助熔剂对绿色荧光粉Ba2 SiO4∶Eu2+ 颗粒形貌及发光性能的影响

采用高温固相法在弱还原气氛下合成了Ba₂SiO₄∶Eu²⁺绿色荧光粉,利用X射线衍射、扫描电子显微镜和荧光分光光度计考察了不同助熔剂对Ba₂SiO₄∶Eu²⁺荧光粉的结晶度、物相纯度、颗粒形貌和发光强度的影响,并详细讨论了不同助熔剂在荧光粉制备过程中的作用机理。结果表明:不加助熔剂时样品存在BaSi₂和SiO₂杂相;利用NH₄F、Na₂CO₃或H₃BO₃作为助熔剂时会抑制BaSi₂杂相的形成,而BaF₂作助熔剂可以得到纯的斜方晶系。与未加助熔剂合成的荧光粉相比,添加质量分数为2% 的BaF₂、NH₄F或Na₂CO₃后合成样品的发光强度分别提高了138%,81%和34%;而质量分数为2%的H₃BO₃作助熔剂时,荧光粉的发光强度反而降低了14%。BaF₂作助熔剂合成的荧光粉颗粒形貌接近球形,以NH₄F、Na₂CO₃或H₃BO₃作助熔剂合成的荧光粉颗粒形貌分别为不规则片状、纺锤体形和不规则多边形大颗粒。     

助熔剂法制备的(Ce0.67,Tb0.33)MgAl11O19绿色荧光粉的发光性能

选取典型的助熔剂,利用助熔剂法制备了节能灯用(Ce0.67,Tb0.33)MgAl11O19绿色荧光粉,并对其发光性能进行了对比测试。研究了各单一或复合助熔剂对(Ce0.67,Tb0.33)MgAl11O19荧光粉的发光亮度及颗粒形貌的作用及影响,并找到了最佳复合助熔剂组分为0.2%H3BO3+2.0%Li2CO3+2.0%AlF3(质量分数)。所制备的(Ce0.67,Tb0.33)MgAl11O19荧光粉样品具有较为规则的形貌,且发光亮度与(Ce0.67,Tb0.33)MgAl11O19现有商用粉的比值为103:100。     

无锂助熔剂B_2O_3对Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3固体电解质离子电导率的影响

采用固相法制备锂离子电池用固体电解质磷酸钛锂铝Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3(LATP),研究了不同烧结温度以及助熔剂对LATP固体电解质离子电导率的影响.采用X射线衍射、能谱分析、扫描电镜和交流阻抗等方法,研究样品的结构特征、元素含量、形貌特征以及离子导电性能.结果表明,在900?C烧结可以获得结构致密、离子电导率较高的纯相LATP陶瓷固体电解质.与添加助熔剂Li BO2的样品进行对比实验发现,采用B_2O_3代替LiBO_2作为助熔剂也可以提高烧结样品的离子电导率,并且电解质的离子电导率随助熔剂添加量的增大,先增大后减小,其中添加质量百分比为2%的B_2O_3的样品具有最高的室温离子电导率,为1.61×10~(-3)S/cm.     

YAG∶Ce发光材料合成的助熔剂研究

采用高温固相法合成YAG∶Ce荧光粉时,传统的以硼酸为助熔剂的产物硬度很大,处理过程中容易破坏晶体形貌,影响发光性能。采用氟化物助熔剂(MgF2、CaF2、SrF2、BaF2、A lF3)及它们与H3BO3混合助熔剂来制备YAG∶Ce,研究了助熔剂种类及其浓度对制得的粉体发光性能的影响,比较了它们的晶体形貌与物相组成。结果表明,采用不同助熔剂合成的YAG∶Ce的激发光谱及发射光谱基本相同,而BaF2、A lF3、SrF2及它们与H3BO3的混合助熔剂系列,可在一定程度上降低产品硬度、提高产品发光亮度;其中H3BO3~SrF2系列、H3BO3~BaF2系列的晶化程度与粒度分布均有改善;H3BO3~BaF2系列的物相组成比较纯,除Y3A l5O12主相外基本无杂相。     

