K3ZrF7:Mn4+红色荧光粉的溶剂热合成及发光性质

用溶剂热法制备了K_3ZrF_7,并利用离子交换法对其进行Mn~(4+)掺杂,获得了发光强度较高的红色荧光粉。分别用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对材料的结构和形貌进行了表征。考察了掺杂浓度(物质的量分数)对材料发光强度的影响。通过对比2种锰掺杂材料的发光行为,发现在掺杂浓度相同的条件下,K_3ZrF_7∶Mn~(4+)的发光强度是K_2ZrF_6∶Mn~(4+)的10倍多。通过对二者晶体结构和掺杂离子配位环境进行分析,从晶体场理论的角度解释了发光强度差异机制。     

单一基质白光荧光粉Ca0.955-xAl2Si2O8:0.045Eu2+,xMn2+的晶胞参数变化和光谱特性

利用高温固相反应制备了Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)(x=0,0.05,0.10,0.15,0.20,0.25,0.30,0.325,0.35,0.375,0.40,0.425)一系列试样,系统研究了Mn~(2+)取代基质中Ca~(2+)进入晶格中对其晶胞参数和光谱特性影响。Mn~(2+)以类质同相替代Ca~(2+)进入晶体晶格中,形成了连续固溶体,试样均为三斜晶系,P空间群。随着Mn~(2+)掺杂量增加,晶胞参数(a,b,c,γ)和晶胞体积V均呈线性递减,且a轴减幅最大,b轴最小,晶面夹角(α,β)呈线性递增。在357 nm激发下,获得的Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)发射光谱均有Eu~(2+)的4f→5d跃迁产生的433 nm和Mn~(2+)的~4T_1(~4G)→~6A_1(~6S)跃迁产生的567 nm两个宽带谱组成。在荧光粉Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)中,Eu~(2+)与Mn~(2+)间存在能量传递,Eu~(2+)→Mn~(2+)间能量传递的临界距离R_(Eu-Mn)=0.947 1 nm,Eu~(2+)→Mn~(2+)能量传递过程为电四极-电四极的多极矩相互作用。通过改变Mn~(2+)掺杂量,在紫外芯片的有效激发下,荧光粉的发射光颜色可从蓝光区(0.158 2,0.086 0)逐渐移至近白光区(0.295 3,0.298 9),可获得一种紫外激发适用于白光LED的单一组分白色荧光粉。     

近紫外激发Sm3+与Sr2+,Ba2+,Bi3+共掺杂的La1/3NbO3的发光性质

通过高温固相反应合成了La1/3NbO3∶Sm3+荧光粉.样品的荧光光谱表明,La1/3NbO3∶Sm3+荧光粉最强的激发带在406 nm,对应于Sm3+的6H5/2→4K11/2跃迁,属于近紫外区(365～410 nm).当激发波长为406nm时,样品的最强发射峰位于596 nm,是由Sm3+的4G5/2→6H7/2跃迁而产生的.因此,La1/3NbO3∶Sm3+可以作为基于近紫外激发的白光发光二极管(LED)的红光材料.而且,La位共掺杂Sr2+,Ba2+和Bi3+使样品的荧光强度大大增加,在最佳掺杂浓度时的量子产率分别为5.4%,7.5%和5.3%.     

形貌可控的NaCaGd(WO4)3:Eu3+红色荧光粉的制备及发光性能

采用水热法成功合成了形貌可控的NaCaGd_(1-x)(WO_4)_3∶x Eu~(3+)红色荧光粉。系统地研究了初始溶液pH值、反应温度和Eu3+掺杂浓度对NaCaGd_(1-x)(WO_4)_3∶x Eu~(3+)荧光粉物相结构、微观形貌和发光性能的影响。结果表明,当pH值为9、反应温度为180℃时,可合成单相四方晶系的NaCaGd(WO_4)_3,且颗粒微观形貌呈现分散性好、尺寸较均一的四方盘状纳米晶。在394 nm激发下,荧光粉显现典型的红光发射,其对应于Eu~(3+)的特征4f-4f跃迁。荧光粉发射光谱的强度随着pH值、反应温度及Eu~(3+)掺杂浓度的变化而变化。当pH=9、反应温度为180℃时,NaCaGd_(1-x)(WO_4)_3∶x Eu~(3+)(x=1)获得最佳发光强度。此外,研究了NaCaEu(WO_4)_3荧光粉的热稳定性,结果显示随着温度的升高,荧光粉发光强度逐渐降低。最后,通过理论计算得到荧光粉的色坐标和色纯度分别为(0.658,0.341)和96.1%,接近标准红色CIE坐标(0.673,0.327)。     

