CaO－Al_2O_3－SiO_2系白色微晶玻璃中的晶相及其演变

应用差热分析和Ｘ射线衍射谱研究了若干以ＺｎＳ为晶核剂的Ｒ２Ｏ－ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系白色微晶玻璃．根据差热结果确定了四个不同的晶化处理温度．晶化结果表明：本系统玻璃在较低温度下即开始晶化，且均以α－硅灰石为主晶相，这可用ＺｎＳ与α－硅灰石间晶核常数的匹配来解释．当晶化处理温度高于９５０℃，多数玻璃中发生主晶相由α－硅灰石向β－硅灰石或透辉石转化，这从键能角度可以理解．     

晶核剂对Li2 O-Al2 O3-SiO2系统微晶玻璃结构和性能的影响

通过传统熔体冷却法制得了以P2O5和TiO2为晶核剂的Li2O-Al2O3-SiO2系统基础玻璃,并经过热处理制得了微晶玻璃.利用红外光谱分析、X射线衍射分析和扫描电子显微镜等对晶化试样的物相和显微结构进行了研究,着重探索了不同晶核剂对玻璃析晶、微晶玻璃结构、微晶玻璃力学和热学性能的影响.结果表明:TiO2更有利于玻璃析晶,但以P2O5为晶核剂的微晶玻璃具有更好的力学和热学性能.     

废玻璃制备蓝色玻璃陶瓷及其力学性能研究

使用废弃窗玻璃粉作为原料,分别加入顽辉石、钙铝黄长石及氟云母三种析晶促进剂,添加蓝色颜料后采用反应析晶烧结法分别制备蓝色透辉石玻璃陶瓷、蓝色硅灰石玻璃陶瓷与蓝色氟闪石玻璃陶瓷。研究蓝色颜料添加量对玻璃陶瓷的物相、形貌和力学性能的影响。结果表明：制得的蓝色透辉石玻璃陶瓷的主晶相为透辉石,次晶相为霞石;蓝色硅灰石玻璃陶瓷的主晶相为硅灰石;蓝色氟闪石玻璃陶瓷的主晶相为氟闪石,次晶相为透辉石。添加适量蓝色颜料时,析出晶体与玻璃基质结合较为紧密,过量添加会降低其性能。当添加1.5 g蓝色颜料时,蓝色硅灰石玻璃陶瓷着色性最好,力学性能最佳,其断裂模数为24.48 MPa。     

Fe2+、Fe3+对CaO-Al2O3-SiO2-MgO系微晶玻璃析晶性能的影响规律

为了利用大量的含铁铝硅酸盐固体废弃物制备具有高附加值的微晶玻璃,采用DTA、XRD、SEM、EDS等手段研究了Fe2+、Fe3+对CASM系微晶玻璃析晶性能的影响.结果表明,Fe2+在微晶玻璃中与Mg2+的作用相同,取代以网络外体形式存在的Al3+,使得微晶玻璃的析晶温度逐渐下降,而对析晶能力几乎没有影响,并当Fe2+掺入量为2%时,主晶相由铝黄长石转变为镁黄长石,在7.5%时,进一步转变为透辉石.Fe3+掺量小于7.5%时,起到补充Si4+不足的作用,当大于7.5%时,部分Fe3+起到与Fe2+、Mg2+相同的作用,使得析晶温度呈先升后降的变化,在掺量为7.5%时,铝黄长石主晶相才开始转变为镁黄长石,在10%时,转变为透辉石,且析晶能力得到大幅提升.随着Fe2+和Fe3+含量增加,虽然微晶玻璃中主晶相的变化顺序相同,但Fe2+具有降低微晶玻璃析晶温度的作用,而一定量的Fe3+可作为晶核剂提高微晶玻璃的析晶能力.     

CaO-MgO-Al2O3-SiO2-F系统微晶玻璃的析晶行为和力学性能

以CaO-MgO-Al2O3-SiO2-F系统微品玻璃为基础,通过调整基础玻璃成分和热处理工艺得到了主晶相为透辉石并含有氟金云母相的微晶玻璃.采用XRD和SEM等测试手段分析了析晶行为和显微组织形貌,并研究了力学性能与显微结构之间的关系.结果表明:CaF2的加入促进了体系的整体析晶并成为其他晶相的异质形核中心;试样的力学性能与显微组织有很大的关系,当试样在800℃热处理2h后,晶粒细小结构致密,具有较高的抗弯强度和断裂韧性.     

