Mg_(3)Ca_(3)(PO_(4))_(4):Eu^(2+)蓝色荧光粉的合成及发光特性研究

采用常规高温固相反应合成法,在炭热还原气氛下制备Mg_(3)Ca_(3)(PO_(4))_(4):Eu^(2+)荧光粉材料.通过测量激发光谱、发射光谱等光谱学手段,对所制备荧光粉样品的发光性质进行研究,讨论激发光波长、Eu^(2+)离子的掺杂浓度等因素对荧光粉光致发光性能的影响.结果显示,Mg_(3)Ca_(3)(PO_(4))_(4):Eu^(2+)在275 nm~350 nm宽带范围内存在高效吸收,在400 nm~500nm内有很强的蓝色荧光发射.该材料可作为潜在的蓝色荧光材料,在LEDs彩色显示等领域有广泛用途.

浸渍Ca_(3)(PO_(4))_(2)溶液对SiC窑具材料晶相结构与性能影响

浸渍Ca3(PO4) 2 饱和溶液对SiC窑具材料晶相结构的转化和性能的优化是有利的。使SiC结构由低温稳定型向高温稳定型转化 ,随浸渍次数 (每次浸渍时间 1 0分钟 )的增加 ,α 型SiC含量增加 ,浸渍 4次的α 型SiC含量最高 (81 .1 % )。材料性能随浸渍次数增加而优化 ,浸渍 4次的显气孔率和吸水率最低 ,体积密度和热稳定性最高。

Tm^(3+)‑Tb^(3+)‑Eu^(3+)共掺含Na_(3)Gd(PO_(4))_(2)晶相荧光玻璃陶瓷的制备及发光性能

采用熔融晶化法制备Tm^(3+)‑Tb^(3+)‑Eu^(3+)掺杂含Na_(3)Gd(PO_(4))_(2)晶相荧光玻璃陶瓷,并对其光学性能进行了研究。利用差示扫描量热分析(DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试,确定了样品的晶相结构和最佳热处理条件(740℃/3 h)。在359 nm激发下,Tm_(2)O_(3)、Tb_(4)O_(7)、Eu_(2)O_(3)掺杂浓度(物质的量分数)分别为0.2%、0.2%、0.95%时,玻璃陶瓷的色度坐标为(0.3332,0.3188),接近标准白光(0.333,0.333)。结合荧光光谱和荧光衰减曲线分析,证实了样品中存在Tm^(3+)→Eu^(3+)、Tb^(3+)→Eu^(3+)的能量传递。

发光材料BaSrMg(PO_4)_2∶Eu^(3+)的水热法制备及发光性能研究

采用水热法制备了可用于白光LED的红色发光材料BaSrMg(PO_4)_2∶Eu^(3+)。通过X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)对其结构和形貌进行测试表征,研究了不同pH值(5,6,7和8)和不同反应温度(120,140,160,180和200℃)对荧光粉的晶体结构和形貌的影响。从XRD的结果可以看到,当pH6时合成的样品的衍射峰为较高强度的锐锋,FESEM扫描图像也显示该制备条件下获得了立方体形状的规则晶体。在pH值分别为5,7,8时所制备的样品XRD图谱中大多是强度很弱的宽峰叠加了极少的锐锋,表明样品为固熔体或者含有混合相,这与FESEM扫描图像所显示的无定形态颗粒的结果相一致。荧光光谱测试结果表明,该荧光粉在394nm波长光的激发下产生的发射谱包含了以下6组发射峰536nm(~5 D1→~7 F_1),578nm(~5 D_0→~7 F_0),590nm(~5 D_0→~7 F_1),613nm(~5 D_0→~7 F_2),646nm(~5 D_0→~7 F_3)和696nm(~5 D_0→~7 F_4)。荧光粉的激发光谱分别由361nm(~7 F_0→~5 D_4),380nm(~7 F_0→~5 L_8),394nm(~7 F_0→~5 L_6)和464nm(~7 F_0→~5 D_2)四组激发峰组成。经过条件优化后制备的荧光粉的主要激发峰在394nm(~7 F_0→~5 L_6),该荧光粉在394nm波长光激发下产生的发射峰主峰在613nm(~5 D_0→~7 F_2)。发射峰的劈裂随着pH值和温度的变化而改变,这一现象说明了荧光粉的发光性质与它的晶体结构和颗粒形貌存在着密切的联系。

