Effects of dopants with various valences on densification behavior and phase composition of a ZrO2–SiO2 nanocrystalline glass-ceramic

Effects of dopants with different valences on the densification behavior and phase composition of a ZrO₂–SiO₂ nanocrystalline glass-ceramic (NCGC) during pressureless sintering were investigated in this study. The raw powder of Ca²⁺, La³⁺, Ce⁴⁺ and Ta⁵⁺ ions doped ZrO₂–SiO₂ (referred to as Ca-ZS, La-ZS, Ce-ZS, Ta-ZS, respectively) and pure ZrO₂–SiO₂ (PZS) sample were synthesized by sol-gel method, followed by pressureless sintering. Compared with the PZS sample, doping of Ca²⁺ and La³⁺ ions significantly promoted the densification of the NCGCs. The “densification promotion” effect was attributed to the formation of oxygen vacancies and the decrease of SiO₂ viscosity due to doping of aliovalent cations. The dopants with various valences showed significant effects on the phase compositions of the NCGCs during sintering. Doping of Ca²⁺ ion accelerated the reaction kinetics between ZrO₂ nanocrystallites and amorphous SiO₂ to yield ZrSiO₄. The La³⁺ ion acted as destabilizer of t-ZrO₂, which resulted in a rapid tetragonal (t) to monoclinic (m) ZrO₂ phase transformation during sintering, while in the Ta⁵⁺ and Ce⁴⁺ ions doped sample, the phase transformation occurred gradually. All the doping ions increased the lattice parameters and the volume of t-ZrO₂ unit cell, while the effects of the doping ions on the lattice parameters of m-ZrO₂ unit cell were more complex.     

Er2Ti2O7烧绿石基玻璃陶瓷固化体的制备工艺研究

为获得含单一钛酸盐烧绿石的玻璃陶瓷固化体，本文以Er₂Ti₂O₇作为钛酸盐烧绿石代表，在传统的烧结法制备工艺基础上，通过热雾喷解和晶核掺入的技术改进，分别研究了烧结温度、烧结时间、玻璃与陶瓷晶核质量配比等参数对Er₂Ti₂O₇基玻璃陶瓷固化体物相及结构的影响规律。XRD结果表明：在不同的烧结温度、烧结时间和质量配比下，均能获得含单一Er₂Ti₂O₇烧绿石的玻璃陶瓷固化体，Er₂Ti₂O₇前驱体在玻璃中的相稳定性好，未发生相分解，玻璃组分亦未受陶瓷相的影响而析出第二相；玻璃组分对陶瓷颗粒存在张应力作用，玻璃含量越高，Er₂Ti₂O₇的晶胞常数越大；提高烧结温度和烧结时间均有利于增强固化体中Er₂Ti₂O₇的结构有序性，但烧结温度效果强于烧结时间。SEM结果表明：Er₂Ti₂O₇在玻璃基体上呈四方形生长，与玻璃界面清晰，相容性好。固化体的物性测试结果表明，玻璃组分占比将直接影响固化体的表观孔隙率和致密度。根据以上结果可知，新工艺制备的样品具有相纯度高、烧绿石相与玻璃相容性好、两相比例可调等优点，较好地解决了钛酸盐烧绿石在玻璃基体中易发生相分解的问题。     

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

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

Tough,strong, hard,and chemically durable enstatite-zirconia glass-ceramic

Strong glass-ceramics (GCs) have been envisaged and widely researched for various applications, including large architectural panels, ballistic impact protection, bioactive medical implants, and odontological prostheses. Here, we report on the development and characterization of a novel hard, strong and tough enstatite-zirconia (MgSiO₃-ZrO₂) glass-ceramic derived from a 51SiO₂–35MgO–6Na₂O–4ZrO₂–4TiO₂ (mol%) glass. The best GC was developed by treating glass samples for nucleation at 700°C for 12 hours, followed by crystal growth at 1090°C for 3 minutes. It was characterized by X-ray fluorescence (XRF), differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HR-TEM), and contained plate-like enstatite, zirconia, and Ti-containing crystals. We investigated the nucleating ability of ZrO₂ and TiO₂ in inducing internal nucleation. In the early stage of crystallization, enstatite spherulites were observed, which were precipitated by heterogeneous nucleation on previously nucleated ZrO₂ nano-crystals. At more advanced stages, at high temperatures, they transformed into plate-like crystals. The ball-on-three-balls strength, elastic modulus, and Vickers micro-hardness of the GC are 323 ± 26 MPa, 146 ± 13 GPa, and 6.9 ± 0.1 GPa (load = 5N), respectively. The indentation (K_C), single-edge notched beam bending (K_IC), and crack tip (K_tip) fracture toughness are 2.8 ± 0.6 MP.m^0.5, 2.2 ± 0.3 MP.m^0.5, 1.9 ± 0.3 MP.m^0.5, respectively. The crack propagation profile after a controlled Vickers indentation was quite intricate. The enstatite and zirconia crystals enhanced crack deflection, bridging and branching, hindering crack propagation. According to the ISO 6872 for dental materials, the chemical solubility of our GC is 80 ± 5 μg/cm². Due to this positive combination of high strength, toughness, hardness, and chemical durability, this new glass-ceramic is envisioned as a candidate for several applications and could be further developed for memory disc substrates, architectural cladding and tiles, ceramic glazes, and dental materials.     

