纳米级SnO2或Yb2O3对熔融石英陶瓷析晶性能的影响

通过XRD分析和热膨胀率实验,从析晶角度探讨了添加纳米级SnO₂或Yb₂O₃对熔融石英陶瓷析晶性能的影响。结果表明:熔融石英陶瓷高温析晶的主要晶化产物为方石英,方石英析出量随烧结温度的提高而逐渐增多;纳米级SnO₂或Yb₂O₃的引入可通过抑制熔融石英中方石英的析出,有效地降低熔融石英材料在升温过程中的热膨胀率,并且随着烧结温度升高需要不断调整添加剂用量,纳米级SnO₂和Yb₂O₃的最佳用量(质量分数)分别为1%和2%。     

石英陶瓷高温熔融工况动态热响应特性试验及仿真研究

本文介绍了一种针对高超声速飞行器石英陶瓷防护罩在高温熔融工况下动态热响应特性试验方法,该试验方法通过燃气流发动机实现了石英陶瓷罩体高温瞬态热冲击性能考核试验条件.针对石英陶瓷罩体试验件开展了石英陶瓷材料晶相转变特性及表面微裂纹机理研究,获得了石英陶瓷材料在高温熔融工况下的烧蚀热响应特性.并对熔融工况试验过程及冷却过程中热应力分布进行了验证分析,对石英陶瓷材料在高超声速飞行器上的应用具有一定的指导意义.     

成型方法对纳米二氧化硅陶瓷烧结行为及微观结构的影响

以二氧化硅纳米粉为原料通过流延成型和模压成型两种不同成型方法制备纳米二氧化硅陶瓷,用X射线衍射仪对原料粉和陶瓷进行物相分析,用场发射扫描电子显微镜分析陶瓷微观形貌.结果表明,用流延成型坯体颗粒在1050℃时出现熔融现象并且开始形成晶格不完整的α-方石英相;而模压成型坯体颗粒在950℃时出现非常明显的熔融现象,并晶化生成晶格完整的α-方石英相,说明纳米氧化硅的烧结温度不仅远低于传统烧结温度,而且其晶化反应直接生成α-方石英结构,不会出现α-石英和鳞石英.同时用微晶学说解释了纳米氧化硅烧结过程的相变.     

晶核剂对锂锌硅系微晶玻璃析晶及显微结构的影响

采用差热分析方法研究了LZS系玻璃陶瓷的析晶动力学,讨论了晶核剂对微晶玻璃的晶相、显微结构及析晶动力学参数的影响.结果表明:与TiO2相比,P2O5能够更加有效地促进玻璃析晶,但两者效果相差不大.使用不同的晶核剂不会影响玻璃析出的晶相,但使用P2O5作为晶核剂能得到均匀细小的晶体.     

Nd3+∶ZnO-B2O3-Al2O3-SiO2系透明玻璃陶瓷的制备及表征

制备了Nd3+∶ZnO-B2O3-Al2O3-SiO2系透明玻璃陶瓷.运用差热分析(DTA)、X射线衍射(XRD)、扫描电镜(SEM)、NV-Vis-Nir(紫外可见近红外分光光度计)、傅里叶变换荧光光谱等测试方法,研究了晶核剂的含量对Nd3∶ZnO-B2O3-Al2O3-SiO2系透明玻璃陶瓷的核化和晶化性能的影响.利用修正的Kissinger方程研究了晶核剂对玻璃析晶动力学参数,析晶活化能E和析晶动力学判据k(Tp),利用Augis-Bennett方程计算出Avrami参数n.并分析其显微形貌同光透过率的关系,对光学性能进行了研究.     

废渣微晶玻璃析晶行为分析及热处理制度的优化

以镍渣及粉煤灰为主要原料,使用熔融法制备了复合渣微晶玻璃,渣的综合利用率达到62;,依据DSC曲线确定基础玻璃的热处理制度,并利用修正的JMA方程,对其进行了析晶动力学分析.借助极差分析、XRD、SEM等测试方法探讨了热处理制度对该系统微晶玻璃的影响.结果表明:复合渣微晶玻璃析晶活化能E=91.4 kJ/mol,动力学参数k(Tp)=0.277,n=3.04,该微晶玻璃以体析晶的方式析晶且析晶能力较强,主晶相为普通辉石和透辉石;热处理制度对玻璃体系的微观组织结构及力学性能均有较大影响,且温度因素大于时间因素;经730℃保温1.5h微晶化热处理后能获得晶粒细小均匀、力学性能良好的复合渣微晶玻璃.     

