灯用稀土荧光粉的若干技术发展和探索（上）

本文简要介绍了灯用稀土三基色荧光粉的组成、结构及发光机理等基本概况,以及灯用稀土三基色荧光粉的技术现状,市场状况及技术发展方向,并介绍了近年来彩虹集团在灯用稀土三基色荧光粉上所做的基础性及应用特性方面的研究工作。     

高镍系Li[(Ni0.88Co0.12)0.90(Ni0.80Co0.15Al0.05)0.10]O2正极材料的制备研究

采用共沉淀法合成Li[(Ni0.88Co0.12)0.90(Ni0.80Co0.15Al0.05)0.10]O2正极材料,通过调控Ni、Co、Al元素在材料内部形成梯度分布来提升材料的稳定性,采用X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)、电子探针(EPMA)及电化学测试等方法对材料性能进行表征。结果表明:三元正极材料具有良好的层状结构,Ni、Co和Al元素呈梯度分布。以0.2 C进行充放电,首次放电比容量为191.2 mAh/g,以0.2 C充1 C放电循环100次,电池比容量由174.4 mAh/g下降到111.1 mAh/g,容量保持率为63.7%。     

Environmental-barrier coating ceramics for resistance against attack by molten calcia-magnesia-aluminosilicate (CMAS) glass: Part I,YAlO3 and γ-Y2Si2O7

The high-temperature (1500?°C) interactions of two promising dense, polycrystalline EBC ceramics, YAlO₃ (YAP) and γ-Y₂Si₂O₇, with a calcia-magnesia-aluminosilicate (CMAS) glass have been explored as part of a model study. Despite the fact that the optical basicities of both the EBC ceramics and the CMAS are similar, they both react with the CMAS. In the case of the Si-free YAlO₃, the reaction zone is small and it comprises three regions of reaction-crystallization products, including Y-Ca-Si apatite solid-solution (ss) and Y₃Al₅O₁₂ (YAG)(ss). In contrast, only Y-Ca-Si apatite(ss) forms in the case of Si-containing γ-Y₂Si₂O₇, and the reaction zone is an order-of-magnitude thicker. These CMAS interactions are analyzed in detail, and are found to be strikingly different than those observed in Y-free EBC ceramics (β-Yb₂Si₂O₇ and β-Sc₂Si₂O₇) in the accompanying Part II paper. This is attributed to the presence of the Y in the YAlO₃ and γ-Y₂Si₂O₇ EBC ceramics.     

Impact of sand and filler materials on the hydration behavior of calcium aluminate cement

In earlier work, we have observed discrepancies relating to the early hydration of calcium aluminate cement (CAC) when comparing data from heat flow calorimetry of CAC paste with results from mortar strength tests using the crushing method. Here, we investigated on this phenomenon and found that the sand which is used as a filler exerts a major influence on CAC hydration resulting in acceleration. Furthermore, in particular fine filler materials such as, for example, microsilica, fine limestone powder, and especially α- and γ-Al₂O₃ also produced a strong hydration accelerating effect which is dependent on their specific surface area. The mechanism underlying the acceleration is that under alkaline conditions their negative surface charge attracts calcium ions as was confirmed via inductively coupled plasma atomic emission measurements. Such a layer generates favourable conditions for the nucleation of CAC hydration products (C-A-H phases). The resulting crystalline hydrates which form on the surface of the filler particles submerged in CAC cement pore solution were visualized via SEM imaging. This way, specifically selected fillers can significantly accelerate CAC hydration and save precious lithium salts which are commonly used to boost the early strength of CAC.     

含镁铝尖晶石的铝酸钙水泥中物相分布状态对流变特性的影响

合成了3种不同配比含镁铝尖晶石的铝酸钙水泥(CAM)。借助X射线衍射和扫描电子显微镜对合成的水泥试样进行了物相组成和显微结构分析,使用电导率仪、维卡仪和流变仪测定了CAM水泥净浆的水化和流变特性。结果表明:当水泥中镁铝尖晶石(MgAl2O4,MA)分布在一铝酸钙(CaAl2O4,CA)周围时,MA阻碍了CA与水的接触,水泥水化较难进行,水泥砂浆凝结时间较长,水泥净浆的屈服应力、表观黏度和触变性较小,储能模量G’增长速率也较小。MA和CA交错分布时,CA晶粒外形不规整,与水接触面积较大,水泥水化较易进行,水泥砂浆凝结时间较短,水泥净浆的屈服应力、表观黏度和触变性较大,储能模量G’增长速率也较大。而当MA分布于CA晶粒之间时,CA晶粒发育完整,水泥溶解过程较慢,水泥凝结时间和流变参数都处于中间值。     

Post-annealing effect on transparent Mg-Zn aluminate solid solutions fabricated by spark plasma sintering