磷灰石结构荧光粉Ba10(PO4)6F2:Ce3+,Tb3+的合成、发光和能量传递

采用高温固相法合成了系列Ce~(3+)和Ce~(3+)/Tb~(3+)激活的具有磷灰石结构荧光粉Ba_(10)(PO_4)_6F_2。用X射线衍射(XRD)、扫描电镜(SEM)、激发和发射(PLE和PL)光谱对样品进行了表征分析。研究结果表明:所合成的荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)具有氟磷灰石结构,样品微观呈现不规则形貌。荧光粉Ba10-x(PO4)6F2∶x Ce~(3+)的相对发射强度随着x增加而增强,当x=0.09时,荧光强度达到最大。荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的激发光谱为240～330 nm的宽带,发射光谱呈现出Ce~(3+)的5d→4f跃迁紫外光(335和358 nm)发射和Tb~(3+)的4f→4f跃迁绿光(542 nm)发射。光谱特性表明,发光过程中存在Ce~(3+)→Tb~(3+)能量传递,能量传递效率可以达到60%。计算Ce~(3+)和Tb~(3+)的临界距离为0.79 nm,能量传递机理是偶极-偶极交互作用。此外,详细论述了Ce~(3+)和Tb~(3+)之间的能量传递和发光的过程。通过调节Tb~(3+)的掺杂浓度,对荧光粉发光色坐标与Tb~(3+)的掺杂浓度之间的关系也进行了研究,随着Tb~(3+)的掺杂量从0增加0.52,荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的发射光谱色坐标可以从(0.149 4,0.045 1)蓝色区变化到(0.280 1,0.585 3)绿色区。     

YAl3（BO3）4∶Eu3+荧光粉的化学沉淀法制备研究

以化学沉淀法制备单相的铕离子掺杂硼铝酸盐红色荧光粉YAl3(BO3)4∶Eu3+,考察了焙烧温度、掺铕量等因素对材料性能的影响,用X射线衍射、扫描电镜、激发光谱和发射光谱对荧光粉的结构、形貌和发光性能进行了表征.以尿素为沉淀剂,900℃焙烧沉淀前驱体可得到单相荧光粉YAl3(BO3)4∶Eu3+,反应温度比传统高温固相法降低了300℃;沉淀法制备的荧光粉粒径分布范围小,无团聚现象,粒径约300nm.掺铕量为10%(物质的量比)时发光强度最大.在260nm的紫外光激发下,Eu3+的5 D0→7 F2的电偶极跃迁最强,发射光为618nm的红光.     

绿色荧光粉KNaCa2（PO4）2:Tb3+的制备及发光性能研究

采用高温固相法成功制备了KNaCa2(PO4)2:Tb3+绿色荧光粉,并研究了其发光性质。测量了其激发和发射光谱,样品发射峰位于418,440,492,545,586,622 nm,分别对应Tb3+的5 D3→7 F5,5 D3→7 F4,5 D4→7 F6,5 D4→7 F5,5 D4→7 F4,5 D4→7 F3能级跃迁,主发射峰位于545 nm。主激发峰位于350～390 nm之间,属于4f→4f电子跃迁吸收,与InGaN管芯匹配。确定了在KNaCa2(PO4)2基质中Tb3+浓度对其发光强度的影响及其自身浓度猝灭机制。研究了不同电荷补偿剂对KNaCa2(PO4)2:Tb3+材料发光的影响,其中Li+离子改善其发光强度最为明显。     

YVO4∶Sm3+红色发光材料的熔盐法合成与光谱性能

采用熔盐法合成了YVO4∶Sm3+红色发光材料. 用X射线粉末衍射对其结构进行表征, 证实样品为具有锆石结构的YVO4相; 测定了样品的激发与发射光谱; 分析了不同的掺杂浓度和烧结温度对样品发光强度的影响. 研究结果表明, 采用熔盐法合成的样品均可以产生Sm3+的特征发射, 但是与其它方法相比, 熔盐法合成样品位于647 nm处Sm3+的4G5/2-6H9/2发射明显得到加强, 从而使得样品发出明亮的红光, 而不是其它合成方法获得的橙色光. 当掺杂浓度为1%(摩尔分数)且在500 ℃下烧结5 h后, 熔盐法得到的YVO4∶Sm3+荧光粉的发光强度最大.     

