Y_2O_2S∶Tb纳米晶的能量传递过程的研究

研究了Y2O2S∶Tb纳米晶的发光性质和能量传递过程,根据浓度猝灭曲线分析了纳米Y2O2S中引起5D3和5D4能级浓度猝灭的相互作用类型分别为电偶极-电偶极和交换相互作用。纳米Y2O2S中Tb离子的5D3-7F5跃迁的发光寿命与相同掺杂浓度的体材料相比明显缩短,根据引起浓度猝灭的相互作用类型对发光衰减曲线进行拟合,得到理论和试验一致的结果。     

微波场作用下Y2O2S：Tb绿色荧光粉的快速合成及其发光特性

采用微波法快速合成了Y2O2S：Tb绿色荧光粉。用X射线衍射（XRD）仪、扫描电镜（SEM）、荧光分光光度计等对合成产物的相结构、形貌、以及发光特性进行了研究。结果表明：材料的晶体结构为六方晶系，与Y2O2S相同。颗粒的形貌为类球形，分散性很好，平均晶粒尺寸在300nm左右。发射光谱由384，418，439，460，475，498，547，590，624nm等一系列窄带发射峰组成，归属于Tb^3＋从^5D3，^5D4到^7FJ（J=0～6）的跃迁。研究发现Tb的掺杂浓度对样品的发射光谱有着很重要的影响，当其浓度为0．5％（摩尔分数，下同）时，^5D3→^7FJ的蓝光发射发生猝灭，当其浓度为9％时，^5D4→^7FJ的绿光发射发生猝灭。     

绿色发光材料NaLa(MoO_4)_2:Tb~(3+)的微波辅助溶胶-凝胶法制备及其性质

采用微波辅助溶胶-凝胶法制备了系列绿色发光粉NaLa31-x(MoO4)2:Tb+x(x=0.02,0.1,0.15)。用X射线粉末衍射仪和荧光分光光度计等分析和表征所合成样品的物相结构和发光性质。结果表明:所合成的NaLa(MoO4)2:Tb3+晶体结构与NaLa(MoO4)2相似,属四方晶系结构;样品的激发光谱为位于250~350 nm的1个宽带,最大激发峰位于300 nm处;发射光谱由一系列尖峰组成,最强的发射峰位于544 nm处,归属于Tb3+的5D4-7F5跃迁。NaLa(MoO4)2:Tb3+的发光强度随Tb3+掺杂浓度的增加逐渐加强,当Tb3+浓度为10 mol%时发光强度最大,而后随Tb3+浓度的增加而降低,发生浓度猝灭。根据Dexter能量共振理论,该浓度猝灭系Tb3+的电偶极-电偶极的相互作用所致。通过含氧酸根阴离子(SO2-4)的掺杂有效提高了NaLa(MoO4)2:Tb3+体系的发光亮度。     

纳米SrAl2O4:Eu,Dy发光特性及浓度猝灭

用溶胶-凝胶法合成了不同Eu2+掺杂浓度的SrAl2O4Eu2+,Dy3+纳米晶体,探讨了纳米晶体的发光性能及浓度猝灭.结果发现纳米晶体与相应的常规尺寸的发光粉末材料相比,发射光谱和激发光谱的主峰位置均出现了明显的蓝移,发光强度和猝灭浓度有明显的提高,余辉衰减速度加快.认为蓝移现象以及余辉衰减变快,主要归因于发光粉体纳米粒子的量子尺寸效应.     

Y2-x-yGdxEuyO3纳米材料制备过程中的固溶行为及其发光性能

用柠檬酸螯合法制备Y2-x-yGdxEuyO3纳米粉体(x+y≤2),通过FTIR,XRD和SEM分析了制备过程中的物相变化以及pH值对粉体形貌的影响.测试了Y2-x-yGdxEuyO3晶格常数和晶胞体积,分析了Gd与Eu在Y2O3中的同溶行为及其发光性能.结果表明:在pH<3的体系中制备Y2-x-yGdxEuyO3粉体较为适合,经900℃煅烧2 h可完全合成出立方相的Y2-x-yGdxEuyO3;在pH=l时,加入少量乙二醇(5%,体积分数)时得到粉体形貌最佳,粒径约90 nm,近球形.样品的发光性能和Y,Gd的配比以及Eu的含量有关,当化学配比为Y0.2Gd1.65Eu0.15O3时样品发光强度最高,y值超过0.15会发生浓度猝灭,导致发光强度降低.     