晶核剂及热处理对锂铝硅系微晶玻璃晶化和性能的影响

采用差热分析法研究了LAS玻璃的析晶动力学,讨论了4.5wt%TiO2和2wt%TiO2 2.5 wt% ZrO2两种晶核剂对该系统玻璃晶化过程的影响.通过正交实验确定了玻璃晶化的最优热处理制度,并研究了热处理对微晶玻璃的晶相、显微结构及热膨胀性能的影响.结果表明:与采用TiO2单一晶核剂相比,采用TiO2 ZrO2复合晶核剂的玻璃析晶活化能E降低,晶化指数n加大,体积析晶趋势增大.热处理制度能控制晶相的析出,析晶初始温度下首先析出的晶体为β石英固溶体,晶化温度升高转变为β锂辉石固溶体,可以使样品的热膨胀性能符合要求,最优的热处理制度(使热膨胀系数最小)为:核化温度720℃,核化时间1.5小时,晶化温度810℃,晶化时间2.5小时.     

CaO—Al2O3—SiO2系白色微晶玻璃中的晶相及其演变

应用差热分析和Ｘ射线衍射谱研究了若干以ＺｎＳ为晶核剂的Ｒ２Ｏ－ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２系白色微晶玻璃。根据差热结果确定了四个不同的晶化处理温度。晶化结果表明：本系统玻璃在较低温度下即开始晶体，且均以α－硅灰石为主晶相，这可用ＺｎＳ与α－硅灰石间晶核常数的匹配来解释。     

复合形核剂对CaO-MgO-Al2O3-SiO2系玻璃陶瓷微观结构与力学性质的影响

以CaO、MgO、Al2O3和SiO2为主要原材料,采用熔融法制备添加复合形核剂Cr2O3和CaF2的CaO-MgO-Al2O3-SiO2 (CMAS)系玻璃陶瓷,借助X射线衍射(XRD)、扫描电子显微镜(SEM)和电子万能试验机等测试手段研究了复合形核剂对CMAS系玻璃陶瓷微观结构与力学性质的影响.结果表明:当试样中复合形核剂的组成变化时,其析出的主晶相类型不变,均为透辉石,主晶相的结构和含量发生变化,引起玻璃陶瓷力学性质的改变.     

Fe2+、Fe3+对CaO-Al2O3-SiO2-MgO系微晶玻璃析晶性能的影响规律

为了利用大量的含铁铝硅酸盐固体废弃物制备具有高附加值的微晶玻璃,采用DTA、XRD、SEM、 EDS等手段研究了Fe₂₊、Fe₃₊对CASM系微晶玻璃析晶性能的影响,结果表明,Fe₂₊在微晶玻璃中与Mgz+的 作用相同,取代以网络外体形式存在的Al₃₊,使得微晶玻璃的析晶温度逐渐下降,而对析晶能力几乎没有影 响,并当Fe₂₊掺入量为2%时,主晶相由铝黄长石转变为镁黄长石,在7.5%时,进一步转变为透辉石．Fe₃₊掺 量小于7.5%时,起到补充S14不足的作用,当大于7.5%时,部分Fe₃₊起到与Fe₂₊、Mg₂₊相同的作用,使得 析晶温度呈先升后降的变化,在掺量为7.5%时,铝黄长石主晶相才开始转变为镁黄长石,在10%对,转变为 透辉石,且析晶能力得到大幅提升．随着Fe₂₊和Fe₃₊含量增加,虽然微晶玻璃中主晶相的变化顺序相同,但 Fe₂₊具有降低微晶玻璃析晶温度的作用,而一定量的Fe₃₊可作为晶核剂提高微晶玻璃的析晶能力     

CaO/SiO2质量比对不锈钢渣微晶玻璃析晶及性能的影响

以不锈钢渣、废玻璃为原料,采用熔融法制备了主晶相为硅灰石相的微晶玻璃.利用DSC、XRD、SEM等测试分析手段研究了CaO/SiO2质量比对微晶玻璃物相组成、显微结构及理化性能的影响.结果表明:随CaO/SiO2质量比增加,玻璃转变温度和析晶放热峰温度逐渐降低,且析晶放热峰变尖锐;硅灰石相XRD衍射峰强度先增强后减弱;显微结构由表面析晶向整体析晶过渡,晶粒形状由球形颗粒变为针叶状晶,最后发育成片状晶,晶体尺寸先增加后减小;当CaO/SiO2质量比为0.72时微晶玻璃性能达到较优,显微硬度为6.49 GPa,密度为3.11 g/cm3,吸水率为0.11％,耐酸性96.51％,耐碱性99.92％.制备出的微晶玻璃有望应用在建筑装饰材料领域.     

