微乳法制备Gd_2O_3：Tb～（3+）、Gd_2O_2S：Tb～（3+）纳米粒子及发光性能研究
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摘要
本论文研究纳米Gd_2O_3:Tb~(3+)、Gd_2O_2S:Tb~(3+)的制备、结构表征和性能。用微乳液法合成了纳米Gd_2O_3:Tb~(3+)和Gd_2O_2S:Tb~(3+),对二者的结构、形貌、大小等进行了表征;测定了纳米Gd_2O_3:Tb~(3+)的前驱体纳米草酸钆的热解机理和热分解反应动力学参数;研究了Gd_2O_3:Tb~(3+)和Gd_2O_2S:Tb~(3+)的发光性能以及Tb~(3+)的最佳发光离子浓度。具体工作包括以下几个方面:
(1)通过滴定作出TX—100/正己醇/正辛烷/水的部分拟三元相图,在W/O型微乳液的纳米反应器中合成了纳米Gd_2O_3:Tb~(3+)荧光粉,结构表征证实其为立方氧化钆。粒子为球形,大小均匀,分散性好。随着w值(w=[H_2O]/[表面活性剂])从0.86减小到0.33,制得的纳米粒子粒径也从20～30nm减小为8～15nm。微乳液法中的晶体形成温度较草酸沉淀法降低了近100℃,具有较快的成晶速度。纳米Gd_2O_3:Tb~(3+)荧光粉的发射光谱显示出Tb~(3+)的4个特征发射,其主要发射峰在543nm处,为~5D_4到~7F_5能级跃迁;并且随着纳米粒子粒径的增大,发光强度逐渐增强。Gd_2O_3:Tb~(3+)中Tb~(3+)的最佳发光离子浓度是1×10~(-3)摩尔/摩尔基质。
(2)在W/O型微乳液的纳米反应器的水滴中合成了纳米Gd_2O_3:Tb~(3+)的前驱体纳米草酸钆,粒子为球形,大小较均匀,粒径为4～10nm。通过纳米草酸钆的TG—DTA分析、XRD图谱和FT—IR分析,研究得到微乳法制得的纳米草酸钆的热解机理为:Gd_2(C_2O_4)_3.10H_2O→Gd_2(C_2O_4)_3+10H_2O,Gd_2(C_2O_4)_3→Gd_2O_2(CO_3)+3CO+2CO_2,Gd_2O_2(CO_3)→Gd_2O_3+CO_2,比体相草酸钆的热解机理复杂。运用Ozawa方法计算第二、三步的热分解反应的活化能分别为194.6kJ.mol~(-1)和110.9kJ.mol~(-1);由TG曲线法确定了相应的反应级数是3.0和0.43。
(3)将制得的Gd_2O_3:Tb~(3+)纳米粒子和无水碳酸钠、升华硫在1200℃煅烧后得到纳米Gd_2O_2S:Tb~(3+),XRD分析证实其为六方Gd_2O_2S:Tb~(3+)。纳米粒子为球形,有利于紧密堆积,改善荧光粉的填充度,粒径为10～20nm;由于高温灼烧,纳米小球聚集在一起形成微米小球,其大小在0.2～0.5μm。纳米Gd_2O_2S:Tb~(3+)荧光粉的主要发射峰在540nm,该处发光强度明显高于草酸沉淀制得的Gd_2O_2S:Tb~(3+),并且在~D_4到~7F_6的能级跃迁中发生蓝移现象。
The preparation, characterization and capability of nanosized Gd_2O_3:Tb~(3+) and Gd_2O_2S: Tb~(3+) were studied in the thesis. nanoparticles Gd_2O_3:Tb~(3+) and Gd_2O_2S:Tb~(3+) were prepared in the reverse microemulsions. With the nanoparticles obtained in this way, their crystal structure, shape and size were characterized. The mechanism of thermal decomposition of precursor nanosized oxalate and the kinetic parameters of thermal decomposition reaction-activation energy E and reaction order n were studied. And the photoluminescence of Gd_2O_3:Tb~(3+) and Gd_2O_2S:Tb~(3+), and the best luminescent ionic content of Tb~(3+) were measured.( 1 ) Gd_2O_3:Tb~(3+) luminescent nanoparticles were prepared in the reverse microemulsions based on triton X-100/n-hexyl alcohol, n-octane, and water. The particles has pure cubic structure proved by XRD, and has shown good dispersion and light agglomeration. With the water-to-surfactant molar(w=[H_2O]/[surfactant]) decreased, the nanoparticles' diameter are reduced from 20~30nm to 8~15nm. Compared with the products which prepared by oxalate precipitation, the nanoparticles' size is small and the crystal forming temperature is decreased. The emission spectra of Gd_2O_3:Tb~(3+) include four