超高镍LiNi_(0.91)Co_(0.06)Al_(0.03)O_(2)@Ca_(3)(PO_(4))_(2)正极材料的储锂稳定性的提升机制

超高镍正极材料具有高比能、高电压和低成本等特点,在新一代锂离子电池中备受关注,但在电池的长循环过程中会出现微裂纹、机械粉化和不可逆相变,导致差的循环性能。本研究采用简便的湿化学法制备了一系列Ca_(3)(PO_(4))_(2)包覆的超高镍LiNi_(0.91)Co_(0.06)Al_(0.03)O_(2)材料(NCA@n CP)。其中,NCA@1CP在1C (1C=200 m A/g)、2.7~4.3 V下可获得204.8 m Ah/g的放电比容量,100圈循环后容量保持率为91.5%,甚至在2C的倍率下循环300圈后仍保留153.4 mAh/g的放电比容量。表征结果证实该包覆层可抑制材料的Li/Ni混排、不可逆相变和机械粉化,从而大幅提升了循环稳定性。本研究表明Ca_(3)(PO_(4))_(2)包覆策略在提升超高镍正极材料储锂稳定性方面具有较大的应用潜力。

高温固相法制Zn_(3)(PO_(4))_(2):Eu^(3+)荧光粉及其发光性质研究

应用高温固相法制备了Zn_(3)(PO_(4))2:Eu^(3+)荧光粉,对Zn_(3)(PO_(4))2:Eu^(3+)的XRD进行实验分析,结果表明:样品的衍射峰值基本对应了PDF#30-1490的标准卡片,其结晶性良好。实验过程中,Zn_(3)(PO_(4))2被成功的制备出来,没有杂质生成。同时,对Zn_(3)(PO_(4))2:Eu^(3+)的发光性质进行实验分析,结果表明:在616 nm为检测波长的前提下,Zn_(3)(PO_(4))2:0.03Eu^(3+)属于Eu^(3+)的f-f特征跃迁,388 nm处激发的峰值较大;在388 nm为监测波长的前提下,Zn_(3)(PO_(4))2:0.03Eu^(3+)的激发光谱图有三个发射峰。其中,以5D0→7F2(616 nm)的电偶极跃迁发射最强,即发出红色光亮。在388 nm为监测波长前提下,得到Zn_(3)(PO_(4))2:0.05Eu^(3+)、Zn_(3)(PO_(4))2:0.04Eu^(3+)、Zn_(3)(PO_(4))2:0.03Eu^(3+)、Zn_(3)(PO_(4))2:0.02Eu^(3+)以及Zn_(3)(PO_(4))2:0.01Eu^(3+)的激发光谱图,分析得出Eu^(3+)的最佳掺杂浓度为0.03。

Synthesis and optical properties of highly efficient Na_(3)KMg_(7)(PO_(4))_(6):Eu^(2+)blue phosphor for full-spectrum white-light-emitting diodes:The role of Li_(2)CO_(3)flux

Full-spectrum phosphor-converted white-light-emitting diodes(pc-WLED)are emerging as a mainstream technology in semiconductor lighting.Nevertheless,high-performance blue phosphor which can be excited efficiently by a 400 nm NUV diode chip is still lacking.Herein,we present a blue-emitting Na_(3)KMg_(7)(PO_(4))6:Eu^(2+)phosphor synthesized by the solid-reaction method.Particularly,we find that the using of Li_(2)CO_(3)as flux can significantly improve the crystal quality and thus the emission efficiency of the phosphor.Meanwhile,the excitation peak of the phosphor shifts from 365 to 400 nm,which is pivotal for efficient NUV(400 nm)diode chip excitation.The practical Eu^(2+)concentration is also enhanced by using Li_(2)CO_(3)as flux,and the absorption efficiency is greatly increased.This phosphor exhibits superior PL thermal stability,namely retains 94%integrated photoluminescence intensity at 150℃of that at 25℃.As a result,the optimized phosphor shows an emission band peaked at 437 nm with a bandwidth of 40 nm and a high external photoluminescence quantum yield of 51.7%.Finally,a pc-WLED was fabricated by using NKMPO:Eu^(2+)blue,Sr_(2)SiO_(4):Eu^(2+)green,CaAlSiN_(3):Eu^(2+)red phosphors,and a 400 nm NUV diode chip.It shows a high color rendering index of R_(a)=96.4 and a correlated color temperature of 4358 K.These results prove that NKMPO:Eu^(2+)is a promising blue phosphor for full-spectrum WLED based on NUV diode chips.