In MgAl₂O₄ (Mg aluminate) fabricated by pressure sintering, carbon contamination, oxygen vacancy, and other defects exist and cannot be completely removed even after post-annealing. ZnAl₂O₄ (Zn aluminate) has the same crystallographic structure as Mg aluminate and excellent light transmission by post-annealing. In this study, the transmission of (Mg_1-XZn_X)Al₂O₄ spinel, which is a solid solution between Mg aluminate and Zn aluminate, was investigated. After post-annealing, the transmission of (Mg_1-XZn_X)Al₂O₄ spinel was higher than Zn aluminate and Mg aluminate, which means that the absorption center disappeared. Besides, the real in-line transmission is improved by up to 30% by post-annealing, which is related to the driving force to increase the configurational entropy and form a more stable solid solution phase. In solid solution spinel, as the Zn content increases, the optical properties can be improved by post-annealing, but the mechanical properties are slightly decreased.     

LaMgAl11O19 synthesis using non-hydrolytic sol-gel methods

Polycrystalline LaMgAl₁₁O₁₉ (LMA) was prepared by four different non-hydrolytic sol-gel methods. From stable solutions, four powder precursors containing an amorphous and nanocrystalline phase with specific reactivity were obtained. The particle size, morphology, thermal behaviour, and phase composition of the powder precursors were studied using DLS, TEM, DSC/TG and XRD. Bulk ceramic samples containing LMA were prepared at 1200?°C for 16?h and examined in terms of phase purity and microstructure using XRD, SEM, and TEM. Raman spectroscopy of pure LMA was used to study the structure in detail. A mechanism of LMA formation and a relation between powder precursor properties and final phase composition is proposed. These findings may be useful for designing modern technologies for fabrication of LMA for optical or protective coating applications.     

铝酸钙玻璃中羟基对红外透过性能的影响

采用不同熔化方法制备了铝酸钙红外玻璃并考察了其红外透过性能。研究了结构中的羟基对玻璃红外透过性能的影响。通过红外光谱和固体核磁共振技术对玻璃中羟基的结构特征、氢键结合状态以及红外吸收情况进行了研究和探讨。结果表明:羟基会引起铝酸钙玻璃在近红外2.9μm左右的宽带吸收,这是由于玻璃中羟基结构形式的多样化所造成的;在玻璃结构中,羟基与氢键结合会造成振动频率下降,红外吸收峰向长波移动,羟基氢键结合强度越大,长波移动越严重,羟基与氢键结合形式越多,羟基的红外吸收范围越宽;在铝酸钙红外玻璃中主要存在3种羟基存在形式:孤立羟基基团、邻近的羟基对和带有氢键的单个羟基。不同制备方法获得的玻璃结构中羟基存在形式基本相同。     

水合硫铝酸钙的性质及脱硅反应研究

应用XRD和IR分析等手段考察了脱硅剂水合硫铝酸钙的性质以及在铝酸钠溶液中的行为.发现水合硫铝酸钙在95℃不含硅的铝酸钠溶液中不稳定,其中的硫酸根能被溶液中的OH-离子置换出来,水合硫铝酸钙被分解成六方晶系的水合铝酸钙.六方的水合铝酸钙又有少部分被转化成立方的水合铝酸钙.据此提出用水合铝酸钙对铝酸钠溶液进行的深度脱硅过程存在2种脱硅机理:一种是水合硫铝酸钙在铝酸钠溶液中先转变成六方的水合铝酸钙,然后SiO2(OH)22-离子进入六方水合铝酸钙晶格内部与之反应,生成水化石榴石;另一种是新生成的六方水合铝酸钙又有部分被转化为立方的水合铝酸钙,SiO2(OH)22-离子在其表面与之反应,生成水化石榴石.水合硫铝酸钙的脱硅过程是以第1种机理为主.     

Preparation of calcium aluminate cement by combustion synthesis and application for corundum‐based castables

Calcium aluminate cement was prepared by combustion synthesis with CaO₂, Al, and Al₂O₃ as raw materials. The effects of CaO/Al₂O₃ (C/A) molar ratios in raw materials on the phase compositions and morphologies of calcium aluminate were investigated in detail. It was found that when the C/A reduced from 1.1 to 0.74, the content of CaO·2Al₂O₃ (CA₂) in products increased, whereas contents of CaO·Al₂O₃ (CA) and 12CaO·7Al₂O₃ (C₁₂A₇) decreased; when the C/A was 0.8, the phase composition of product (CS71) was equal to that of Secar71. Additionally, the crystallines of CA and CA₂ in the product were reduced when the C/A molar ratio was decreased. And then, the bulk density, apparent porosity, permanent linear change, cold crushing strength (CCS), and cold modulus of rupture (CMOR) of the corundum‐based castables bonded with CS71, Secar7 were compared. The castables bonded with CS71 demonstrate obviously improved CCS, CMOR, and volume stability.