Ca_xSi合金前驱物常压氮化制备Ca_(1-x)AlSiN_3∶xEu~(2+)红色荧光粉及发光性能研究

采用CaxSi合金前驱物和Eu B6常压氮化制备了Ca Al Si N3∶Eu2+氮化物红色荧光粉。研究了不同烧结温度、添加助熔剂及二次烧结对发光性能的影响。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、荧光分光光度计对发光材料的形貌、晶体结构、发光性能与热稳定性进行了研究。分析结果表明:通过合金前驱物常压氮化法得到的氮化物荧光粉具有Ca Al Si N3结构,空间群为Cmc21。Ca Al Si N3∶Eu2+红色荧光粉的最佳烧结温度为1 550℃。添加质量分数为6%的Sr F2助熔剂后,荧光粉发光强度的提升效果最好。添加6%Sr F2助熔剂及二次烧结后得到的荧光粉的晶粒生长更加完整,颗粒度明显改善,发射光谱的相对强度也明显提高,比未加助熔剂单次烧结的荧光粉相对强度提高了近一倍。将发射峰位在640 nm的Ca0.98Al Si N3∶0.02Eu2+红色荧光粉应用在白光LED的封装中,获得了色温为3 109 K、显色指数为92.5以及色温为4 989K、显色指数为95.8的高显色白光LED,说明本文合成的氮化物红色荧光粉可以实现暖白光和正白光高显色的白LED发光器件。     

Ca_3La(BO_3)_3∶Tb~(3+)的合成与发光性质

高温固相反应法合成了Ca3La(BO3)3∶Tb3 光致发光材料。利用扫描电镜和激光衍射分析仪测定了样品的晶粒形貌及粒径大小分布,利用荧光分光光度计研究了Ca3La(BO3)3∶Tb3 的光致发光特性。确定了在Ca3La(BO3)3基质中Tb3 离子浓度对其发光强度的影响及其自身浓度猝灭机理;探讨了助熔剂L i2CO3、敏化剂Ce3 离子的加入对荧光粉发光强度的影响。     

Li2CO3/K3PO4复合助熔剂对新型Y2O2S：0.09Ti长余辉磷光体发光性能的影响

采用高温还原法合成了一种新型无稀土掺杂Y₂O₂S:0.09Ti长余辉发光材料。基于助熔剂种类对长余辉发光材料特性的重要作用,选择了对余辉衰减初期和后期余辉强度有明显作用的Li₂CO₃和K₃PO₄两种助熔剂,研究了不同配比(以下用x表示,x=Li₂CO₃/(Li₂CO₃+K₃PO₄))的复合助熔剂对Y₂O₂S:0.09Ti磷光体晶体结构和发光性能的作用,以获得具有较好综合发光性能的Y₂O₂S:0.09Ti磷光体。采用PL光谱和余辉测试仪对材料的发光特性进行了表征,用XRD研究了其晶体结构的变化。XRD结果表明,在复合助熔剂范围内(x=0~1.0)均可获得单相性的Y₂O₂S:0.09Ti磷光体。同时发现复合助熔剂比例不同制备的样品中,Y₂O₂S:0.09Ti磷光体晶体择优取向也发生明显的变化,且高比例Li₂CO₃有助于Y₂O₂S:0.09Ti磷光体的晶体形成。复合助熔剂比例x对样品的激发峰与发射谱主峰位置(565nm)基本没有影响;但助熔剂比例x对发射峰强度则有明显影响,随着x增加,该磷光体的发光强度先增后减,在x=0.8时发光强度最大。     

YAG：Ce发光材料合成的助熔剂研究

采用高温固相法合成YAG:Ce荧光粉时,传统的以硼酸为助熔剂的产物硬度很大,处理过程中容易破坏晶体形貌,影响发光性能.采用氟化物助熔剂(MgF₂、CaF₂、SrF₂、BaF₂、AlF₃)及它们与H₃BO₃混合助熔剂来制备YAG:Ce,研究了助熔剂种类及其浓度对制得的粉体发光性能的影响,比较了它们的晶体形貌与物相组成.结果表明,采用不同助熔剂合成的YAG:Ce的激发光谱及发射光谱基本相同,而BaF₂、AlF₃、SrF₂及它们与H₃BO₃的混合助熔剂系列,可在一定程度上降低产品硬度、提高产品发光亮度;其中H₃BO₃~SrF₂系列、H₃BO₃~BaF₂系列的晶化程度与粒度分布均有改善;H₃BO₃~BaF₂系列的物相组成比较纯,除Y₃Al₅O₁₂主相外基本无杂相.     