ABF4：Eu^2＋和A2SiF6：Eu^2＋中Eu^2＋的光谱结构

合成了Eu~(2+)激活的ABF_4和A_2SiF_6(A=Na、K、Rb、Cs)复合氟化物磷光体,得到了与ASTM一致的结晶学数据,在这些体系中都观察到了Eu~(2+)的f→跃迁锐峰发射,其中NaBF_4:Eu~(2+)和Na_2SiF_6:Eu~(2-)中Eu~(2+)所处基质晶格的配位数较低。     

白光LED用黄色荧光粉Ba(Y1-0.5x-yAly)2S4:xHo3+的合成和发光特性

采用高温固相法合成了Ba(Y1-0.5x-yAly)2S4:xHo3+系列荧光粉。在465 nm蓝光激发下,荧光粉的发射光谱呈多谱带发射,主峰位于492、543和661 nm处,分别对应于Ho3+的5F3→5I8,(5S2,5F4)→5I8和5F5→5I8跃迁发射。研究了Ho3+和Al3+掺杂量对BaY2S4:Ho3+发光性能的影响。结果表明,随着Ho3+掺杂量的逐渐增大,荧光粉的发光颜色由绿色逐渐向红色转变;适量Al3+取代Y3+可以提高BaY2S4:Ho3+荧光粉的发光强度。荧光粉Ba(Y0.665Al0.3)2S4:0.07Ho3+在蓝光(465 nm)激发下发射黄光,是一种潜在的白光LED用黄色荧光粉。     

Phase relations in the K2W2O7-K2WO4-KPO3-Bi2O3 system and structure of K6.5Bi2.5W4P6O34

The phase relations in the cross-section of the K₂W₂O₇-K₂WO₄-KPO₃ containing 15 mol% Bi₂O₃ were undertaken using flux method. Crystallization fields of K_6.5Bi_2.5W₄P₆O₃₄, K₂Bi(PO₄)(WO₄), Bi₂WO₆, KBi(WO₄)₂ and their cocrystallization areas were identified. Novel phase K_6.5Bi_2.5W₄P₆O₃₄ was characterized by single-crystal X-ray diffraction: sp. gr. P−1, a=9.4170(5), b=9.7166(4), c=17.6050(7) Å, α=90.052(5)°, β=103.880(5)° and γ=90.125(5)°. It has a layered structure, which contains {K₇Bi₅W₈P₁₂O₆₈}_∞ layers stacked parallel to ab plane and sheets composed by potassium atoms separating these layers. Sandwich-like {K₇Bi₅W₈P₁₂O₆₈}_∞ layers are assembled from [W₂P₂O₁₃]_∞ and [BiPO₄]_∞ building units, and are penetrated by tunnels with K/Bi atoms inside. FTIR-spectra of K₂Bi(PO₄)(WO₄) and K_6.5Bi_2.5W₄P₆O₃₄ were discussed on the basis of factor group theory.     

Sol-gel synthesis of K3InF6 and structural characterization of K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18

K₃InF₆ is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K₂InC₁₀O₁₀H₆F₉, K₃InC₁₂O₁₄H₄F₁₈ and K₃InC₁₂O₁₂F₁₈. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K₃InF₆ by decomposition at high temperature. The crystal structure of K₃InC₁₂O₁₄H₄F₁₈ is characterized by complex anions [In(CF₃COO)₄(OH_x)₂]^(5−2x)− and isolated [CF₃COOH_2−x]^(x−1)− molecules with x=2 or 1, surrounded by K⁺ cations. The crystal structure of K₃InC₁₂O₁₂F₁₈ is only constituted by complex anions [In(CF₃COO)₆]³⁻ and K⁺ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K₂InC₁₀O₁₀H₆F₉ and K₃InC₁₂O₁₂F₁₈ were also performed at room temperature on pulverized crystals.     

KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems

phase diagrams of KCl-KBO₂-K₂CO₃, K₂MoO₄-KBO₂-K₂CO₃, and K₂WO₄-KBO₂-K₂CO₃ ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E ₁: 622°C, 8.5 mol % KBO₂, 56.5 mol % KCl, and 35 mol % K₂CO₃; E ₂: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂MoO₄; E ₃: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂WO₄. The specific heats of melting of the eutectics were determined.     

