【作者】 邵晶；

【导师】 苏春辉；

【作者基本信息】 长春理工大学 ， 材料物理与化学， 2008， 博士

【摘要】 本文综述了玻璃陶瓷的产生与发展过程。概述了玻璃陶瓷的组成、结构、合成方法、应用以及ZnO-Al₂O₃-SiO₂（ZAS）透明玻璃陶瓷的发展前景。采用熔融和晶化技术制备出以TiO₂为晶核剂的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷。根据差热分析结果制定玻璃的晶化热处理制度,基于X-ray衍射（XRD）分析结果确定了晶相组成和结构。析晶性能良好的ZAS系玻璃在670℃核化,740～810℃晶化,可获得主晶相为ZnAl₂O₄,次晶相为Zn₂SiO₄、SiO₂的锌铝硅透明玻璃陶瓷。组成的微小变化对晶相影响不明显。采用扫描电子显微镜（SEM）分析了样品的显微结构,采用X射线能量散射仪（EDX）对样品中的元素作了定性的分析。采用分光光度计测定ZAS玻璃陶瓷的光透过率,讨论了晶化热处理制度对光透过率的影响。采用熔融和晶化技术制备出以TiO₂为晶核剂,掺杂Nd₂O₃的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷。根据差热分析结果制定玻璃的晶化热处理制度,基于XRD分析结果确定了晶相组成和结构,讨论了热处理制度对晶相结构的影响。析晶性能良好的ZAS系玻璃在660℃核化,740～880℃晶化,可获得主晶相为立方锌尖晶石ZnAl₂O₄,次晶相为四面体β-SiO₂的锌铝硅透明玻璃陶瓷。热处理温度在1050℃以下的玻璃陶瓷中,主晶相只有唯一的立方锌尖晶石ZnAl₂O₄晶相析出。热处理温度在1050℃时,主晶相中四面体β—石英晶相开始析出,锌尖晶石变成次晶相,并且次晶相中有Zn₂SiO₄析出。由XRD结果计算出立方锌尖晶石晶体的晶格参数为α=0.8087nm（±0.0012）。采用分光光度计测定ZAS玻璃陶瓷的光透过率,讨论了晶化热处理制度对光透过率的影响。场发射-环境扫描电子显微镜（SEM）分析了样品的显微结构。采用X射线能量散射仪（EDX）对样品中的元素作了定性的分析。采用了傅立叶红外光谱仪（FT-IR）分析了样品的基团振动。测量了基质玻璃和不同热处理制度下样品的荧光光谱,探讨了晶相组成、结构对钕离子发光性能的影响。钕离子发光光谱与晶相组成和晶粒大小密切相关。中心波长位于885nm、1064nm和1337nm处的三个发光谱带分别对应于钕离子的⁴F_3/2→⁴I_9/2、⁴F_3/2→⁴I_11/2和⁴F_3/2→⁴I_13/2跃迁。并且对采用同一晶核剂,未掺杂稀土的样品1-1#和掺杂稀土的样品2-2#进行了光透过率的比较,发现掺入的Nd³⁺离子降低了玻璃陶瓷的光透过率。采用熔融和晶化技术制备出以TiO₂为晶核剂,掺杂NdF₃的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷。根据差热分析结果制定玻璃的晶化热处理制度,基于XRD分析结果确定了晶相组成和结构,讨论了热处理制度对晶相结构的影响。析晶性能良好的ZAS玻璃在670℃,1h核化,730℃,1h晶化,可分别获得主晶相为立方锌尖晶石ZnAl₂O₄,次晶相为四面体β-SiO₂、Zn₂SiO₄的锌铝硅透明玻璃陶瓷。当提高核化时间和晶化时间后,ZnF₂开始析出。当晶化温度提高到1040℃时主晶相只有唯一的四面体β-SiO₂析出,ZnAl₂O₄变为次晶相的玻璃陶瓷。采用X射线能量散射仪（EDX）对样品中的元素作了定性的分析。采用X射线光电子能谱（XPS）研究了玻璃陶瓷的近程结构。测量了基质玻璃和不同热处理制度下样品的荧光光谱。中心波长位于881nm、1063nm和1334nm处的三个发光谱带分别对应于钕离子的⁴F_3/2→⁴I_9/2、⁴F_3/2→⁴I_11/2和⁴F_3/2→⁴I_13/2跃迁。样品的受激发射截面比基质玻璃提高了。钕离子富集在具有降低声子能量的ZnF₂晶相中。并且对采用同一晶核剂,掺杂Nd₂O₃的样品2-2#和掺杂NdF₃的样品3-3#进行了光透过率和荧光光谱的比较,发现掺入的NdF₃的样品3-3#因为增加了ZnF₂次晶相降低了玻璃陶瓷的光透过率;但是提高了样品的发光强度。采用熔融和晶化技术制备出以CaF₂为晶核剂,掺杂NdF₃的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷。根据差热分析结果制定玻璃的晶化热处理制度,基于XRD分析结果确定了晶相组成和结构,讨论了热处理制度对晶相结构的影响。ZAS基质玻璃在670℃核化,740℃-800℃晶化,可分别获得SiO₂为主晶相,Zn₂SiO₄、CaF₂为次晶相的玻璃陶瓷样品;SiO₂为主晶相,Zn₂SiO₄、ZnAl₂O₄、CaF₂为次晶相的锌铝硅透明玻璃陶瓷样品。采用X射线能量散射仪（EDX）对样品中的元素作了定性的分析。采用X射线光电子能谱（XPS）研究了玻璃陶瓷的近程结构。测量了基质玻璃和不同热处理制度下样品的荧光光谱。中心波长位于896nm、1064nm和1329nm处的三个发光谱带分别对应于钕离子的⁴F_3/2→⁴I_9/2、⁴F_3/2→⁴I_11/2和⁴F_3/2→⁴I_13/2跃迁。样品的受激发射截面比基质玻璃提高了。钕离子富集在具有降低声子能量的CaF₂晶相中。并且对采用不同晶核剂,掺杂NdF₃的样品3-3#和4-4#进行了光透过率和荧光光谱的比较,发现晶核剂为CaF₂的样品光透过率和发光强度提高。用自动图像分析技术后获得了掺杂NdF₃以CaF₂为晶核剂的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷样品的显微结构参数,运用体视学的原理和方法研究了掺杂NdF₃以CaF₂为晶核剂的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷的显微结构,探究了显微结构与光学性能的关系。光透过率随着晶粒三维球相当径和单位体积内晶粒平均比表面积的增加而降低;光透过率随着晶粒三维平均自由距离的增加和单个晶粒的平均比表面积的增加而增加。对掺杂NdF₃以CaF₂为晶核剂的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷的显微结构进行了分形描述,证明了掺杂NdF₃以CaF₂为晶核剂的ZnO-Al₂O₃-SiO₂（ZAS）系透明玻璃陶瓷具有分形特征。更多还原

【Abstract】 This dissertation presented that the origin and development.The compositions, structure and processes of glass-ceramics were discussed.The synthetic methods and applications of glass-ceramics were outlined,and the developing trend of ZnO-Al₂O₃-SiO₂（ZAS） was forecasted.Transparent ZnO-Al₂O₃-SiO₂（ZAS） system glass-ceramics using TiO₂ as nucleating agent were prepared by the melting method and crystal technique.The crystallization heat-treated schedules were based on DTA results.The compositions and structure of crystal phases were determined on the base of XRD results.The transparent ZAS glass-ceramics with main crystal phase- ZnAl₂O₄ and minor crystal phase- SiO₂ solid solutions,Zn₂SiO₄,SiO₂ were obtained after ZAS system glasses with good