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.     

Microstructure,cytocompatibility, and chemical durability of chemically strengthened LAS (Li2O-Al2O3-SiO2) glass-ceramic materials

The K⁺-Na⁺ ion exchange was used to strengthen LAS glass-ceramic materials prepared by hot-pressing sintering. The microstructure, cytocompatibility, and chemical durability of the chemically strengthened LAS glass-ceramics were characterized. The XRD results showed that the K⁺-Na⁺ ion exchange mainly occurred between the glass phase of the LAS glass-ceramics and molten salt baths. The ion-exchange process was mainly responsible for the improved chemical durability of the LAS glass-ceramics. The dissolution in acetic acid was significantly reduced from 72 to 15 μg·cm^?2 after the ion-exchange treatment, which was attributed to residual compressive stress and increased contents of Q³ and Q⁴ structural units in the surface region of the LAS glass-ceramics. In addition, the chemically strengthened LAS glass-ceramic samples exhibited good biocompatibility determined by the CCK-8 process using the L929 cell line, having a promising potential as dental restorative materials.     

High toughness transparent glass-ceramics with petalite and β-spodumene solid solution as two major crystal phases

Lithium aluminosilicate glass-ceramics are well known for good transparency, high fracture toughness, low thermal expansion, and good ion exchange ability. In this study, new transparent Li₂O-Al₂O₃-SiO₂ (LAS) glass-ceramics with petalite and β-spodumene solid solution as the major crystalline phases were invented for favorable mechanical properties and potential for application in the hollowware, tableware, container, and plate glass industries. Crystal phases are mainly influenced by the ratio of Al₂O₃ to SiO₂ concentrations. The concentration of SiO₂ required to form specific crystalline phases in the glass-ceramics is higher than that inferred from the ternary phase diagram. Al₂O₃ content is required to be sufficiently high for the formation of crystals, instead of balancing excess amounts of Li₂O in the glass. The average transmittances of 2.0 ± 0.1 mm thickness samples in visible light regions (400–700 nm) can reach more than 80% with crystal sizes of 20–40 nm. Transmittance is significantly decreased for heat treatments around 710°C, due to the high growth rate of β-spodumene solid solution crystals. Vickers hardness, indentation toughness, and crack probabilities of transparent LAS glass-ceramics are significantly improved compared with standard soda lime silicate glass, due to the crack bridging and deflection of crystal grains.     

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.     

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.     

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。     

MgO,ZnO和BaO对Li2O-Al2O3-SiO2微晶玻璃结晶化和热膨胀性能的影响

通过传统熔融法制备了添加MgO,ZnO和BaO的Li2O-Al2O3-SiO2(Las)微晶玻璃.并通过微分热分析、X射线衍射和扫描电镜研究了MgO, ZnO和BaO对LAS玻璃的结晶化影响.测量了LAS的热膨胀系数(coefficient ofthermal expansion.CTE).结果表明:添加1.0%～1.5%质量分数,不同)MgO,1.0%～3.0%ZnO或1.5%～3.5%BaO的LAS微晶玻璃在500℃以下都表现出负的热膨胀性.随着MgO含量的减少,形成了β锂辉石固溶体(LiAlSi3O8)并导致CTE显著增大.当添加0.5%MgO时,从100~700℃具有0.5120×10-6℃到1.691 3×10-6/℃的正膨胀系数.     

The dielectric,thermal properties and crystallization mechanism of Li–Al – B–Si – O glass – Ceramic systems as a new ULTCC material

Li–Al–B–Si–O (LABS) glass-ceramics with a sintering temperature of 600 °C were studied for ultra-low temperature co-fired ceramics (ULTCC) applications. The crystal phase of LABS glass-ceramics is dendritic β-spodumene. The permittivity and dielectric loss of LABS glass-ceramics are ε_r = 5.8 and tgδ = 1.3 × 10⁻³ at 10 MHz, respectively. The coefficient of thermal expansion (CTE) of LABS glass-ceramics is 3.23 ppm/°C, which is close to that of silicon. The dielectric and thermal properties of LABS glass-ceramics are closely correlated to the degree of its crystallization. The permittivity decreases continually while the dielectric loss decreases first and slightly increases with the increasing of crystallization of β-spodumene. The CTE of LABS glass-ceramics decreases as β-spodumene crystallized from LABS glass. The crystallization kinetic and mechanism of LABS glass-ceramics indicate that the β-spodumene crystallizes in a two-dimensional interfacial growth mechanism due to the migration of Li-ions. The diffusion coefficients derived from energy-dispersive X-ray spectroscopy (EDS) results indicated that both Al and Ag electrodes have good compatibilities with ULTCC tapes, which could reduce the cost of multilayer electro-ceramic devices dramatically by using the ULTCC and base metallization.     

高强度Li2O-Al2O3-SiO2体系微晶玻璃研究进展

Li₂O-Al₂O₃-SiO₂(LAS)体系微晶玻璃因具有优异的力学性能和光学性能,近年来得到了广泛应用。本文针对LAS微晶玻璃的析出晶相、制备工艺和应用进行了介绍。鉴于当前对高硬耐划玻璃材料的迫切需求,重点阐述了LAS微晶玻璃强韧化技术和表面增强方法的研究进展,对今后研发高强度LAS微晶玻璃具有重要指导作用。     

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.     

