【作者】 胡伟；

【导师】 孟鸿；

【作者基本信息】 北京大学 ， 材料与化工（专业学位）， 2025， 博士

【摘要】 自2007年iPhone 1首次采用超薄高强度盖板玻璃以来,该类材料在智能终端领域得到广泛应用。随着设备功能集成度提升及轻薄化发展趋势,对盖板玻璃提出了“更薄、更强”的技术要求。传统高铝硅玻璃通过扩大网络结构来优化离子交换(IOX)已显性能瓶颈。为实现强度、透明性与工业化制备的协同突破,高晶体含量的透明微晶玻璃逐步成为新一代盖板材料的候选方向。然而,当前国内外在高强度特种玻璃及透明微晶玻璃的体系设计、机理研究与工程化工艺方面仍相对薄弱。受华为终端与华为技术委托,本研究以高强度锂铝硅(LAS)玻璃及其透明微晶玻璃为研究对象,系统开展组分设计、计算模型修正、微观结构调控与工艺适配等系列研究,旨在建立玻璃强度优化的理论方法和工程实现路径。采用梯度掺杂策略,结合干福熹模型修正与力学性能预测方法,构建以张应力线密度(CTLD)为主的可量化的应力分析机制;通过差示扫描量热、X射线衍射、拉曼光谱和透射电子显微镜等技术,分析微晶玻璃在不同热处理温度下的成核、结构变化和晶相演化机理,建立面向透明纳米晶析出的双阶段晶化热处理制度;同时,开发适用于LAS玻璃浮法成型与微晶玻璃压延成型的温度-黏度曲线拟合体系,为高强度透明玻璃的工程化制备提供基础。在 LAS 玻璃方面,系统研究了 Al2O3/SiO2比、B2O3、ZrO2、CaO/MgO比及Na2O/Li2O比对玻璃结构和力学性能的影响,建立了与IOX相关的应力存储与安全评估体系。优化后代表性配方 E3 玻璃(66.4SiO2-2.1B2O3-10.0Al2O3-3.5MgO-4.0Na2O-10.0Li2O-1.5ZrO2-2.5CaO)具有优异的力学性能,弹性模量达84.36GPa,CTLD＿max为75213.98 MPa,CTLD＿saf为52293.06MPa,温度-黏度特性适用于浮法成型,具备工业化可行性。在LAS透明微晶玻璃方面,构建了基于纳米晶体析出的晶化路径,明确了P2O5等成核剂作用机制,控制晶体尺寸与相对密度。通过CaO与Na2O/Li2O比例调控,实现力学与光学性能协同提升。代表配方LN15(22.0Li2O-1.5Na2O-4.0Al2O3-0.9P2O5-2.5ZrO2-1.0CaO-0.1SnO2-67.5SiO2)具备高达74.7%的晶体体积分数,弹性模量为102.92 GPa,CTLD＿saf为45504.31 MPa,Lab值为 96.37、-0.03、1.82,雾度仅为 0.62%,具有优异的结构强度与光学透过性。其温度-黏度性能匹配压延工艺要求,是本研究开发的最优透明微晶玻璃配方。本研究围绕强度提升与光学透过性之间的协同优化,构建了一套从玻璃到微晶玻璃、从材料设计到工艺实现的系统方法,为高性能盖板玻璃、特种光学玻璃及防护玻璃的自主研发提供了理论支撑与技术路径,推动国产高端功能玻璃材料的工程化进程。更多还原

【Abstract】 Since the first-generation iPhone adopted ultra-thin high-strength cover glass in 2007,such materials have found widespread application in smart terminals.With increasing functional integration and the drive for thinner and lighter devices,cover glass is now expected to meet the technical demand for being "thinner and stronger." Conventional high-alumina silicate glass has reached a performance plateau by expanding the network structure to optimize ion exchange（IOX）channels.To achieve a breakthrough in strength,transparency,and industrial scalability,transparent glass-ceramics with high crystalline content have gradually emerged as promising candidates for next-generation cover materials.However,systematic studies on the composition design,mechanism understanding,and engineering processes of high-strength specialty glass and transparent glass-ceramics remain limited both domestically and internationally.Commissioned by Huawei Terminal and Huawei Technologies,this study focuses on high-strength lithium aluminosilicate（LAS）glass and its transparent glass-ceramics,undertaking a comprehensive investigation encompassing compositional design,computational model refinement,microstructural regulation,and process compatibility.The goal is to establish a theoretical and engineering framework for optimizing glass strength.A gradient doping strategy,combined with modifications to the Gan-Fuxi model and mechanical property prediction methods,is used to construct a quantifiable stress analysis system based on central tension linear density（CTLD）.Differential scanning calorimetry（DSC）,X-ray diffraction（XRD）,Raman spectroscopy,and transmission electron microscopy（TEM）are employed to elucidate the nucleation,structural evolution,and phase transformation mechanisms of glass-ceramics under various heat treatment conditions.A two-stage crystallization schedule targeting transparent nanocrystal precipitation is developed.Additionally,a temperature-viscosity fitting model suitable for LAS float forming and glassceramic calendering is proposed,providing a foundation for scalable manufacturing.For LAS glass,the effects of the Al2O3/SiO₂ ratio,B2O3,ZrO₂,CaO/MgO ratio,and Na2O/Li2O ratio on structure and mechanical properties were systematically investigated.A safety evaluation and stress storage system related to ion exchange was established.The optimized composition E3 glass（66.4SiO₂-2.1B2O3-10Al2O3-3.5MgO-4Na2O-10Li2O1.5ZrO₂-2.5CaO）exhibited excellent mechanical properties with an elastic modulus of 84.36GPa,CTLD＿max of 75,213.98MPa,and CTLD＿saf of 52,293.06MPa.Its temperatureviscosity profile meets the requirements for industrial float forming,indicating high manufacturability.For LAS transparent glass-ceramics,a crystallization pathway based on nanocrystal precipitation was constructed,and the nucleation mechanism of P2O5 and related agents was clarified to control crystal size and phase density.By adjusting the CaO and Na2O/Li2O ratios,simultaneous improvements in mechanical and optical properties were achieved.The representative composition LN15（22Li2O-1.5Na2O-4 Al2O3-0.9P2O5-2.5ZrO₂-1 CaO0.1SnO₂-67.5SiO₂）reached a crystalline volume fraction of 74.7%,with an elastic modulus of 102.92GPa,CTLD＿saf of 45,504.31MPa,Lab values of 96.37,-0.03,1.82,and a haze of only 0.62%,indicating outstanding structural strength and optical transmittance.Its temperature-viscosity behavior aligns with the requirements of roll-forming processes,making it the optimal transparent glass-ceramic formulation developed in this study.Focusing on the synergistic optimization of mechanical strength and optical transmittance,this research establishes a systematic methodology—from glass to glass-ceramics and from material design to process realization.It provides theoretical support and technological pathways for the independent development of high-performance cover glass,specialty optical glass,and protective glass,thereby advancing the engineering and industrialization of highend functional glass materials in China.更多还原