新型红色荧光粉Na2Ca4(PO4)2SiO4:Eu3+,Bi3+的制备及发光特性

用高温固相法合成了用于白光LED的Na2Ca4(1-x-y)(PO4)2SiO4:xEu3+,yBi3+红色荧光粉.研究了助熔剂H3BO3、二次煅烧时间和稀土掺杂量等制备条件对样品发光性质的影响.结果表明,在1 200℃、助熔剂H3BO3加入量为样品质量的3.8%时可得到更有利于发光的α-NCPS基质,而且掺入Eu3+...     

一类电子俘获型红外可激发材料的制备和光学性质

采用硫化助熔剂法(SFM)合成了具有红外上转换及光存储特性的稀土激活光子学材料CaS:Eu,Sm和CaS:Ce,Sm.利用X射线衍射(XRD)、扫描电镜(SEM)等测试了合成材料的物相结构和微观形貌,结果表明,合成材料具有单一相,相纯度在98.5%以上;采用CaCO₃制备的合成材料晶化程度更好,生成的晶粒更大.利用荧光光谱仪和分光光度计测量了合成材料的光学性质,结果表明,这类电子俘获材料在紫外线或短波长可见光有效激发下,能通过电子俘获实现光存储,并对近红外光有上转换作用.通过对合成材料及有关稀土元素原子结构分析,提出了两种新的稀土激活剂.     

HI-13串列加速器生物用新终端7Li离子束流监测诊断研究

7Li离子属于高LET辐射,是辐射生物学基础研究中常用的重离子射线之一,它是硼中子俘获治疗癌症中起关键作用的离子,在辐射诱变育种等领域也有较好的应用前景。实验在北京HI-13串列加速器R20支线生物用新终端上进行,对43 MeV 7Li离子束斑大小、均匀性和监测注量的准确性进行测量和评估,结果表明:均匀性好于90%的最大束斑面积为5.0cm×5.0cm;4.2×104 ～1.5×105 particles/cm2/s注量率范围内,两种不同探测器测得的注量率变化呈线性关系,闪烁体探测器监测的注量与CR39探测器测得的绝对注量的误差小于10%。这些束流特性能够满足辐射生物学实验要求,有利于进一步开展与硼中子俘获治疗癌症或辐射诱变育种中7Li离子的辐射生物学相关研究。7Li ion with high linear energy transfer (LET) radiation has been used in radiobiological research, takes main effect in Boron Neutron Capture Therapy and is applied in radiation mutagenic breeding. This experiment was carried on the new terminal established for radiobiological application, located at the end of R20 branch beam line of HI-13 tandem accelerator. The beam qualities of 7Li ions of 43MeV generated by HI-13 tandem accelerator, including spot size and uniformity and particle fluence accuracy were measured using different detection methods. The results showed that beam uniformity was over 90% at 5cm×5cm area, the flux of S1 and M3 had a good linear relationship as particle flux ranged from 4.2×104 particles/cm2/s to 1.5×105 particles/cm2/s, and particle fluence accuracy was better than 90%. All the results showed that the beam qualities of 7Li ions finely met the basic requirements for radiation biological experiment. It provides important method to study biological effects for fundamental research and tumor therapy or radiation mutagenic breeding application associated with 7Li ions.     