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.     

Conditions for Crystallization of LAS Glass-Ceramics as a Function of Nucleating Agent Amount and Heat Treatment

The effect of nucleating agent content and of the crystallization heat treatment have been explored on a commercial lithium-aluminosilicate (LAS) composition (Eurokera Kerablack). Using X-ray diffraction (XRD) on treated samples and differential scanning calorimetry (DSC), we have observed that crystallization occurs differently in nucleating agent-depleted materials than in standard LAS. In particular, we found larger grain size and β-spodumene content than in KeraBlack. We also assessed the decisive effect of the heating rate: although nucleation can take place under almost arbitrary conditions (except with no nucleating agent), the final materials depend on the crystallization cycle applied. They contain more β-quartz with smaller grain size if the cycles and the soak treatments are short; they consist mainly of β-spodumene with large grains if the ramps and soak times are long. We also observed that a soak heat treatment does not influence the crystallization in the case of low content of nucleating agents, but can be used to obtain crystallization if only ZrO₂ is added. The impact of nucleating agents underlines the importance of heterogeneous nucleation in these glass-ceramics. We conclude that it is not possible to create a fine-grained LAS glass-ceramic without the proper amount of nucleating agents.     

玻璃组成对Li_2O–Al_2O_3–SiO_2微晶玻璃热膨胀系数的影响(英文)

通过传统熔融法制备了具有低膨胀系数的Li2O-Al2O3-SiO2(LAS)微晶玻璃.利用扫描电镜、X射线衍射、差热分折及热膨胀系数测定等分 析手段,研究了玻璃组成中Li2O,Al2O3,SiO2的含量对微晶玻璃热膨胀系数的影响.结果表明:在标准样品的基础上,Li2O的含量对热膨胀系数影 响很大:Li2O的含量提高,由于形成β-锂辉石,微晶玻璃的结晶程度增加与晶粒尺寸增大,导致热膨胀系数增大.与此相比较,Al2O3和SiO2成分 的变化对膨胀系数的影响较小.当玻璃组成(质量分数,下同)为4%～6%Li2O,16%~18%Al203,66%~68%Si02时,Li2O-Al2Oy-SiO2玻璃的膨胀 系数为-1.5～1.5×10-7/℃(0~700℃)     

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.     

Dielectric properties of CaO–B2O3–SiO2 glass-ceramic systems in the millimeter-wave frequency range of 20–60 GHz

The dielectric and structural properties of the as-quenched melts of three CaO–B₂O₃–SiO₂ compositions (denoted CBS-1, CBS-2, and CBS-3) were investigated to determine their suitability for use in millimeter-wave applications. The CBS-1 glass-ceramic exhibited the lowest coefficient of thermal expansion (CTE = 3.2 ppm/°C), lowest dielectric constant (ε_r = 4.04) at 60 GHz, and highest dielectric loss (tan δ = 0.0029) at 60 GHz, which were attributed to the presence of quartz (SiO₂) as the major phase. In contrast, as the major phase constituent of the CBS-2 and CBS-3 glass-ceramics was β-CaSiO₃, they presented relatively high CTEs (6.6 and 5.9 ppm/°C, respectively), relatively high dielectric constants at 60 GHz (6.29 and 7.61, respectively), and relatively low dielectric losses at 60 GHz (0.0020 and 0.0012, respectively). The CBS-1 glass-ceramic exhibited the highest dielectric loss because of the presence of SiO₂ as the major phase constituent as well as lattice scattering induced by the high glassy phase content. The thermal conductivities (κ) of the CBS-1, CBS-2, and CBS-3 glass-ceramics were determined to be 2.43, 1.06, and 0.82 W/mK, respectively. Structural analysis using Raman and Fourier transform infrared spectroscopy revealed an absence of nonbridging oxygen in the CBS-1 glass-ceramic, while the high CaO content (>40 mol%) of the CBS-2 and CBS-3 glass-ceramics triggered the formation of nonbridging oxygen in the tetrahedral silicate units. The increase in CaO content of the glass-ceramics increased the number of nonbridging oxygen atoms, thereby resulting in the relaxation of the structure. Consequently, the CBS-2 and CBS-3 glass-ceramics exhibited low thermal conductivity. All the prepared glass-ceramics presented high electrical resistivities of greater than 5 × 10¹¹ Ω cm. The CBS-1 glass-ceramic displayed the highest breakdown strength of 15.20 kV/mm. Overall, the excellent microwave dielectric properties and thermal properties of the CBS glass-ceramics will facilitate the utilization of these materials in millimeter-wave applications.     