新型SiC/SiBCN复合陶瓷的析晶性能

通过热解聚碳硅烷(PCS)和聚硼硅氮烷(PBS)两种有机先驱体混合物,制得非晶态SiC/SiBCN复合陶瓷,然后对复合陶瓷进行高温热处理,研究其析晶规律及影响因素.利用热分析(TG-DTA)、X射线衍射(XRD)及透射电子显微镜(TEM)分别研究先驱体的热解机理,先驱体的组成、热解温度和时间对SiC/SiBCN复合陶瓷结晶性的影响,以及复合陶瓷的微观结构.结果表明,先驱体的组成和热处理温度对复合陶瓷的析晶行为有重要影响.当PBS/PCS=1(w/w),1100 ℃/2 h制得非晶态SiC/SiBCN复合陶瓷;1400 ℃/4 h PCS热解转变的非晶SiC开始结晶,晶粒尺寸～3 nm;1500 ℃/4 h 得到产物的相结构为～10 nm 的SiC纳米晶均匀弥散在PBS热解得到的非晶态SiBCN中;1700 ℃/2 h SiC的晶粒尺寸～16 nm;1800 ℃/2 h非晶态SiBCN开始析晶,SiC晶粒尺寸～35 nm.     

CaF2对自然冷却黄磷炉渣微晶玻璃析晶行为影响

借助DTA、SEM、XRD等分析测试手段,研究氟化钙晶核剂含量对自然冷却态黄磷炉渣微晶玻璃析晶及其性能的影响规律.利用修正后的JMA方程计算微晶玻璃的析晶活化能E及晶体生长指数n动力学参数.结果表明:CaF2晶核剂的引入可以促进微晶玻璃的析晶,改变析晶峰温度和活化能.随着CaF2进一步添加并不能改变主晶相(硅灰石)类型,而是生成新的CaF2晶相,同时改晶粒尺寸.当添加2.5wt; CaF2时,微晶玻璃的析晶动力学参数最优,产品性能优异,可以作为优良的建筑装饰材料.     

晶核剂对白云鄂博东尾矿微晶玻璃析晶及性能的影响

以白云鄂博东尾矿及粉煤灰为主要原料,采用熔融法制备得到了CaO-MgO-Al2O3-SiO2 (CMAS)系特种微晶玻璃.制备流程包括熔融、退火、核化及晶化过程.基于X射线衍射和拉曼光谱研究了微晶玻璃的晶相结构及分子振动模式、借助于扫描电子显微镜及原子力显微镜对微晶玻璃的耐磨及断裂特性进行了表征;利用差热分析研究了共生晶核剂对微晶玻璃核化及晶化过程的作用机理.结论表明:随着尾矿含量的逐渐降低,微晶玻璃的析晶特性及性能先增强后减弱.微晶玻璃的耐磨性主要由晶相决定,其断裂特性属于沿晶断裂,热膨胀系数的变化规律与析晶特性相一致.     

基于电沉积技术的纳米晶材料晶粒细化工艺研究

纳米晶材料电沉积工艺是在传统电沉积工艺的基础上,通过控制适当的工艺条件,最终获得具有各种性能的纳米晶电沉积层的过程.研究表明,由电沉积工艺制备的纳米晶材料,晶粒细小且组织均匀,具有耐磨、耐蚀、耐高温氧化等特殊性能.本文分析了在电沉积过程中纳米晶形成的机理,探讨了工艺参数、复合电沉积和脉冲电沉积、有机添加剂以及采用其它工艺措施对晶粒细化过程的影响.介绍了电沉积纳米晶材料的各种性能及应用.     