Study of bulk crystallization in MgO-CaO-SiO2-Na2O glasses in the presence of CaF2 and MoO3 nucleant

The crystallization process of MgO-CaO-SiO₂-Na₂O glasses in the presence of CaF₂ and MoO₃ nucleating agents was investigated by DTA, XRD and SEM. The effect of compositional changes on bulk crystallization and growth morphology has been studied. After a two-stage heat treatment, the phases such as wollastonite, diopside and cristobalite, were identified. The ability of CaF₂ and MoO₃ pair as nucleating agents in inducing bulk nucleation in these glasses was attributed to the surface tension and viscosity reductions. The observed pore formation phenomenon upon the increase of MgO content in these glass-ceramics was related to the difference in density between the residual glass and diopside as the main crystalline phase.     

Effect of heating rate on the responses of CaF2:Cu,CaF2:Tm,CaF2:Dy and CaF2:Mn

Recent development of CaF2:Cu (the most sensitive material for radiation dosimetry) exhibiting a TL glow peak around 270 degrees C similar to that of CaF2:Mn has made it attractive to study the influence of heating rate on the response of CaF2 based TLDs. Influence of heating rate on CaF2:Mn (known to reduce the response with increasing heating rate) was confirmed in view of the reported controversy about other TLDs. Responses of TL glow peaks around 270 degrees C in CaF2:Cu, CaF2:Tm, CaF2:Dy and CaF2:Mn were studied. Except CaF2:Mn, no other CaF2 based TLD exhibited a reduction in response with increasing heating rate. On the contrary, in some cases a small increase (10-15%) was noted with increasing heating rate from 1 degrees Cs(-1) to 50 degrees Cs(-1). The shape and the position of the glow peak and the parameters derived from the shape of the glow curve appear to have no relation to reduction of TL efficiency at higher heating rates. Apart from the increased probability of non-radiative transitions at higher temperatures, the observed effects have been assigned to the effect of heating rate on the migration of charge carriers released during the TL readout.     

Ion-assisted codeposition of CaF2-rich CaF2-TiO2 composites as infrared-transmitting films

The influence of the TiO(2) concentration (相似文献   

CaF2在真空铝热还原炼镁过程中的行为研究

对CaF2在以白云石和菱镁石为原料的铝热还原过程中的行为进行了研究,通过X射线衍射对还原渣和结晶产物的物相进行了分析,对CaF2在铝热还原过程的反应过程以及加速还原反应的机理进行了探讨。实验研究结果表明,在还原过程中加入CaF2可降低还原反应的活化能,加快还原反应速率,可使还原过程中的氧化镁还原率提高3%以上,但添加CaF2的效果随还原温度的升高而降低。加入CaF2后一部分CaF2参与还原反应生成了11CaO.7Al2O3.CaF2,另外一部分CaF2被铝还原在结晶器上生成了一种主要成分为MgF2和Al的结晶物。CaF2对铝热还原反应的促进作用是化学反应促进和提高煅白表面活性共同作用的结果。     

利用Langmuir单层膜诱导合成CaF2单晶

利用SEM、XPS、XRD等手段研究了以山嵛酸（BA）Langmuir单层膜为模板在位诱导氟化钙单晶的生长情况．结果表明，在山嵛酸单分子膜诱导作用下，形成的氟化钙晶体形状比较规则、边缘清晰、尺寸较大，且沿（111）晶面取向生长．这一结果可以通过CaF2晶体的（111）面与山嵛酸Langmuir膜之间存在的一定晶格匹配得到合理解释．     

Novel SiO2-deposited CaF2 substrate for vibrational sum-frequency generation (SFG) measurements of chemisorbed monolayers in an aqueous environment

A novel SiO(2)-deposited CaF(2) (SiO(2)/CaF(2)) substrate for measuring vibrational sum-frequency generation (SFG) spectra of silane-based chemisorbed monolayers in aqueous media has been developed. The substrate is suitable for silanization and transparent over a broad range of the infrared (IR) probe. The present work demonstrates the practical application of the SiO(2)/CaF(2) substrate and, to our knowledge, the first SFG spectrum at the solid/water interface of a silanized monolayer observed over the IR fingerprint region (1780-1400 cm(-1)) using a back-side probing geometry. This new substrate can be very useful for SFG studies of various chemisorbed organic molecules, particularly biological compounds, in aqueous environments.     

