Effects of Nucleating Additives on Crystallization and Properties of CaO-B_2O_3-SiO_2 Glass-ceramics

ZrO2, TiO2 and P2O5 were doped in CaO-B2O3-SiO2 glass-ceramics as nucleating additives. Effects of different nucleating additives on the phase separation and crystalline behaviors were investigated by using gradient temperature furnace, DTA and XRD. Then, sintering process of the glass-ceramics was investigated by testing sintering shrinkage, dielectric constant and loss. The experimental results shows that the glass-ceramics doped with nucleating additives represents higher crystallization, with ZrO2 as an exceptional effective dopant to promote the precipitation of wollastonite crystal. Finally, ZrO2 containing glass-ceramics was chosen to study the influence of sintering temperature and soaking time with the help of X-ray diffraction analysis and density measurement. The glass-ceramics can be well consolidated at 850 ℃ for 10 min, with low dielectric constant （5.87） and loss （3.21×10^-4）, which is desirable for LTCC application.

Preparation and Optical Properties of Er^3+:Na2O-Al2O3-SiO2 Transparent Glass-Ceramics

Na2O-Al2O3-SiO2 glass-ceramics doped with Er^3＋ ions were synthesized by the conventional melt quenching technique at a low melting temperature.The samples were characterized by differential scanning calorimetry（DSC）,X-ray diffraction（XRD）,scanning electron microscopy（SEM）,UV-vis-NIR scanning spectrophotometry,and fluorescence spectrometry.The results show that the main crystalline phase of glass-ceramics is nepheline.The best heat-treatment process is at 520 ℃ for 2 h.Because the up-conversion luminescence and near infrared luminescence properties of glass doped with Eu^3＋ are studied in detail.

Effect of nucleating agents on microstructure and mechanical properties of SiO_2-Al_2O_3-ZrO_2 glass-ceramics

SiO2-Al2O3-ZrO2 glasses with different nucleating agents were crystallized under special processing schedule. The microstructure and mechanical properties of the glass-ceramics in SiO2-Al2O3-ZrO2 system were investigated by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction and three-point bending method. The results show that ZrO2 is not an effective nucleating agent in SiO2-Al2O3-ZrO2 system, while TiO2 is effective for the separation of spinel, and P2O5 facilitates solubility of ZrO2 in glass and crystallization. The main crystalline phases of the glass-ceramics are spinel, anorthite and tetragonal zirconia. With the increase of ZrO2 content in the glass, glass-ceramics show higher bending strength （120MPa） than others.

Thermal Behavior and Lithium Ion Conductivity of L_2O-Al_2O_3-TiO_2-SiO_2-P_2O_5 Glass-ceramics

A lithium ion conductive solid electrolyte, L20-AI203-TiO2-SiO2-P20s glass with NASICON- type structure have been synthesized and transformed into glass-ceramic through thermal-treatment at various temperatures from 700 to 1 000 ~C for 12 h. The differential scanning calorimetry （DSC）, X-ray diffraction （XRD）, scanning electron microscopy （SEM） and complex impedance techniques were employed to characterize the samples. The experimental results indicated that the capability of glass forming in this system is superior to that of L20-A1203-TiO2-PzO~. The glass has an amorphous structure and resultant glass-ceramic mainly consisting of LiTi2（PO4）3 phases. Impurity phases AIPO4, TiO2, TiP207 and unidentified phase were observed. With the enhanced heat-treatment temperature, grain grew gradually and lithium ion conductivity of glass-ceramics increased accordingly, the related impedance semicircles were depressed gradually and even disappeared, which could be analytically explained by the coordinate action of the ＇Constant phase element＇ （CPE） model and the ＇Concept of Mismatch and Relaxation＇ model （CMR）. When the sample is devitrified at 1 000 ~C, the maximum room temperature lithium ion conductivity comes up to 4.1 x 10-4 S/cm, which is suitable for the application as an electrolyte of all-solid-state lithium batteries.