Strong flux pinning enhancement in YBa2Cu3O7-x films by embedded BaZrO3 and BaTiO3 nanoparticles

YBa2Cu3O7-x (YBCO) films with embedded BaZrO3 and BaTiO3 nanoparticles were fabricated by metalorganic deposition using trifluoroacetates (TFA-MOD). Both X-ray diffraction and transmission electron microscopy revealed that these BaZrO3 and BaTiO3 nanoparticles had random orientations and were distributed stochastically in the YBCO matrix. The unique combined microstructure enhances the critical current density (Jc) of the BaZrO3/BaTiO3 doped-YBCO films, while keeping the critical transition temperature (Tc) close to that in the pure YBCO films. These results indicate that BaZrO3 and BaTiO3 nanoparticles provide strong flux pinning in YBCO films.     

Li+共掺杂GdTaO4:Eu3+发光增强效应的研究

测量了不同浓度Li+共掺杂下GdTaO4:Eu3+荧光粉材料的X射线衍射谱(XRD)、发射光谱以及红外透射谱,并应用Judd-Ofelt理论,由发射光谱得到Eu3+的光谱跃迁强度参数Ω2.发现Li+共掺杂有助于提高GdTaO4:Eu3+的发光强度,当x=0.06和0.10时,612 nm处的发光强度分别被提升了1.7倍和1.5倍.发光增加的原因是因为Li+的助熔剂效应有效提高了GdTaO4材料的结品性能,并抑制了Cd2O3和Ta2O5杂相的产生,而非所推测的掺Li+引起了配位场对称性降低,从而导致宇称禁戒的放宽.此时Gd0.92-xLixTaO4:Eu3+0.08材料不仪结晶性能较好,而且Gd2O3和Ta2O5杂相也相对较少,故而发光增强最为明显.     

The synthesis of (Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>)<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu phosphor particles by flame spray pyrolysis with LiCl flux

(Y_1-xGd_x)₂O₃:Eu phosphor particles with dense morphology were prepared by flame spray pyrolysis and the effect of LiCl flux on the crystallinity, morphology, and photoluminescence characteristics of the particles was investigated. All as-prepared particles had monoclinic phase regardless of flux and had different luminescence characteristics from those of commercial Y₂O₃:Eu particles of cubic phase. The addition of LiCl flux reduced the post-treatment temperature by 300 °C for phase transformation from the monoclinic phase to the cubic phase. The post-treatment temperature of (Y_0.75Gd_0.25)₂O₃:Eu particles for phase transformation decreased from 1100 °C to 700 °C when LiCl flux was used. The morphology of the particles was also influenced by the Y/Gd ratio and the LiCl flux. The as-prepared particles had spherical shape and non-aggregation characteristics regardless of Y/Gd ratio and flux. The sphericity of the as-prepared particles prepared without flux was maintained after post-treatment for phase transformation in all Y/Gd ratios. However, LiCl addition promoted the aggregation between product particles. The prepared particles had high photoluminescence intensities comparable to that of the commercial product. PACS 64.70.Kb; 78.55.-m; 81.20.Rg; 75.50.Tt     

沉淀法制备Li~+、Na~+掺杂Gd_2O_3:Eu~(3+)荧光粉及发光特性研究

用沉淀法制备Li~+、Na~+和Eu~(3+)共掺Gd_2O_3荧光粉,并与微波-固相法制备的样品进行了比较。通过测量该粉体的XRD、激发光谱和发射光谱,比较了样品的微观结构和讨论了不同合成条件对Gd_2O_3:Eu~(3+)荧光粉发光特性的影响。结果显示在相同的条件下,对于未掺入Li~+的Gd_2O_3:Eu~(3+)样品比较,沉淀法制备样品的发光强度是微波-固相法制备样品的1.68倍;掺入Li~+的Gd_2O_3:Eu~(3+)样品比较,沉淀法制备样品的发光强度是微波—固相法制备样品的1.82倍。当使用草酸作为沉淀剂,掺杂浓度为Li~+(4.5 mol%)、Na~+(4.5mol%)、Eu~(3+)(4.5mol%),在800℃煅烧2h后获得样品的发光强度,是Gd_2O_3:Eu~(3+)荧光粉的5.91倍。     

Synthesis of high tap density Li3V2(PO4)3 cathode materials using mixed lithium precursors