Eu/Tb共掺杂Y2O3荧光粉的发光性质研究

稀土掺杂荧光粉在固态照明中有良好的应用前景。这里用固相法合成了Y2O3:Eu3 ,Tb3 ,材料结构用X-射线衍射仪进行了表征,发现合成了纯相的Y2O3,掺杂的稀土离子未对基质结构产生影响。稀土离子单掺杂的Y2O3荧光粉在各自特征领域表现出良好的发光性质Y2O3:Tb3 发射出亮绿光,而Y2O3:Eu3 发射出亮红光颜色。调控它们的浓度,可以在Y2O3:0.2% Eu3 , 2%Tb3 处实现白光,详细分析了它们的发光光谱,计算了它们的色坐标,对应的CIE色坐标分别标记在色坐标图中。     

黄色发光材料Gd2O3:Dy3+的水热法合成及发光性能

以尿素为沉淀剂,采用水热方法制备Gd2O3:Dy3+黄色发光粉。通过红外光谱、X射线衍射、扫描电镜以及荧光分光光度计对水热前驱体及目标产物进行分析表征。结果表明:水热前驱体为水合碳酸钆,经900℃焙烧后得到纯立方相的Gd2O3:Dy3+。其微观形貌为针状结构,长度约为10～200μm。Gd2O3:Dy3+的激发光谱由峰值为239,279,314,353nm的一系列激发峰组成,最强峰位于279nm处;发射光谱主要由两部分组成,分别为460～500nm的蓝光和560～590nm的黄绿光的发射峰(带),最强峰位于573nm处,归属为Dy3+的4F9/2-6H13/2跃迁。Dy3+的掺杂浓度对Gd2O3:Dy3+的发光强度有着重要的影响,发光强度随着Dy3+掺杂量的增加呈现先增大后减小的趋势,掺杂浓度为0.8%时发光强度最大,其浓度猝灭主要是由电偶极-电偶极相互作用所致。     

化学共沉淀法制备BaAl_2Si_2O_8:Eu~(2+)荧光粉及其发光特性

采用化学共沉淀法一次煅烧工艺制备BaAl2Si2O8:Eu2+荧光粉。用X射线衍射仪、荧光分光光度计和扫描电镜等对BaAl2Si2O8:Eu2+荧光粉的相结构、发光性能、形貌进行表征。结果表明,化学共沉淀法合成了单相的BaAl2Si2O8:Eu2+,且粒度小,分布均匀,呈类球形。在320nm激发下,其发射主峰位于465nm附近,当Eu2+的掺杂浓度为3.5%,发光强度达到最大值,猝灭浓度有所提高,这主要是由于纳米微粒边界对能量共振传递的阻断和猝灭中心在纳米晶内分布的涨落性引起的。     

Y2-x-yGdxEuyO3纳米材料制备过程中的固溶行为及其发光性能术

用柠檬酸螯合法制备Y2-x-yGdxEuyO3纳米粉体（x＋y≤2）,通过FTIR,XRD和SEM分析了制备过程中的物相变化以及pH值对粉体形貌的影响．测试了Y2-x-yGdxEuyO3晶格常数和晶胞体积,分析了Gd与Eu在Y2O3中的固溶行为及其发光性能．结果表明：在pH〈3的体系中制备Y2-x-yGdxEuyO3粉体较为适合,经900℃煅烧2h可完全合成出立方相的Y2-x-yGdxEuyO3;在pH=1时,加入少量乙二醇（5％,体积分数）时得到粉体形貌最佳,粒径约90nm,近球形．样品的发光性能和Y,Gd的配比以及Eu的含量有关,当化学配比为Y0.2Gd1.65Eu0.15O3时样品发光强度最高,y值超过0．15会发生浓度猝灭,导致发光强度降低．     

（Y，Gd）2O3：Eu^3＋纳米粒子制备及光谱特性

用湿化学共沉淀法制备了(Y,Gd)2O3:Eu3 纳米粒子.用XRD,TEM,SEM及差示/热重分析(DSC/TG)手段对粉体进行了表征.用荧光光度计分析了样品的激发光谱和发射光谱.结果表明:在煅烧温度为800℃保温2 h时,合成出近似球形、粒径均匀且分散性好的(Y,Gd)2O3:Eu3 纳米粒子,一次颗粒尺寸约为20 nm.样品在波长为612.0 nm监控光下激发,出现235和250 nm两个激发峰,分别为(Y,Gd)2O3基质吸收和Eu3 迁移态(CTS)吸收造成的.两个波长激发下的发射光谱峰强度前者高于后者.当掺杂Eu3 的摩尔浓度为3%时,发射光谱对应5D0→7F2能级跃迁的相对峰强度最大,当Eu3 掺杂的摩尔浓度为7%时,相对峰强度反而降低,这是由于Eu3 的浓度猝灭造成的.     

Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2气氛下的腐蚀

研究了600℃时Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2 3种气氛中的腐蚀行为，Fe-15Ce合金腐蚀后发生了Ce的内氧化或形成了复杂的腐蚀产物膜，而未出现Ce的选择性氧化或硫化，这主要是合金中存在着两相及Ce在Fe中极低的溶解度的结果。Fe-15Ce合金在本实验条件下的氧化-硫化腐蚀速度低于相同温度、压力下的纯硫化。     

用氢-氧取代氧-乙炔作焊接切割的必要性及可行性

阐述了用氢代乙炔的必要性．通过时HGQU2000／315火焰电孤焊割机的考察和试用证实了用氢代乙炔的可行性，比较了两种气体的性质并提出了使用特性差异和注意事项．提出了进一步探索的问题。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极制备及性能

通过热分解法制备了含IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极,采用SEM、EDX、XRD、CV等检测方法对中间层进行表征,同时采用强化加速寿命试验对电极电化学稳定性进行表征。结果表明:450℃时前躯体完全氧化并形成固溶体,制备的中间层晶粒细小,表面结构致密,电化学孔隙率小。添加中间层使Ti/RuO2-TiO2-SnO2电极强化寿命由未加中间层的7.5h提高到995.8h,远高于国家标准20h。     

ACTIVITY OF La_2O_3 IN LIQUID La_2O_3-CaF_2 AND La_2O_3-CaF_2-CaO-SiO_2 SLAGS

用石墨为还原剂,将渣中La_2O_3还原入液态Sn,以测定1500℃下La_2O_3-CaF_2和La_2O_3-CaF_2-CaO-SiO_2渣中La_2O_3的活度.对La_2O_3-CaF_2系,并用Gibbs-Duhem积分法求得CaF_2的活度. 根据液态渣的离子结构模型,对上述二渣系中La_2O_3的活度数据进行了简单的讨论.     

Mechanoluminescence in BaSi2O2N2:Eu

Mechanoluminescence (ML), a general term for the phenomenon in which light emission occurs during any mechanical action on a solid, can be divided roughly into two classes: destructive ML and non-destructive ML. For practical use in high-end applications (e.g. pressure sensors), materials with non-destructive ML properties are preferred. This paper reports on the strong non-destructive ML in BaSi₂O₂N₂:Eu. When irradiated in advance with ultraviolet or blue light, this phosphor shows intense blue-green light emission upon mechanical stimulation such as friction or pressure. The ML has an emission band peaking at 498 nm, which is ～4 nm red-shifted compared to the steady-state photoluminescence. The origin of the ML is discussed and related to the persistent luminescence of BaSi₂O₂N₂:Eu. The same traps are responsible for both phenomena. Based on the occurrence of ML in this phosphor, we were able to show that the predominant crystallographic structure of BaSi₂O₂N₂:Eu belongs to space group Cmc2₁.     

氢分子在贮氢材料Li2MgN2H2表面的吸附与解离

采用第一性原理计算方法研究了Li-Mg-N-H体系贮氢材料的放氢产物Li2MgN2H2的吸氢反应过程中的过渡态、表面电子态密度和表面能。结果表明:氢分子在Li2MgN2H2低指数表面中最低能量(100)表面的Mg-Mg-Li穴位吸附位置能够形成最稳定的吸附结构并发生解离,氢分子吸附能为-0.1898eV,解离能约为0.84eV(81kJ/mol),表明该反应所需的反应活化能仍较高,吸氢反应速度缓慢。     

Thermodynamic evaluation of phase equilibria in the CaCl2-MgCl2-CaF2-MgF2 system

The phase diagram of the CaCl₂-CaF₂-MgCl₂-MgF₂ reciprocal ternary system was calculated thermodynamically from available data on the common-ion binary subsystems and from available data on the CaCl₂-MgF₂ join. This join is very nearly quasibinary and divides the system into two quasiternary systems: the CaCl₂-MgF₂-CaF₂ system with a ternary eutectic calculated at 724 +-5 °C and the CaC₂-MgF₂-MgCl₂ system with a ternary eutectic calculated at 561 +-5 °C.     

High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.     

The Quasi-Ternary System Cu2Se-Ga2Se3-GeSe2

The quasi-ternary system Cu₂Se-Ga₂Se₃-GeSe₂ was investigated using the methods of differential thermal and x-ray analysis. An isothermal section at 770 K and a liquidus surface projection of the phase diagram were constructed. The existence of the quaternary phase CuGaGeSe₄, the boundaries of solid solutions ranges of the system compounds were established.