Multi-site occupancies and luminescence properties of cyan-emitting Ca_(9-x)NaGd_(2/3)(PO_(4))_(7):Eu^(2+)phosphors for white light-emitting diodes

Cyan-emitting Ca_(9)NaGd_(2/3)(PO_(4))_(7):Eu^(2+)phosphors were synthesized via high temperature solid-state route.X-ray powder diffraction(XRD)and scanning electron microscopy(SEM)were used to verify the phase and morphology of the Ca_(9)NaGd_(2/3)(PO_(4))_(7):Eu^(2+)(CNGP:Eu^(2+))phosphors.The as-obtained phosphor exhibits a broad excitation band of 250-420 nm,which is near the ultraviolet region.An intense asymmetric cyan emission at 496 nm corresponds to the 5 d-4 f transition of Eu^(2+).The multiplesite luminescent properties of Eu^(2+)ions in CNGP benefit from versatile structure ofβ-Ca3(PO4)2 compounds.The effective energy transfer distance is 5.46 nm(through the spectral overlap calculation),validating that the resonant energy migration type is via dipole-dipole interaction mechanism.Compared to the initial one at room temperature,the luminescent intensity of CNGP:Eu^(2+)phosphor can maintain 77%as it is heated up to 420 K.A white light-emitting diode(WLED)with excellent luminesce nt properties was successfully fabricated.Moreover,the CIE chromaticity coordinates of fabricated WLED driven by changing current just change slightly.

Photoluminescence properties and energy transfer of novel orange–red emitting phosphors:Ba_(3)Bi_(2)(PO_(4))_(4):Sm^(3+),Eu^(3+) for white light-emitting diodes

Sm^(3+), Eu^(3+)co-coped Ba_(3)Bi_(2)(PO_(4))_(4) phosphors,as potential phosphors for white light-emitting diode applications, were synthesized through the solid-state reaction method for the first time. The crystal structure,absorption spectra, photoluminescence properties, decay time, energy transfer mechanism, temperature-dependent properties, and Commission International De L’Eclairage(CIE) chromaticity coordinates were investigated systematically. The pure eulytite-type Ba_(3)Bi_(2)(PO_(4))_(4) phase was obtained after heating at 980 ℃ for 5 h. A notably enhanced absorption efficiency at 393 nm was observed when Sm^(3+), as a sensitizer, was doped into Ba_(3)Bi_(1.82)(PO_(4))_(4): 0.18 Eu^(3+)and the band gap of the Ba_(3)Bi_(2)(PO_(4))_(4) host was estimated to be 4.19 eV. The emission intensity of Ba_(3)Bi_(1.82)(PO_(4))_(4): 0.18 Eu^(3+)was significantly enhanced when Sm^(3+)was co-doped. The existence and mechanism of energy transfer from Sm^(3+) to Eu^(3+)were evaluated by photoluminescence spectra and decay time measurements. The CIE chromaticity coordinate of Ba3 Bi1.75(PO4)4: 0.07 Sm^(3+), 0.18 Eu^(3+) phosphor was calculated to be(0.5746, 0.4197), respectively.

Effect of monovalent charge compensators on the photoluminescence properties of Ca_(3)(PO_(4))_(2):Tb^(3+),A^(+)(A=Li,Na,K)phosphors

Ca_(3-x)(PO_(4))_(2):xTb^(3+)(0.2≤x≤0.4),Ca_(2.3)(PO_(4))_(2):0.35 Tb^(3+),0.35 A^(+)(A=Li,Na,K),and Ca_(2.3)(PO_(4))_(2):0.35 Tb^(3+),yLi^(+)(0.35≤y≤0.455)phosphors were prepared by solid-state reaction.All the prepared phosphors formed a rhombohedral unit cell with the R3c space group.To improve the photoluminescence(PL)properties of the Ca_(2.65)(PO_(4))_(2):0.35 Tb^(3+)phosphor,monovalent charge compensators such as Li^(+),NA^(+),and K^(+)were added to the Ca_(2.65)(PO_(4))_(2):0.35 Tb^(3+)phosphor.The charge compensators acted as fluxes,so they improved the crystallinity.The excitation and emission properties were significantly improved through the incorporation of charge compensators.In particular,among the charge compensators,Li^(+)ion substantially enhanced the emission intensity and color purity.Furthermore,considering the evaporation of Li_(2)CO_(3)during the annealing process,we optimized the concentration of Li^(+)charge compensator to enhance its PL performance.Impressively,the green emission intensity of the Ca_(2.3)(PO_(4))_(2):0.35 Tb^(3+),0.385 Li^(+)phosphor was 260%higher than that of the Ca_(2.65)(PO_(4))_(2):0.35 Tb^(3+)phosphor.We believe that the effect of charge compensators on the PL properties and the optimum concentration of Li^(+)cha rge compensator are useful for the design of phosphors in light-emitting diodes.

