost of CaO in the glass network led to a reduction in its thermal stability. The thermal treatment carried out on glasses helped to derive their glass-ceramic counterparts. The amorphous and crystalline features of samples were characterized using X-ray diffraction patterns. The crystalline species that emerged out of the calcium phosphate phases confirmed the dominance of Q¹ and Q² structural distributions in the investigated glass-ceramics. The obtained scanning electron micrographs and atomic force microscopic images confirmed the surface crystallization and textural modification of the samples after thermal treatment. The N₂-adsorption–desorption studies explored the reduction of porous structures due to thermal treatment on the melt-driven glass surface. The measured elastic moduli and Vicker's hardness values of the glasses showed an increase after thermal treatment, which were reduced against the inclusion of alkali content in both glass and glass-ceramics.     

Effect of TiO2 on crystallization and mechanical properties of MgO–Al2O3–SiO2 glasses containing P2O5

MgO–Al₂O₃–SiO₂ glass-ceramics have been widely used in military, industrial, and construction applications. The nucleating agent is one of the most important factors in the production of glass-ceramics as it can control the crystallization temperature or the grain size. In this study, we investigated the effect of replacing P₂O₅ with different amounts of TiO₂ on the crystallization, structure, and mechanical properties of an MgO–Al₂O₃–SiO₂ system. The crystallization and microstructure were investigated by differential scanning calorimetry, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The mechanical properties were investigated by measuring the Vickers hardness, Young's modulus, and fracture toughness. The results showed that adding TiO₂ favored the precipitation of fine grains and significantly increased the Vickers hardness, Young's modulus, and fracture toughness of the glasses. Introducing an appropriate amount of TiO₂ can make a glass structure more compact, promote crystallization, and improve the mechanical properties of MgO–Al₂O₃–SiO₂ glass-ceramics.     

Synthesis, characterization and in vitro bioactivity of magnesium-doped sol-gel glass and glass-ceramics

Bioactive glass and glass-ceramics in the system CaO-MgO-SiO₂-P₂O₅ have been prepared by the sol-gel and high temperature sintering techniques. The obtained samples were characterized by thermogravimetric and differential thermal analysis (TG/DTA), N₂-adsorption measurement, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). In vitro bioactivity tests were also conducted in simulated body fluid (SBF). The studies of crystallization kinetics under non-isothermal conditions showed the activation energy for crystallization to be 381 kJ/mol and the crystallization mechanism gradually changed from three-dimension growth to two-dimension crystallization with the increase of heating rate. Sintering temperature had great influence on the samples texture and structure. In addition, the apatite-formation on glass and glass-ceramics was confirmed by in vitro tests, and crystallization decreased the samples bioactivity.     

Structure and crystallization behaviour of some MgSiO3-based glasses

We report on the structure and crystallization behaviour of four enstatite based glasses. Two glasses with nominal compositions of Y_0.125Mg_0.875Si_0.875B_0.125O₃ and Y_0.125Mg_0.725Ba_0.15Si_0.875B_0.125O₃ were prepared as parent glasses while the other two glasses were derived by the addition of 8 wt.% Al₂O₃ to the parent glass compositions, respectively. Structural features of the glasses were accessed by Fourier transform infrared spectroscopy (FTIR). Non-isothermal crystallization kinetics and thermal stability of Al₂O₃-free glasses were studied using differential scanning calorimetry (DSC). It has been shown that these glasses exhibit higher activation energy of viscous flow and are prone to surface crystallization. Activation energy of crystallization decreases with the addition of BaO in the glasses. Crystallization behaviour of all the experimental glasses in the temperature range of 800–1000 °C was followed by X-ray diffraction (XRD) and FTIR. Clinoenstatite and orthoenstatite were the major crystalline phases in the BaO-free glass-ceramics while BaO-containing compositions featured the early formation and stabilization of protoenstatite.     

Phase evolution and microwave dielectric properties of MgO-B2O3-SiO2-based glass-ceramics

The densification and crystallization behaviors of MgO-B₂O₃-SiO₂ (MBS) glass with various amounts of TiO₂ additions (0-10 wt.%) were investigated by means of thermal analysis, X-ray powder diffraction and scanning electron microscopy. A microwave dielectric characterization was performed in order to evaluate the suitability of MBS glass-ceramics as a low-permittivity dielectric substrate. The densification of the MBS glass started below 700 °C. The main crystalline phases of Mg₂B₂O₅ and MgSiO₃ appeared at 800 and 950 °C, respectively. The Mg₃TiB₂O₈ and TiB_0.024O₂ phases additionally crystallized in TiO₂-added MBS glass-ceramics at 1000 °C. The permittivity increased from 6.1 in pure MBS glass to 6.9 in MBS glass with 10 wt.% of TiO₂. The addition of TiO₂ enhanced the crystallization and consequently increased the Qxf-values of the MBS glass (11 300 GHz) up to 16 500 GHz. The improvement of the Qxf-values became the most evident at 1050 °C. Dense MBS glass-ceramics sintered at 850 ≤ T ≤ 950 °C exhibited Qxf-values of 5000-8000 GHz (at ∼12 GHz), which are comparable with the values of CaO-B₂O₃-SiO₂-based glass-ceramics.     