Solubility in the Na2Cr2O7-(NH4)2Cr2O7-K2Cr2O7-H2O system

Solubility in the Na₂Cr₂O₇-(NH₄)₂Cr₂O₇-K₂Cr₂O₇-H₂O four-component water-salt system at 25, 50, and 75°C was studied for the first time. Phase field boundaries for individual salts and potassium and ammonium dichromate solid solutions, monovariant lines, and invariant points were determined. Experimental data were used to optimize the looped isohydric process of potassium dichromate preparation involving additional salts.     

Li2SO4-Na2SO4-H2O和Li2SO4- K2SO4-H2O溶液的体积性质

本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li₂SO₄ + Na₂SO₄ + H₂O和 Li₂SO₄ + K₂SO₄ + H₂O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg_–1,混合溶液中Na₂SO₄和K₂SO₄的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θ_V和 ψ_V,模型的计算值与实验值的偏差在±0.002 g.cm_–3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。     

NaBO2-NaCl-Na2CO3, NaBO2- Na2CO3-NaMoO4, NaBO2- Na2CO3-NaWO4, and NaBO2-NaCl-Na2WO4 ternary systems

The phase diagrams of the NaBO₂-NaCl-Na₂CO₃, NaBO₂-Na₂CO₃-Na₂MoO₄, NaBO₂- Na₂CO₃-Na₂WO₄, and NaBO₂-NaCl-Na₂WO₄ ternary systems were studied by a calculation-experimental method and differential thermal analysis. The coordinates of ternary eutectics were determined: E ₁: 612°C, 16 mol % NaBO₂, 42 mol % NaCl, and 42 mol % Na₂CO₃; E ₂: 568°C, 12 mol % NaBO₂, 28 mol % Na₂CO₃, and 60 mol % Na₂MoO₄; E ₃: 575°C, 12 mol % NaBO₂, 32 mol % Na₂CO₃, and 56 mol % Na₂WO₄; E ₄: 628°C, 8 mol % NaBO₂, 20 mol % NaCl, and 72 mol % Na₂WO₄; and E ₅: 655°C, 9 mol % NaBO₂, 53 mol % NaCl, and 38 mol % Na₂WO₄.     

Extension of the La7Mo7O30 structural type with La7Nb3W4O30 and La7Ta3W4O30 compounds

Two compounds of formula La₇A₃W₄O₃₀ (with A=Nb and Ta) were prepared by solid-state reaction at 1450 and 1490 °C. They crystallize in the rhombohedric space group R-3 (No. 148), with the hexagonal parameters: , and , . The structure of the materials was analyzed from X-ray, neutron and electronic diffraction. These oxides are isostructural of the reduced molybdenum compound La₇Mo₇O₃₀, which are formed of perovskite rod along [111]. An order between (Nb, Ta) and W is observed.     

Preparation and structure of NaSr0.5Al2B2O7 and NaCa0.5Al2B2O7

Two compounds NaSr_0.5Al₂B₂O₇ and NaCa_0.5Al₂B₂O₇, have been found to crystallize into a new structure type by Rietveld refinement from X-ray powder diffraction data. Their structure belongs to hexagonal space group P6₃/m, with lattice parameters of , for NaSr_0.5Al₂B₂O₇ and , for NaCa_0.5Al₂B₂O₇, respectively. The structure is built up by [Al₂B₂O₇]²⁻ double layer and Na⁺/Ca²⁺ or Na⁺/Sr²⁺ ions alternatively stacking along the c-axis. The sites in the inter-double layer are fully occupied jointly by Na and Ca or Sr, but the intra-double layer sites are only half occupied solely by Na. A mechanism of the transition of the structure from CaAl₂B₂O₇ to present structure type by replacing only 1% Ca by Na (2%) as observed by Chang and Keszler (Mater. Res. Bull. 33 (1998) 299) is also proposed.     

SnSbBiS4-SnS and SnSbBiS4-Sn2Sb6S11 sections of the SnS-Sb2S3-Bi2S3 ternary system

SnSbBiS₄-SnS and SnSbBiS₄-Sn₂Sb₆S₁₁ sections were studied by physicochemical methods (DTA, X-ray powder diffraction, microstructure observation, and microhardness measurements). These sections were found to be eutectic quasi-binary sections of the SnS-Sb₂S₃-Bi₂S₃ ternary system. Solid solution regions based on the initial components were found on either side of the sections. Alloys in the solid solution region are p-type semiconductors.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…