Crystallization and Luminescence Properties of Sm3＋-Doped SrO-Al2O3-SiO2 Glass-Ceramics

The Sm^（3＋）-doped SrO-Al2O3-SiO2（SAS） glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated by DTA, XRD, SEM and luminescence spectroscopy. The results indicate that the crystal phase precipitated in this system is monocelsian（SrAl2Si2O） and with the increase of nucleation/crystallization temperature, the crystallite increases from 66 % to 79 %. The Sm（3＋）-doped SAS glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm under the excitation of 475 nm blue light which can be assigned to the 4 G5/2→6 Hj/2（j=5, 7, 9, 11） transitions ofSm^（3＋）, respectively. Besides, by increasing the crystallization temperature or the concentration ofSm^（3＋）, the emission lights of the samples located at 565, 605 and 650 nm are intensified significantly. The present results demonstrate that theSm^（3＋）-doped SAS glassceramics are promising luminescence materials for white LED devices by fine controlling and combining of these three green, orange and red lights in appropriate proportion.

Rubidium-modified bioactive glass-ceramics with hydroxyapatite crystals for bone regeneration

In order to study the influence of rubidium(Rb)addition on the phase composition,microstructure,mechanical properties and cell response of bioactive glass-ceramics,CaO−SiO2−Na2O−B2O3−MgO−ZnO−P2O5 glass system was designed with and without addition of Rb.The results show that hydroxyapatite(HA)and Mg−whitelockite(Ca18Mg2H2(PO4)14)crystalline phases are formed in the glass matrix without Rb.After the addition of Rb,only HA phase is detected.The grain size of the crystals in the glass-ceramics is larger with the addition of Rb than that of samples without Rb.Rb addition can improve the bending strength of glass-ceramics.The cultivation of human bone marrow mesenchymal stem cells(hBMSCs)on Rb-containing glass-ceramics demonstrates enhanced cell adhesion,proliferation and ALP activity.In conclusion,Rb-modified glass-ceramics exhibit good mechanical property,excellent bioactivity and biocompatibility,which have potential for bone regeneration application.

Preparation and Characteristic of Glass-Ceramics with Super Low Thermal Expansion Coefficient

The preparation technics of glass-ceramics with super low coefficient of thermal expansion containing β-quartz solid solution as a main crystal phase based on the glass in the system Li2O-Al2O3-SiO2 was introduced. The composition of base glass, technics of melting and heat treatment effecting on characteristic of glass-ceramics was described. Specimens were prepared by melting, anneal and controlled two steps heat treatment. Crystal phase, microstructure and elementary distributing were studied by using XRD, SEM and EDS respectively. Prepared specimens show excellent transparency and super low thermal expansion coefficient of 2×10-8 ·K-1, which reaches international advanced level.

Preparation and Microstructure of Glass-ceramics and Ceramic Composite Materials

The technology and microstructure of glass-ceramics and ceramic composite materials were studied. A suitable ceramic body was chosen on the basis of the sintering temperature of CaO-Al2O3-SiO2 system glass-ceramics. According to the expansion coefficient of the ceramic body, that of CaO-Al2O3-SiO2 system glass-ceramics was adjusted, fl-wollastonite was found present as the major crystalline phase in glass- ceramic. The CaO-Al2O3-SiO2 system glass-ceramic layer and ceramic body could be sintered together by adjusting the sintering period. The compositions of glass-ceramic layer and ceramic body diffuse mutually at 1 100 ℃, resulting in an interface between them. To achieve good sintered properties of glass-ceramics and the chosen ceramic body, at least a four-hour sintering time is used.