Enhancement of glass-ceramic performance by TiO2 doping: In vitro cell viability,proliferation, and differentiation

A new TiO₂-containing bioactive glass and glass-ceramics based on 50SiO₂-(45-X)CaO-(XTiO₂)-5P₂O₅ system was designed using a sol–gel technique (where X = 5, 7.5 and 10 wt %). The roles of the crystallization behavior and physicochemical characteristics of the designed glass and glass-ceramics which were played in the introduction of TiO₂ substitutions were investigated. Moreover, cell proliferation and differentiation were evaluated against human osteosarcoma cells (Saos-2). The TiO₂/CaO replacements led to the formation of a stronger glass structure and thus increased thermal parameters and the chemical stabilization of the designed materials. The FTIR data confirmed the existence of Ti within the glass and glass-ceramics samples, and no remarkable effect on their chemical integrity was observed. The XRD patterns indicated that calcium-containing minerals, including Ca₂SiO₄,Ca₃(PO₄)₂, Ca(Ti,Si)O₅, CaTiSiO₅, and Ca₁₅(PO₄)₂·(SiO₄)₆ phases were developed as a role of structure/texture under the applied heat-treatment. The results of the cytotoxicity test proved that a safe sample dose is 12–50 μg/ml, at which cell viability is ≥ 85%. The cell differentiation determined by ALP test proved the superiority of glass-ceramics compared with their native glasses. Therefore, the obtained materials could be safely used as novel biocompatible materials for the regeneration of bone tissue.     

镍渣微晶玻璃核化及晶化制度的研究

以金川镍渣为主要原料采用熔融法制备建筑装饰用微晶玻璃。在成分研究的基础上，通过DSC测试、XRD、SEM和光学显微镜等分析手段，对添加了10wt％TiO2作为晶核剂的CaO-MgO-Al2O3-SiO2系统镍渣微晶玻璃试样的主晶相及微观结构进行了分析，得出了适用于该系统镍渣微晶玻璃的最佳热处理制度。     

压电微晶玻璃定向析晶工艺研究

本文研究了BSTS压电微晶玻璃的定向析晶工艺,分析了热处理温度,温度梯度、及保温时间对析晶性能的影响,探讨了BSTS压电微晶玻璃的定向析晶机理。     

烧结法制微晶玻璃的机理研究

微晶玻璃是近些年来在材料科学上的一项重大发现,在国防尖端技术和建筑业等多种领域起到了举足轻重的作用。微晶玻璃更具有高机械强度、绝缘性和良好的耐酸耐碱性等优点,本文通过烧结法就微晶玻璃的材料特征、微观结构和性能、降低烧结温度的方法等做了详细的介绍。     

Adhesion and interfacial characterization of biomimetically texturized lithium disilicate

Lithium disilicate glass-ceramic (LS2) can be biomimetically textured by crystal orientation, mimicking the microstructure of dental enamel and inducing anisotropic mechanical responses to crack growth. The deliberate texturization of LS2 plays to the clinical advantage of reinforcing weak sites of typical fracture initiation in dental prosthetic constructs. Similar to enamel, adhesion of biomimetically textured LS2 could also show anisotropic behavior. Therefore, tensile bond strength (TBS) before and after thermocycling (TC) and interfacial characterization of biomimetically textured LS2 (parallel (PAR) or perpendicular (PER) crystal orientation) after different pre-treatment modes (hydrofluoric acid etching (HFE), grit blasting (GBL) and self-etching glass-ceramic primer (SGP)) were investigated. TC reduced significantly TBS for all specimens except for GBL. Biomimetic textured LS2 after HFE showed anisotropic behavior regarding adhesion. Crystal orientation reduced TBS for the PER HFE specimens after TC significantly. In general, the TBS of HFE specimens was still higher or not significantly lower compared to other pre-treatment modes like GBL or SGP. For the GBL and SGP specimens, crystal orientation had no influence on TBS and interfacial characteristics. In contrast HFE specimens showed different interfacial characteristics depending if they were PAR or PER texturized. Based on these findings, HFE of biomimetic textured LS2 can be recommended. For bonding, the PAR orientation is recommended as its adhesion potential is less prone to degrade.     

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.