crystallization ability were nucleated at 670℃and crystallized at 740～810℃.It was shown that the little change to the compositions influenced the crystal phases unmarkedly.The element composition of the sample were analyzed by determining the nature by EDX.The optical transmittances of the ZAS glass-ceramics were measured by spectrophotometer.The influences of crystallization heat-treated schedules to the optical transmittance were discussed.Transparent ZnO-Al₂O₃-SiO₂（ZAS） system glass-ceramics Nd₂O₃-doped using TiO₂ as nucleating agent were prepared by the melting method and crystal technique. The crystallization heat-treated schedules were based on DTA results.The compositions and structure of crystal phases were determined on the base of XRD results.The transparent ZAS glass-ceramics with main crystal phase- cubic gahnite ZnAl₂O₄ and minor crystal phase-tetrahedronβ-SiO₂ solid solutions were obtained after ZAS system glasses with good crystallization ability were nucleated at 660℃and crystallized at 740～880℃.The unique crystal phase-gahnite was precipitated below 1050℃,tetrahedronβ-SiO₂ solid solutions begin to precipitate at1050℃and become to the main crystal phase at 1050℃,and at the same time,gahnite became to the minor crystal phase and minor crystal phases-Zn₂SiO₄ was precipitated The lattice parameter of cubic gahnite calculated by XRD results isα=0.8087nm（±0.0012）.The optical transmittances of the glass-ceramics were measured by spectrophotometer. The influences of crystallization heat-treated schedules to the optical transmittance were discussed.The microstructure of the transparent ZAS system glass-ceramics was analyzed by SEM,The element composition of the sample were analyzed by determining the nature by EDX.The fluorescence spectra of the base glass and glass-ceramic heat-treated at different schedules were measured.The influences of crystal phase compositions and microstructure were discussed.Phase compositions and grain size of glass-ceramics were found to affect their fluorescent characteristics considerably.Three main fluorescence bands centering at about 885nm,1064nm and 1337nm were observed,which were correspondent to the transitions of ⁴F_3/2→⁴I_9/2, ⁴F_3/2→⁴I_11/2 and ⁴F_3/2→⁴I_13/2,respectively.The optical transmittances of the ZAS glass-ceramics decreased with the Nd³⁺doped after comparing sample 1-1# without Nd³⁺- doped and 2-2# with Nd³⁺- doped. Transparent ZnO-Al₂O₃-SiO₂（ZAS） system glass-ceramics NdF₃-doped using TiO₂ as nucleating agent were prepared by the melting method and crystal technique. The crystallization heat-treated schedules were based on DTA results.The compositions and structure of crystal phases were determined on the base of XRD results.The transparent ZAS glass-ceramics with main crystal phase- cubic gahnite ZnAl₂O₄ and minor crystal phase-tetrahedronβ-SiO₂ solid solutions and Zn₂SiO₄ were obtained after ZAS system glasses with good crystallization ability were nucleated at 670℃for 1h and crystallized at 730℃for 1h.The crystal phase- ZnF₂ was precipitated with time of crystallization and nucleation increasing.The unique main crystal phase-tetrahedronβ-SiO₂ solid solutions were precipitated and gahnite became to the minor crystal phase in the transparent glass-ceramics when nucleation temperature reached 1040℃.The element composition of the sample were analyzed by determining the nature by EDX.The short-range structure of the transparent glass-ceramics samples was researched by XPS.The