characteristic peak which are located in 485、 543、 586 and 621nm. These emission peaks show the transition from ~5D_4 to ~7F_6、 ~7F_5、 ~7F_4 and ~7F_3 of Tb~(3+) respectively. And the major emission peak is 543nm. The intensity of the peaks in the emission spectra are connected with the particles size of the powders. With the increase of nanoparticles' diameter, the intensity are enhanced. And the best luminescent ionic content of Tb~(3+) is 1 × 10~(-3) mol/mol.(2) Proved by TG-DTA 、 XRD and FT-IR analyse of nanosized oxalate, the mechanism of thermal decomposition of precursor nanosized oxalate prepared by microemulsions are: Gd_2(C_2O_4)_3.10H_2O → Gd_2(C_2O_4)_3 + 10H_2O, Gd_2(C_2O_4)_3 → Gd_2O_2(CO_3) + 3CO+2CO_2, Gd_2O_2(CO_3) → Gd_2O_3 + CO_2. Which are complicated than bulk materials. The kinetic parameters of thermal decomposition
reaction-activation energy E of stage 2 and 3 are 194.6 kJ.mor1, 110.9 kJ.mol"1 by using Ozawa method. And the reaction order n are 3.0 and 0.43, respectively, according to the TG curves.( 3 ) Nanosized Gd2O2S:Tb3+ can be prepared by the calcinations of nanoparticles Gd2O3:Tb3\ Na2CO3 and S in 1200°C. According to the PDF, the products has pure hexagonal structure. TEM photo show the nanoparitcles are sphere, having uniform diameter size of 10~20nm. And Because of high temperature calcinations, the nanoparticles conglomerate to form micron balls, whose diameter size are 0.2-0.5um. Compared with the microemulsion, the products prepared by oxalate deposition are anomaly micron flake. In addition, the emission spectra of nanosized Gd2O2S:Tb + are different to the micron materials. The intensity of the major emission peaks is enhanced obviously. And blue-shift are happened in the transition from 5D4 to 7F6.
(1)通过滴定作出TX—100/正己醇/正辛烷/水的部分拟三元相图,在W/O型微乳液的纳米反应器中合成了纳米Gd_2O_3:Tb~(3+)荧光粉,结构表征证实其为立方氧化钆。粒子为球形,大小均匀,分散性好。随着w值(w=[H_2O]/[表面活性剂])从0.86减小到0.33,制得的纳米粒子粒径也从20～30nm减小为8～15nm。微乳液法中的晶体形成温度较草酸沉淀法降低了近100℃,具有较快的成晶速度。纳米Gd_2O_3:Tb~(3+)荧光粉的发射光谱显示出Tb~(3+)的4个特征发射,其主要发射峰在543nm处,为~5D_4到~7F_5能级跃迁;并且随着纳米粒子粒径的增大,发光强度逐渐增强。Gd_2O_3:Tb~(3+)中Tb~(3+)的最佳发光离子浓度是1×10~(-3)摩尔/摩尔基质。
(2)在W/O型微乳液的纳米反应器的水滴中合成了纳米Gd_2O_3:Tb~(3+)的前驱体纳米草酸钆,粒子为球形,大小较均匀,粒径为4～10nm。通过纳米草酸钆的TG—DTA分析、XRD图谱和FT—IR分析,研究得到微乳法制得的纳米草酸钆的热解机理为:Gd_2(C_2O_4)_3.10H_2O→Gd_2(C_2O_4)_3+10H_2O,Gd_2(C_2O_4)_3→Gd_2O_2(CO_3)+3CO+2CO_2,Gd_2O_2(CO_3)→Gd_2O_3+CO_2,比体相草酸钆的热解机理复杂。运用Ozawa方法计算第二、三步的热分解反应的活化能分别为194.6kJ.mol~(-1)和110.9kJ.mol~(-1);由TG曲线法确定了相应的反应级数是3.0和0.43。