Thermal properties and devitrification behaviour of (1+x)CaO·(1−x)MgO·2SiO2 glasses

The thermal properties (glass transformation, T _g, and softening, T _s, temperatures), the crystalline phases formed during heating in a differential thermal analysis (DTA) apparatus, the kinetic parameters and the mechanism of the devitrification process, of glasses of the system diopside-wollastonite were investigated. The substitution of CaO by MgO induces an increase in T _g and the crystal growth activation energy, E _c; this is probably linked to the greater coordination number of Ca^z+ ions with respect to the Mg²⁺ ions. The substitution of CaO by MgO lowers the nucleation rates of the diopside phase; wollastonite solid solution nuclei form whose growth appears to leave a glassy matrix in which diopside formation is inhibited. Only surface nucleation was observed, but, in finely powdered samples, which soften and efficiently sinter before devitrifying, surface nuclei behave as bulk nuclei. When bulk crystallization occurs, the Avrami parameter m was found to be 2 for all glasses, except the diopside one, for which m=3.     

ATP/CaF_2∶Ln~(3+)(Ln∶Eu,Tb,Ce/Tb)纳米粒子的制备及其荧光性能

采用两步法制备了三磷酸腺苷二钠(ATP)修饰的ATP/CaF_2∶Ln~(3+)(Ln∶Eu,Tb,Ce/Tb)纳米粒子。采用红外光谱(IR)、X-射线衍射分析(XRD)、透射电子显微镜(TEM)对所合成的纳米粒子进行结构表征,并通过荧光光谱(FS)研究了纳米粒子的荧光性能。结构研究结果表明,ATP成功地包覆在纳米粒子的表面,纳米粒子的晶相为CaF_2的立方结构,ATP/CaF_2∶Eu~(3+)、ATP/CaF_2∶Tb~(3+)、ATP/CaF_2∶Ce~(3+)/Tb~(3+)纳米粒子的平均粒径分别约为14nm、15nm、11nm。荧光性能研究表明,ATP/CaF_2∶Eu~(3+)、ATP/CaF_2∶Tb~(3+)纳米粒子基本不发射稀土离子的特征荧光,而发射出修饰剂ATP的荧光,由于Ce~(3+)对Tb~(3+)的敏化作用,ATP/CaF_2∶Ce~(3+)/Tb~(3+)纳米粒子发射出Tb~(3+)的特征荧光。     

Initial stages of high-temperature CaF2/Si(001) epitaxial growth studied by surface X-ray diffraction

Surface X-ray diffraction was applied to study structure of the fluorite-silicon interface forming upon epitaxial growth of CaF2 on Si(001) surface kept at 750 degrees C. Samples with CaF2 coverage of 1.5-4 (110)-monolayers were grown and in-situ characterized using synchrotron radiation. The 3 x 1-like surface reconstruction was observed in agreement with the previous studies by electron diffraction. Interestingly, a well pronounced splitting of the fractional x 1/3 reflections was revealed. This splitting was ascribed to the effect of antiphase domain boundaries in the row-like structure of the interface layer. The in-plane integrated intensities were used to reconstruct two-dimensional atomic structure of the high-temperature CaF2/Si(001) interface.     

Solid state compatibilities in CaO–CaO.Al2O3–CaSO4–CaF2 system

The determination of the phases assemblages in equilibrium in the CaO–CaO.Al2O3–CaSO4–CaF2 system at 1100°C has been performed. Four assemblages are found and one more is deduced. 3CA.CaSO4 appears in all compatibility tetrahedra in solid state or in melt presence. It is compatible with C3A, C12A7ss, CA, C11A7.CaF2 and the aluminate formed depends on Al2O3 and CaF2 proportion, (cement chemistry abbreviations: C=CaO, A=Al2O3). © 1998 Kluwer Academic Publishers