Tunable emission properties of tri-doped Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+) phosphors with warm white emitting based on energy transfer

Tri-doped Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+)phosphors were prepared by a high-temperature solid state method.Under UV light excitation,Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+)samples exhibit a broad band ranging from 320 to 500 nm.At 77 K,the emission spectra of Ca_(9)LiY_(2/3)(PO_(4))7:Ce^(3+)samples present two obvious emission peaks,indicating that Ce^(3+)ions occupy two different kinds of lattice sites(Ca(1/2)and Ca(3)),As a good sensitizer for Tb^(3+),Ce^(3+)ions in Ca_(9)LiY_(2/3)(PO_(4))_(7)lattice can effectively transfer part of energy to Tb^(3+),and the energy trans fer mechanism is determined to be dipole-dipole interaction.Consequently,the emitting color for Ce^(3+)and Tb^(3+)co-doped Ca_(9)LiY_(2/3)(PO_(4))_(7)samples can be tuned from bluish violet to green.In order to further enlarge the emission gamut,Mn^(2+)ions as red emission components were added,forming tri-doped single-phase Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+)phosphors.The Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+)phosphors exhibit tunable emission properties through controlling the relative doping concentration of Ce^(3+),Tb^(3+)and Mn^(2+).Especially,Ca_(9)LiY_(2/3)(PO_(4))_(7):0.09 Ce^(3+),0.12 Tb^(3+),0.30 Mn^(2+)can emit warm white light.The sample shows good thermal stability.At 150℃,the emission intensity for Ce^(3+)(360 nm),Tb^(3+)(545 nm)and Mn^(2+)(655 nm)decreases to 63%,69%,and 72%of its initial intensity,respectively.Moreover,the sample obtains good stability after 10 cycles between room temperature and150℃.

Color-tunable Ca10Na(PO4)7：Ce^3＋/Tb^3＋/Mn^2＋ phosphor via energy transfer

A series of Ca10Na(PO4)7:Ce3+/Tb3+/Mn2+(CNPO:Ce3+/Tb3+/Mn2+) phosphors with high brightness were synthesized by high-temperature solid-state method. X-ray diffraction(XRD), scanning electron microscopy(SEM), diffuse reflectance spectra(DRS), photo luminescence(PL) spectra, luminescence decay curves and thermally stability were performed to characterize the as-prepared samples. For Ce3+-doped samples, an intense and broad band emission is present under 265 nm excitation. When Ce3+and Tb3+are codoped, energy transfer(ET) process from Ce3+ to Tb3+ is demonstrated with electric dipole-dipole interaction. The internal and external quantum efficiencies(QEs) of CNPO:0.15 Ce3+, 0.04 Tb3+, 0.005 Mn2+are measured to 76.79% and 54.11% under 265 nm excitation and temperature-dependent PL intensity can remain 51.78% at 150 ℃ of its initial intensity at 25 ℃. It is indicated that single-phased white lightemitting CNPO:Ce3+/Tb3+/Mn2+phosphor can serve as a promising phosphor for illumination devices.

三元共聚物阻垢分散剂的合成及阻垢性能研究

合成了一系列丙烯酸─丙烯酸甲酯─丙烯酰胺阻垢分散剂，研究了共聚物浓度、钙离子浓度、水质ｐＨ值、温度及恒温时间对阻垢性能的影响。研究结果表明：该阻垢分散剂对碳酸钙、硫酸钙、磷酸钙具有较优异的阻垢性能，且对循环水硬度、ｐＨ值及温度适用范围广，可广泛用作工业循环冷却水的阻垢分散剂。

磷酸钙对缓解准东高钠-富铁混煤结渣倾向的影响

针对新疆地区高钠煤与富铁煤掺混燃烧中发生的严重结渣难题,本文采用沉降炉探究Ca_(3)(PO_(4))_(2)在降低高钠-富铁混煤结渣倾向方面的潜力,并结合多种表征方法对探针收集的渣样的成分、矿物相和形貌进行了详细分析。结果表明:添加3%Ca_(3)(PO_(4))_(2)即可显著提升准东混煤的灰熔点,软化温度提升幅度高达200℃,变形温度提升150℃;对于高钠与富铁质量比为40:60的原混煤,炉内1200℃位置非冷却探针表面黏附的灰渣呈熔融状,其致渣组分主要为Fe_(2)O_(3)和含Si-Al-Ca矿物相的低温共熔体系;添加Ca_(3)(PO_(4))_(2)后,1200℃区域探针表面黏附的灰渣基本呈颗粒状,熔融度降低,而在1000℃区域探针表面收集的灰样变为松散状且易于吹除;掺混3%Ca_(3)(PO_(4))_(2)后黏附灰渣的熔融度降低的主要原因为Ca_(3)(PO_(4))_(2)能结合含Na、Ca组分生成高熔点的Ca_(5)(PO_(4))_(2)SiO_(4)和Na_(3)Ca_(6)(PO_(4))_(5),有效固留气态含钠组分,减少含碱金属/碱土金属组分的冷凝以及它们同含Si、Al矿物相结合发生低温共熔反应的可能性,该添加剂在减小高钠-富铁混煤结渣倾向方面具有较好的效果。