Surface crystallization of rare-earth aluminosilicate glasses

Surface crystallization in a rare-earth aluminosilicate glass (Nd₂O₃–Al₂O₃–SiO₂–TiO₂) was studied using an isothermal method and the crystal growth rate of the glasses was evaluated as a function of the composition. For measuring the surface crystal growth rate, two different methods: measurement of the crystal layer in the longitudinal and lateral growth direction. It was found that crystallization proceeded by surface crystallization only and TiO₂ did not act as a nucleating agent. The growth rate was strongly dependent on the viscosity of glass and agreed with prediction from the Preston model using the known viscosity and melting temperature. As the Si/Nd and Si/Al ratios decreased, the crystal growth rate increased. TiO₂ and Nd₂O₃ played the role of network modifier, which decreased the viscosity of the glass, facilitating crystallization of the rare-earth aluminosilicate glass.     

Structural and thermal properties of some tellurite glasses

Tellurium oxide glasses were prepared by the hammer and anvil technique. The glass systems are (0.85TeO₂ + 0.15Z), where Z = K₂O, TiO₂, V₂O₅, MnO, Fe₂O₃, CoO, NiO or CuO. A second group is a ternary system 0.85TeO₂+(0.15 − x)TiO₂ + xFe₂O₃) with x=0.0, 0.05, 0.1, 0.15 mol. X-ray diffraction, infrared spectroscopy and differential thermal analysis measurements were carried out. The present study showed the different glass-forming groups, the glass transition and crystallization temperatures as well as the crystallization processes.     

微波加热制备含稀土(La2O3)矿渣微晶玻璃研究

利用矿渣制备微晶玻璃是提高矿产资源利用率的主要形式之一。本文以白云鄂博尾矿为原料,采用微波一步法制备了CaO-MgO-Al₂O₃-SiO₂(CMAS)系辉石相矿渣微晶玻璃。选择835 ℃作为晶化温度,研究了微波加热对微晶玻璃析晶行为和微观组织的影响。以La₂O₃作为研究变量探讨了La₂O₃添加对矿渣微晶玻璃析晶行为的作用。与传统的热处理制度相比,微波加热可以在较短的时间内达到较高的析晶效果。同时La₂O₃的添加促进了晶粒细化。由拉曼光谱分析,La离子添加会导致玻璃网络中桥氧的增多,促进了辉石相析晶。在La的添加量为4%(质量分数)时硬度最高,达到了829.22 MPa。     

Influence of alternating electric fields on the crystallization of barium titanate glasses

The paper is concerned with the question as to how far low-frequency electric fields exert an influence on the crystallization process. The results for a glass of the composition 75 mol.% BaO---TiO₂, 19 mol.% SiO₂, 6 mol.% Al₂O₃ show that the samples which are influenced by electric fields have a higher degree of crystallization than the electrically uninfluenced samples under well-defined annealing conditions.     

In vitro degradation studies of calcium phosphate glass ceramics prepared by controlled crystallization

Calcium phosphate glass ceramics with incorporation of small additions of two nucleating agents, MgO and K₂O were prepared in the metaphosphate and pyrophosphate region, using an appropriate two-step heat treatment of controlled crystallization defined by differential thermal analysis results. Identification and quantification of crystalline phases precipitated from the calcium phosphate glass were performed using X-ray diffraction and Rietveld analysis. The β-Ca₂P₂O₇ (β-DCP), KCa(PO₃)₃, β-Ca(PO₃)₂ and Ca₄P₆O₁₉ phases were detected in the glass ceramics. In order to evaluate the degradation of the glass ceramics prepared, degradation studies were carried out during 42 days in Tris-HCl solution at 37 °C, pH 7.4, using granules in the range of 355–415 μm. The materials presented a weight loss ranging up to 12%. The ions leached during the immersion mainly originated from the KCa(PO₃)₃ phase, probably due to the presence of K⁺ ion in the calcium metaphosphate, and the residual glassy phase. The structural changes at the surface of materials during degradation have been analyzed by Fourier transform infrared spectroscopy and X-ray diffraction. Results showed that significant surface changes occurred with immersion time, with the decrease of KCa(PO₃)₃, β-Ca₂P₂O₇ and β-Ca(PO₃)₂ phases occurring at different periods of immersion. This study has demonstrated an easy way to prepared calcium phosphate materials with specific calcium phosphate phases and crystallization, and therefore specific degradation rates.     