Sol–gel La2O3–ZrO2 mixed oxide catalysts for biodiesel production

Different La2O3 contents（0, 1, 2, 3, and 5 wt%） were used to prepared La2O3-ZrO2 mixed oxides calcined at 600 ℃ by the sol-gel method. The catalytic activity was measured as biodiesel production from canola oil through a transesterification reaction. The characterization results indicate that the La2O3 monolayer formation and extent of basicity of m-ZrO2 have a large influence on biodiesel production.Greater biodiesel conversion（56% at 4 h） was obtained with the 3% La2O3-ZrO2 catalyst in the presence of basic sites and the formation of a monolayer of La2O3. The decrease in the catalytic activity for 5% La2O3-ZrO2 resulted from the loss of active sites on the catalyst because of agglomeration, which was suggested by XPS and the isoelectric point. The kinetic data fit to a pseudo-first order constant, and the largest kinetic constant corresponds to 3% La2O3-ZrO2, currently the largest heterogeneous non-alkaline metal catalyst reported for a transesterification reaction.

Surface termination effects on the electrical characteristics of La2O3/Al2O3 nanolaminates deposited by atomic layer deposition

Effects of initial surface termination on electrical characteristics of La2O3/Al2O3 nanolaminates deposited by atomic layer deposition are studied by conductive atomic force microscopy working in contact mode and standard electrical characterization methods.It is found that,compared with La2O3/Al2O3 nanolaminates with LaOx as termination,lower interface trap density,less current leakage spots,and higher breakdown voltage are obtained in the La2O3/Al2O3 nanolaminates with AlOx as termination after annealing.A clear promotion of interface silicate layer is observed for La2O3/Al2O3 nanolaminates with AlOx as termination compared with LaOx as termination under the same annealing condition.In addition,the current conduction mechanism in La2O3/Al2O3 nanolaminates is considered as the Poole-Frenkel conduction.All results indicate that the AlOx is a more appropriate termination to deposit La2O3/Al2O3 nanolaminates on Si substrate,which is useful for the high-κ process development.

Mechanism of La2O3 as combustion improver in blast furnace coal injection

La2O3 is a combustion improver suitable for burning pulverized coal in blast furnace. La2O3 forms the active species La3＋（CO-）3 that weakens the bridge adhesion of carbon structural units and alters the lattice structures, thus reducing the activation energy of the pulverized coal and accelerating the burning process. Research shows that La2O3 can form the active species La3＋（CO-）3, which weakens the bridge adhesion of carbon structural units and alters the lattice structures of the fixed carbon, hence decreasing the activation energy of the pulverized coal and accelerating the burning process.

Fe、La掺杂和氧缺陷对CeO_(2)表面吸附As_(2)O_(3)的密度泛函理论研究

采用密度泛函理论研究了As_(2)O_(3)(g)在Fe、La掺杂CeO_(2)(110)表面及氧缺陷LaCeO(110)表面的吸附行为,探索了LaCeO表面砷吸附能力显著高于FeCeO表面的主要原因。结果表明,As_(2)O_(3)(g)的吸附效果与吸附位点数量、吸附能、键长和电荷转移密切相关。纯CeO_(2)表面的吸附主要为化学吸附,吸附能绝对值大于−4.22 eV,电荷转移量为(−0.19)−(−0.31)e,As_(2)O_(3)得到电荷带负电,起表面受主作用,因此吸附量较小。FeCeO(110)表面新增Fe顶位和Bridge-2桥位两个吸附位,其中,Fe顶位为化学吸附,Fe掺杂改变了FeCeO表面电子分布和晶格结构,但并未改变As_(2)O_(3)与FeCeO之间的电荷转移方向,因此,As_(2)O_(3)仍呈负离子形式吸附。LaCeO(110)表面新增了三个吸附位:La顶位、Bridge-3桥位和Hollow-2空位,La掺杂改变了As_(2)O_(3)与LaCeO之间的电荷转移方向,使得As_(2)O_(3)失电子呈正离子吸附,起表面施主作用,因此,吸附能力增强。无O_(2)环境下,单一O缺陷LaCeO(110)表面吸附能力低于完整LaCeO表面;有O_(2)环境下,O缺陷有利于As_(2)O_(3)的吸附。