Processing and luminescence of Eu/Dy-doped Sr2MgSi2O7 glass-ceramics

Glass-ceramics based on the Eu/Dy-doped Sr₂MgSi₂O₇ phosphor have been obtained from sintering and crystallization of glass powders. Electric and gas furnaces were employed for glass melting. The doped parent glasses show red emission under excitation of UV light whereas the corresponding glass-ceramics show blue emission.The microstructure of the glass-ceramics and the crystals responsible for the blue emission were observed by scanning electron microscopy-cathodoluminescence. The composition of the crystallised phases and the distribution and incorporation of rare-earth (RE) ions into the crystals and remaining glassy phase were determined by X-ray diffraction and energy dispersive X-ray analysis, respectively.Photoluminescence emission spectra showed a main peak at 484 nm assigned to the typical Eu²⁺ transitions under excitation at 390 nm in the glass-ceramics. The presence of Dy³⁺ improved persistence in the samples melted in the gas furnace. The glass-ceramics are sensitive to temperature, which modifies both the persistence time and red-blue luminescence.     

Glass-ceramics from a zinc-electroplating solid waste: Devitrification promoted further crystallization of parent glass upon heat treatment

A solid waste from a zinc electroplating production line was successfully used as a main raw material for synthesizing glass-ceramics with a fine microstructure. X-ray fluorescence spectroscopy analysis on dried solid waste shows that the waste mainly contains iron and zinc oxides. X-ray diffraction (XRD) analysis identifies Fe₃O₄ and ZnO phases in calcined waste samples. Based on the above results, silica sand, lime stone and potassium feldspar were proportionally added to make parent glasses by melting the batches at 1450?°C for 2?h. The as-synthesized products show typical DSC and thermal expansion curves with obvious glass transition phenomenon. However, XRD patterns reveal that they had devitrified to form ZnFe₂O₄ phase during the shaping and cooling of the melts. The devitrification became weaker when more potassium feldspar was added. It is interesting to find that the pre-crystallization of ZnFe₂O₄ in the devitrified sample was beneficial to its further crystallization during the following heat-treatment. The result implies that the devitrification of parent glasses is not necessarily a detriment to the preparation of glass-ceramics via controlled crystallization process.     

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.     

Synthesis of glass-ceramics in the Na2O/K2O-CaO-MgO-SiO2-P2O5-CaF2 system as candidate materials for dental applications

This study reports on the sintering behavior, crystallization process, and mechanical properties of novel glass-ceramics (CGs) produced by the glass powder compact consolidation method. Substitution of K₂O for Na₂O and MgO for CaO was attempted in the parent glasses belonging to Na₂O-CaO-MgO-SiO₂-P₂O₅-CaF₂ system. Glass powder compacts were heat treated at various temperatures between 700°C and 900°C, taking under consideration the glass transition (T_g) and the crystallization peak (T_p) temperatures, which were experimentally determined for each investigated glass by thermal analysis (dilatometry and differential scanning calorimetry). The experimental results showed that sintering always preceded crystallization, regardless of the type of substitution. In the case of MgO substitution for CaO, crystallization was advanced in the range of 800°C-850°C, resulting in the formation of an assembly of crystalline phases, such as diopside, fluorapatite, and wollastonite. The substitution of K₂O for Na₂O increased the activation energy for crystallization, shifting crystallization process to a high temperature region, with the formation of alpha-potassium magnesium silicate, instead of wollastonite. The GCs produced had values of 22-31 GPa regarding the modulus of elasticity, 5.0-6.1 GPa concerning the microhardness, and 1.4-1.9 MPa⋅m^0.5 as regard the fracture toughness, which are similar to those of the human jawbone.     

Fabrication and properties of cordierite based glass/AlN composites by sol–gel and pressureless sintering

In this study, the effect of AlN content on the crystallization behavior of cordierite based glass, was firstly investigated. Results show that μ-cordierite appeared in the composites with high AlN content even at high temperatures, which implied that the AlN may broad the crystallization temperature range of μ-cordierite and depress the transformation of μ→α-cordierite. The crystallization temperature of α-cordierite was about 980 °C for the pure glass and the temperature increased with AlN content for composites, but the crystallization temperature of μ-cordierite had reverse trend. The composites owned excellent bending strength when the AlN content was 20 wt%. With increasing of AlN content, the dielectric loss was increased which was caused mainly by the structural loss and the appearance of μ-cordierite, but the dielectric constant had crosscurrent. It was observed that the composites were beneficial in producing LTCC material which can be highlighted with high strength, low shrinkage and good dielectric properties at 1 MHz.     

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.     

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..     

Rapid preparation of low thermal expansion transparent LAS nanocrystalline glass by one-step thermoelectric treatment

The Li₂O–Al₂O₃–SiO₂ (LAS) glass ceramics are prepared by one-step thermoelectric treatment. The influence of thermoelectric treatments on LAS glass-ceramics were studied. The crystal phase composition and microstructure of the LAS glass-ceramics were investigated by DSC, SEM, XRD and FTIR. Moreover, the thermal expansion performance and light transmittance of LAS nanocrystalline glass were characterized. The results show that low-expansion transparent LAS nanocrystalline glass can be produced in a short time by thermoelectric treatment. The free energy of nucleation and the degree of polymerization of the glass network are reduced by the electric field. The key is that the electric field polarizes Ti and Zr ions at the crystallization temperature, so that the crystal nuclei repel the same poles. This allows uniform crystal distribution, promotes crystallization and reduces one-step crystallization of crystal agglomeration. This proves that the rapid preparation of nanocrystalline glass by the one-step method is feasible, and provides a reference for the future one-step processing of glass-ceramics.