Spark Plasma Sintering of fine alpha-silicon nitride ceramics with LAS for spatial applications

Many space systems such as satellite mirrors and their supporting structures require to be made from very low-thermal expansion materials combining both high hydrostability and relatively high mechanical properties. In this study, we have applied the “composite concept” in order to explore the possibility of fabricating near zero thermal expansion silicon nitride based ceramics. Consequently, a negative thermal expansion material belonged to the lithium aluminosilicate family (LAS powder crystallized under de β-eucryptite structure) was introduced in an alpha-silicon nitride fine powder (5 and 20 vol% of LAS) and the resulting composite system was sintered by Spark Plasma Sintering (SPS) at 1400 and 1500 °C. In the case of 20 vol% LAS compositions, relatively well-densified ceramics (94.4% of the theoretical density) were produced without adding any further sintering additive. The addition of yttria and alumina oxides allowed enhancing the densification level up to 98.2% (20 vol% LAS compositions) or from 62.3% up to 96.7% of the theoretical density in 5 vol% LAS materials. Nevertheless, it was impossible to full consolidate silicon nitride/LAS composite ceramics at temperatures lower than the temperature at which β-eucryptite melts, even by using SPS technology. Moreover, because of the relatively low temperatures involved in SPS, the α to β-Si₃N₄ transformation was avoided, resulting in microstructures composed of fine equiaxed α-Si₃N₄ grains (<200 nm) and of a glassy phase. Even if the effect of having a very large negative thermal expansion material was lost during the sintering step (because of the β-eucryptite melting), ceramics containing only 20 vol% of LAS-based phase exhibited very interesting values as regards of mechanical properties (strength, hardness, toughness, and Young's modulus), thermal conductivity and thermal expansion coefficient. We discuss in this work why we are so interested in developing dense silicon nitride/LAS ceramics sintered without any further additive addition, even though β-eucryptite is melted during the process and the transformation to the β phase is avoided.     

Microstructure,residual stresses,and mechanical performance of surface crystallized translucent glass-ceramics

Mechanical properties of glasses can be significantly increased by inducing surface crystallization of a low coefficient of thermal expansion phase. In this work, we produced surface crystallized lithia-alumina-silica glass-ceramics with different crystallized layer thicknesses and analysed the resulting residual stresses and their effect on mechanical properties. The residual stress magnitude was estimated by analytical and experimental methods, as well as numerical modeling. The surface compressive stress reached 390 MPa and 490 MPa, as given by the analytical and experimental determination, respectively. These stresses prevented radial cracking in microhardness and scratch tests. The best glass-ceramic achieved a Vickers hardness of 7.5 GPa and fracture strength of 680 ± 50 MPa in a ball-on-three-ball test. These glass-ceramics are translucent, providing 50–60% transmittance over the visible wavelength spectrum (1.3 mm-thick-sample). This study unveiled the causes of improved mechanical properties and validates the concept that surface crystallization is a valuable technique for developing high strength glass-ceramics.     

Microstructures and mechanical properties of Cf/LAS composite and Ti60 alloy joints brazed with TiZrNiCu + Cf mixed powders

In this paper, carbon fiber reinforced lithium aluminosilicate (LAS) glass-ceramics matrix composites (C_f/LAS composites) are joined to Ti60 alloy using TiZrNiCu + C_f mixed powders by proper process parameters. The carbon fibers distribute uniformly in the brazing interlayer and react with Ti, Zr elements in the brazing alloy to form (Ti, Zr)C thin reactive layers, which are between the carbon fibers and the Ti, Zr elements. The effect of C_f content on the mechanical properties and microstructure of brazed joints are investigated. The microstructure of brazed joints varied obviously with the increasing of C_f content. The thickness of reactive layer between interlayer and C_f/LAS composites and Ti solid solution (Ti (s.s)) decrease gradually, and the volume of eutectic structure (Ti(s,s) + (Ti,Zr)₂(Ni,Cu)) decrease gradually. The obtained brazed joints exhibit a maximum shear strength of 73.5 MPa at room temperature using TiZrNiCu + 0.3 wt% C_f mixed powders. The enhanced shear strength can be attributed to the reduction in thermal stress and the reinforcing effect originated from the carbon fiber addition.     

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-triggered bubbles in glass-ceramics

Bubbles appear sometimes in glass-ceramics and degrade most properties, especially light transmission and fracture strength. In this work, we deduced microstructural conditions that trigger bubble genesis during crystallization of bubble-free glasses. We related bubble formation to some microstructural parameters in two model glass compositions that exhibit internal crystallization: 1.07Na₂O.2CaO.3SiO₂ (1.07N2C3S) and Li₂O.2SiO₂ (L2S). In this way, we constructed bubble maps – experimental diagrams showing a region of bubble nucleation and growth in a crystal size versus crystallinity plot. Both glass-ceramics show bubbles having similar geometry that emerge from crystal/liquid interfaces and propagate into the residual liquid. These diagrams show that holes of the order of the crystal size tend to form in glass-ceramics containing a high-volume fraction crystallized (>50%) and relatively large crystal size (>10 μm). Mass spectroscopy experiments revealed that bubble formation in the 1.07N2C3S system is caused by O₂. We believe the knowledge generated by this work and resulting maps provide a very useful tool for the design of bubble-free glass-ceramics.