La掺杂氧空位的α-Bi_(2)O_(3)电子结构和光学性质的第一性原理研究

基于第一性原理的方法研究了本征α-Bi_(2)O_(3)、La掺杂、氧空位掺杂和共掺杂体系的电子结构与光学性质,以期获得性能比较优异的α-Bi_(2)O_(3)光催化材料。研究结果表明:掺杂后,体系结构变形较小,其中氧空位(V_(O))掺杂和La-V_(O)共掺杂体系的禁带宽度价带和导带同时下移且在禁带中引入杂质能级,说明掺杂可以减小电子从价带激发到导带所需能量,有利于电子的跃迁。特别是相对于氧空位单掺杂,La-V_(O)共掺杂使杂质能级向导带底靠近,这个倾向可能使该复合缺陷成为光生电子捕获中心的概率大于成为光生电子-空穴对复合中心的概率;同时,La-V_(O)共掺杂导致导带底附近的能带弯曲的曲率增大即色散关系增强,从而降低了电子的有效质量,加速电子的运动,因此,La-V_(O)共掺杂能大幅改善光生电子-空穴对的有效分离。另一方面La-V_(O)共掺杂在显著扩展可见光吸收范围的同时,还极大地增强了可见光吸收强度。因此,La-V_(O)共掺杂有效改善了α-Bi_(2)O_(3)的光催化活性。本研究为利用稀土离子掺杂改善其他光催化材料的性能提供了一个新的思路。

Structural characteristics and dielectric properties of glass-ceramic nanocomposites of(Pb,Sr)Nb_2O_6-NaNbO_3-SiO_2

The structure and dielectric properties of （Pb,Sr）Nb2O6-NaNbO3-SiO2 glass-ceramics with different Pb and Sr contents were investigated. The XRD pattern of glass-ceramics without Sr substitution is different from that with Sr substitution, which indicates the existence of orthorhombic phase in the latter ones. TEM bright field observation shows nanosized microstructures, while for samples with Sr, typical eutectic microstrncture with separated crystallized bands is found in the glass matrix. Dielectric properties measurement of the samples indicates an obvious improvement of dielectric constant, dielectric loss, DC field and temperature dependence of dielectric constant when the molar ratio of Sr to Pb is 4：6.

Z型La-SrTiO_(3)/Ag/Ag_(2)O异质结光催化降解亚甲基蓝研究

采用溶胶-凝胶法、化学沉淀法和光还原法合成了具有高催化活性的Z型La-SrTiO_(3)/Ag/Ag_(2)O异质结光催化剂。对该光催化剂进行了SEM、TEM、XRD、XPS、UV-Vis、PL和EPR的表征分析,并考察了初始亚甲基蓝(MB)浓度、pH和H_(2)O_(2)浓度等相关运行参数对光催化剂催化性能的影响。结果表明,成功制备的La-SrTiO_(3)/Ag/Ag_(2)O复合材料对光具有较大的吸光度,可以有效抑制了光致电子-空穴对的复合。该催化剂具有较高的光催化降解活性,光照120min后对30×10^(-6)的MB降解效率可达到98%。

Stress Analysis of CaO-Al_2O_3-SiO_2 System Glass-ceramic with Different Thickness

In order to study the relationship between thickness and residual stress in CaO-Al2O3-SiO2 glass-ceramics.The residual stress was measured in CaO-Al2O3-SiO2 system glass-ceramic with different thickness,and the formation mechanism and characterization of residual stress in CAS system Glass-ceramic were analyzed by the X-ray diffraction analysis.The experimental results show the compressive residual stress increass with thickness of glass-ceramic increasing.

Crystallization and dielectric properties of lead-free glass-ceramic composites with Gd_2O_3 addition

Lead-free glass-ceramic composites in barium sodium niobate silica system with Gd2O3 addition were synthesized through melt-casting fol-lowed by controlled crystallization technique. Crystallization and dielectric properties of the Gd2O3 adding glass-ceramic composites were investigated. With the increase in the concentration of Gd2O3, the glass transition temperature and the crystallization temperature of the pre-cursor glass shift towards the higher temperature. The crystallization behavior that occurred during the heat treatment procedure leads to the enhancement of dielectric constant. All the three compositions of glass-ceramic composites exhibit ferroelectricity when tested at room tem-perature. Both the values of the remanent polarization and coercive field are enhanced regularly with the gradual increase in the concentration of Gd2O3 additive under the same testing field.