Nanocrystallization of fresnoite glass. I. Nucleation and growth kinetics

We determined the internal nucleation, crystal growth and overall crystallization kinetics of fresnoite crystal (2BaO · TiO₂ · 2SiO₂) in an almost stoichiometric fresnoite glass. Due to the extremely high nucleation rates (10¹⁷ m⁻³ s⁻¹) that limit the maximum crystal size to 700 nm the nucleation densities and crystal sizes were estimated by scanning electron microscopy (SEM). The volume fraction crystallized was measured by X-ray diffraction. The nucleation rates obtained directly from SEM measurements reasonably agree with those calculated from the combination of overall crystallization with crystal growth kinetics. The activation enthalpies for viscous flow, transport of structural units across the nucleus/melt interface (nucleation) and crystal growth: ΔH_η, ΔH_τ and ΔH_U respectively, follow a similar trend to that observed for other stoichiometric silicate glasses that nucleate internally: ΔH_η=294>ΔH_τ=87>ΔH_U=61 kJ/mol. Fresnoite glass displays the highest internal nucleation rates so far measured in inorganic glasses. These rates are comparable to some metallic glasses and can lead to nanostructured glass-ceramics.     

Influence of the nucleation time-lag on the activation energy in non-isothermal crystallization

In the present work, the influence of the nucleation time-lag on the non-isothermal glass crystallization is discussed. Differential thermal analysis (DTA) results of an iron-rich glass nucleated by Cr₂O₃ were obtained at different heating rates. The activation energy of crystallization, E_c, and the Avrami parameter, m, estimated by Kissinger's and Ozawa's equations were shown to be dependent on the heating rate. The value of E_c, obtained at 2.5, 5 and 7.5 K/min heating rates was calculated as 299 kJ/mol, while the value of E_c, obtained at 10, 15 and 20 K/min was as 499 kJ/mol. The value of m for ‘low' and ‘high' heating rates were 2.57 and 1.45, respectively. The results were interpreted on the basis of the non-steady state nature of the nucleation process. It was assumed that at high heating rates no nucleation takes place and the crystals grow on a existing fixed number of nuclei; the activation energy of crystal growth, E_g, can be estimated by applying the Kissinger equations. At low heating rates nucleation occurs and the number of nuclei formed is influenced by the heating rate; E_g can be estimated by the Matusita and Sakka equation.     

Eu:Lu2O3透明闪烁陶瓷的制备与性能

采用湿化学法合成了Eu原子掺量5%的Lu₂O₃陶瓷前驱体,通过SEM、XRD研究了煅烧前后前驱体和1 100 ℃煅烧4 h后粉体的形貌、结构以及物相。结果表明煅烧后的粉体为纳米类球形、高分散且结晶性良好的颗粒。颗粒尺寸为68.5 nm。使用煅烧后的粉体为原料,在1 650 ℃真空烧结30 h制备了高透过率的Eu:Lu₂O₃陶瓷,晶粒尺寸为46 μm,在611 nm处的直线透过率可以达到66.3%。此外对陶瓷的吸收曲线、光致激发和发射光谱特性以及X射线激发发射光谱进行研究。可观察到,Eu:Lu₂O₃陶瓷存在基质和激活离子两类吸收,光致发光光谱和X射线激发发射光谱均可以看出Eu:Lu₂O₃陶瓷存在极强的⁵D₀→⁷F₂跃迁发光,位于611 nm处。对比商业的BGO单晶的X射线发射光谱,可得本实验中制备的陶瓷的光输出为85 000 ph/MeV。Eu:Lu₂O₃陶瓷本身有着高X射线以及高能粒子的阻止能力,结合高光输出特性,表明Eu:Lu₂O₃陶瓷在X射线成像等领域具有巨大的潜在应用价值。     

Precipitation of In2O3 nano-crystallites from glasses in the system Na2O/B2O3/Al2O3/In2O3

Glasses in the system Na₂O/B₂O₃/Al₂O₃/In₂O₃ were melted and subsequently tempered in the range from 500 to 700 °C. Depending on the chemical composition, various crystalline phases were observed. From samples without Al₂O₃, In₂O₃ could not be crystallized from homogeneous glasses, because either spontaneous In₂O₃ crystallization occurred during cooling, or other phases such as NaInO₂ were formed during tempering. The addition of alumina, however, controlled the crystallization of In₂O₃. Depending on the crystallization temperature applied, the crystallite sizes were in the range from 13 to 53 nm. The glass matrix can be dissolved by soaking the powdered glass in water. This procedure can be used to prepare nano-crystalline In₂O₃-powders.