fluorescence spectra of the base glass and glass-ceramic heat-treated at different schedules were measured.Three main fluorescence bands centering at about 881nm,1063nm and 1334nm were observed, which were correspondent to the transitions of ⁴F_3/2→⁴I_9/2,⁴F_3/2→⁴I_11/2 and ⁴F_3/2→⁴I_13/2, respectively.The effectively induced cross sectionσ_in of Nd³⁺ ions locating in crystal phase-ZnF₂ of the transparent glass-ceramics sample at 1065nm advanced than in base glass.The fluorescence spectra and the optical transmittances of the Nd₂O₃-doped 2-2# ZAS transparent glass-ceramics and NdF₃-doped 3-3# ZAS transparent glass-ceramics respectively with the same nucleating agent were compared.The optical transmittances decreased and the illuminant intensity improved when the minor crystal phase-ZnF₂ was precipitated in NdF₃-doped 3-3# ZAS transparent glass-ceramics.Transparent ZnO-Al₂O₃-SiO₂（ZAS） system glass-ceramics NdF₃-doped using CaF₂ as nucleating agent were prepared by the melting method and crystal technique. The crystallization heat-treated schedules were based on DTA results.The compositions and structure of crystal phases were determined on the base of XRD results.The transparent ZAS glass-ceramics with main crystal phase- SiO₂ solid solutions and minor crystal phase-Zn₂SiO₄,CaF₂ and the transparent ZAS glass-ceramics with main crystal phase- SiO₂ solid solutions minor crystal phaseZn₂SiO₄, ZnAl₂O₄ and CaF₂ were obtained after ZAS system base glasses were nucleated at 670℃and crystallized at 740℃-800℃.The element composition of the sample were analyzed by determining the nature by EDX.The short-range structure of the transparent glass-ceramics samples was researched by XPS.The fluorescence spectra of the base glass and glass-ceramic heat-treated at different schedules were measured.Three main fluorescence bands centering at about 896nm,1064nm and 1329nm were observed,which were correspondent to the transitions of ⁴F_3/2→⁴I_9/2, ⁴F_3/2→⁴I_11/2 and ⁴F_3/2→⁴I_13/2,respectively.The effectively induced cross sectionσ_in of Nd³⁺ ions locating in crystal phase-CaF₂ of the transparent glass-ceramics sample at 1064nm advanced than in base glass.The fluorescence spectra and the optical transmittances of the NdF₃-doped 3-3# ZAS transparent glass-ceramics NdF₃-doped using TiO₂ as nucleating agent and NdF₃-doped 4-3# ZAS transparent glass-ceramics NdF₃-doped using CaF₂ as nucleating agent respectively with the same nucleating agent were compared.The optical transmittances and the illuminant intensity improved of 4-3# ZAS transparent glass-ceramics NdF₃-doped using CaF₂ as nucleating agent.The microstructure of the transparent ZAS glass-ceramic samples NdF₃-doped using CaF₂ as nucleating agentwas analyzed by SEM,and the microstructure parameters were obtained by means of automatic image analysis technique.The microstructure was studied by stereology principles and method,and the relationship between the microstructure and the optical properties was explored.The optical transmittance decreased with the increasing of the three-dimensional sphere diameters and the mean specific area of grains per volume.The optical transmittance increased with the enhancing of the mean three-dimensional free distance of grain boundaries and the mean specific area of single grain.The microstructure of ZAS transparent glass-ceramics was described by using fractal theory,it was proved that transparent ZnO-Al₂O₃-SiO₂（ZAS） system glass-ceramics are of fractal characterizations.更多还原