High tap density Li₃V₂(PO₄)₃ cathode materials were synthesized using mixed LiF and LiNO₃ as lithium precursors, LiNO₃ was used as the sintering agent. Rietveld refinement results show that no impurities phases are detected in products. Particle size distribution and tap density measurement results show that particle size and tap density of products can be increased by the addition of LiNO₃. Electrochemical characterization results show that electrochemical performance of products is declined with the increase in contents of LiNO₃ in the lithium precursors. Only a small amount of LiNO₃ added in the lithium precursors (mole ratio of LiNO₃ to LiF is 1:9) can increase the tap density and also retain the good performance of products. Scanning electron microscopy (SEM) images indicate that the samples prepared by mixed lithium precursors present particles agglomerate, and the particle size increased with increase in contents of LiNO₃. Large amount of LiNO₃ added in the lithium precursors induces the particles to become spheric and smooth, which worsens the performance. The particles obtained with the mole ratio of LiNO₃ to LiF in 1:9 show a flake-like shape with a high specific surface area, which leads to good electrochemical performance.     

Spin exchange polarization and measurement of the hyperfine splitting of short-lived8Li

Free⁸Li (T _1/2=0.84 sec) atoms were polarized by spin exchange with optically pumped rubidium vapour. The⁸Li nuclei were produced by the reaction⁷Li(d, p)⁸Li in a thin LiF target. They recoiled into helium which was used as a buffer gas for optical pumping as well. Nuclear polarization up to 2% was detected by β-decay asymmetry. Rf transitions between hfs levels of the atomic ground state yielded the hfs separation ΔW=382.543(7) MHz. The nuclear spin assignmentI=2 was confirmed.     

Y2SiO5:Tb phosphor particles prepared from colloidal and aqueous solutions by spray pyrolysis

Green-emitting Y₂SiO₅:Tb phosphor particles with fine size, spherical shape, filled morphology, high crystallinity, and good brightness were synthesized by a spray pyrolysis process. The effect of silicon precursor type on the morphology, crystal structure, crystallinity, and photoluminescence efficiency of Y₂SiO₅:Tb phosphor particles was investigated. The particles prepared from an artificial colloidal solution obtained by dispersing fumed silica particles had a pure monoclinic X2 crystalline phase, which is more appropriate for application to displays, after post-treatment at 1300 °C. On the other hand, the particles prepared from 100% tetraethyl orthosilicate (TEOS) reagent had an X2 phase and small amounts of X1 and impurity phases such as Y₂Si₂O₇ and Y_4.67Si₃O₁₃ due to the phase-segregation characteristics of the TEOS precursor. The photoluminescence characteristics of Y₂SiO₅:Tb phosphor particles were strongly affected by the silicon source used. The photoluminescence intensities increased with the fumed silica/TEOS ratio. The particles prepared from 100% fumed silica showed the maximum photoluminescence intensity, which is 22% higher than that of particles prepared from 100% TEOS. PACS 81.20.Rg; 78.55.Hx; 78.40.Ha; 81.05.Hd; 81.40.Tv     

锂电池中负极表面固体电解质膜的SERS研究

本文对锂电池中负极材料表面固体电解质膜 (SEI膜 )的SERS谱进行了研究 :极化低电位下对贵重金属的研究表明 ,非水电解质溶液中痕量水的存在将对SEI膜产生重要影响。在微量水存在的情况下 ,RCOCO2 Li不是SEI膜的稳定成份 ,Li2 CO3、LiF、LiOH或LiOH·H2 O等物种才是其稳定组成。进一步的研究表明 :SEI膜的某些谱带具有不同的光吸收特性 ;它是对外界条件非常敏感的一种表面膜。通过对比分析 ,SEI膜的特征谱带得到了进一步归属 ,并对其形成机理做了讨论。     

Study of desorption activation energy on Rh-CO systems

The adsorption of CO on an Rh foil and small Rh particles supported by Al₂O₃ polycrystalline surfaces was studied using the temperature programmed desorption (TPD). The supported Rh particles were prepared by evaporation, using the principles of electron bombardment. The activation energy of desorption was calculated. The results show the dependence on the CO exposure of the sample as well as the size effect. The desorption and the recombination peaks were measured. The dissociation of CO and the influence of C atoms on the surface are discussed.