Effect of alumina content and heat treatment on microstructure and upconversion emission of Er^(3+)ions in oxyfluoride glass-ceramics

The effect of alumina content and heat treatment temperature and time, on microstructure and Er3＋ （0.5 mol.%） emission of oxyfluoride glass-ceramics were investigated in this research. Two values of 1.8 （SA1.8Er0.5） and 2.18 （SA2.18Er0.5） were selected in this research for SiO2/Al2O3 ratio. According to DTA results, precursor glasses were heat treated at 630, 660 and 690 ℃ for 4 h and some glasses were also heat treated at 630 ℃ for 48 and 72 h. The results indicated that alumina content had significant effect on phase separation and viscosity of the glasses. Therefore the size, size distribution, and volume concentration of nano CaF2 crystals which precipitated during the heat treatment depended on alumina content of the glass. Due to the much smaller size of the precipitated CaF2 crystals in the glasses of low alumina content, these samples maintained excellent transparency and had narrower crystal size distribution than the high alumina glasses. The crystal size was increased markedly with the temperature increasing from 630 to 690 ℃. On the other hand a slight increase was observed in the crystal size by raising the heat treatment time in both glasses. Results indicated that in low alumina content glass （SA2.18Er0.5） the size of CaF2 nanocrystals was controlled in one order of magnitude. The increase of heat treatment time and temperature led to the incorporation of Er3＋ ions into CaF2 crystalline phase, increasing significantly the upconversion intensity. After heat treatment at 690 ℃for 4 h, atomic force microscope （AFM） revealed the development of small crystals with an average size of 80 and 30 nm in SA1.8Er0.5 and SA2.18Er0.5 samples, respectively.

Effect of Rare Earth on the Crystallization Behavior of Li_2O-Al_2O_3-SiO_2 Glass-ceramic

X-ray powder diffraction and Fourier transform infrared spectroscopy were applied for characterization of Li2O-Al2O3-SiO2 glass-ceramic powders doped with Eu2O3,Gd2O3 and Er2O3,respectively,in the conditions of different heat-treatment temperatures and with various amounts.The powders were derived from the polyacrylamide gel method.The results show that,the wet gels prepared by polyacrylamide perform a unique crystallization behavior in the process of drying,comparing with some customary preparation such as melt processing.The main crystal phase and crystallization sequence of Li2O-Al2O3-SiO2 micro-powders have no distinct with addition of Eu2O3,Gd2O3 or Er2O3,while the crystallization temperature of the β-spodumene decreased and the amount of the β-spodumene increased.

Eu^3＋激活的La2Mo2O9红色荧光粉的制备与性能

利用高温固相法制备了Eu3+掺杂的La2Mo2O9红色荧光粉,并对这种荧光粉的结构及发光性质进行了研究。XRD结果表明,实验合成了单一立方相的La2Mo2O9荧光粉体。该荧光粉的激发光谱由一宽带和一系列的锐峰组成;发射光谱由一系列锐峰组成,这些都与Eu3+的特征跃迁5DJ(J=0,1)和7FJ(J=1~4)相对应。结果表明该荧光粉可被395nm的紫外光和470nm的可见光有效激发,并发出峰值位于620nm左右的红光,亮度可达到传统红色荧光粉Y2O2S∶Eu3+的1.5倍以上,这表明它可以作为'蓝+黄'模式白光LED的红色补光粉,也可以作为UV-LED激发三基色荧光粉体系中的红色荧光粉。研究了Eu3+的掺杂浓度以及不同助熔剂对样品发光性质的影响。Eu3+的摩尔分数为0.3时,发光强度达到最强。质量分数为3%的NH4Cl作为助熔剂时效果最好。