(3)将制得的Gd_2O_3:Tb~(3+)纳米粒子和无水碳酸钠、升华硫在1200℃煅烧后得到纳米Gd_2O_2S:Tb~(3+),XRD分析证实其为六方Gd_2O_2S:Tb~(3+)。纳米粒子为球形,有利于紧密堆积,改善荧光粉的填充度,粒径为10～20nm;由于高温灼烧,纳米小球聚集在一起形成微米小球,其大小在0.2～0.5μm。纳米Gd_2O_2S:Tb~(3+)荧光粉的主要发射峰在540nm,该处发光强度明显高于草酸沉淀制得的Gd_2O_2S:Tb~(3+),并且在~D_4到~7F_6的能级跃迁中发生蓝移现象。
The preparation, characterization and capability of nanosized Gd_2O_3:Tb~(3+) and Gd_2O_2S: Tb~(3+) were studied in the thesis. nanoparticles Gd_2O_3:Tb~(3+) and Gd_2O_2S:Tb~(3+) were prepared in the reverse microemulsions. With the nanoparticles obtained in this way, their crystal structure, shape and size were characterized. The mechanism of thermal decomposition of precursor nanosized oxalate and the kinetic parameters of thermal decomposition reaction-activation energy E and reaction order n were studied. And the photoluminescence of Gd_2O_3:Tb~(3+) and Gd_2O_2S:Tb~(3+), and the best luminescent ionic content of Tb~(3+) were measured.( 1 ) Gd_2O_3:Tb~(3+) luminescent nanoparticles were prepared in the reverse microemulsions based on triton X-100/n-hexyl alcohol, n-octane, and water. The particles has pure cubic structure proved by XRD, and has shown good dispersion and light agglomeration. With the water-to-surfactant molar(w=[H_2O]/[surfactant]) decreased, the nanoparticles' diameter are reduced from 20~30nm to 8~15nm. Compared with the products which prepared by oxalate precipitation, the nanoparticles' size is small and the crystal forming temperature is decreased. The emission spectra of Gd_2O_3:Tb~(3+) include four characteristic peak which are located in 485、 543、 586 and 621nm. These emission peaks show the transition from ~5D_4 to ~7F_6、 ~7F_5、 ~7F_4 and ~7F_3 of Tb~(3+) respectively. And the major emission peak is 543nm. The intensity of the peaks in the emission spectra are connected with the particles size of the powders. With the increase of nanoparticles' diameter, the intensity are enhanced. And the best luminescent ionic content of Tb~(3+) is 1 × 10~(-3) mol/mol.(2) Proved by TG-DTA 、 XRD and FT-IR analyse of nanosized oxalate, the mechanism of thermal decomposition of precursor nanosized oxalate prepared by microemulsions are: Gd_2(C_2O_4)_3.10H_2O → Gd_2(C_2O_4)_3 + 10H_2O, Gd_2(C_2O_4)_3 → Gd_2O_2(CO_3) + 3CO+2CO_2, Gd_2O_2(CO_3) → Gd_2O_3 + CO_2. Which are complicated than bulk materials. The kinetic parameters of thermal decomposition
reaction-activation energy E of stage 2 and 3 are 194.6 kJ.mor1, 110.9 kJ.mol"1 by using Ozawa method. And the reaction order n are 3.0 and 0.43, respectively, according to the TG curves.( 3 ) Nanosized Gd2O2S:Tb3+ can be prepared by the calcinations of nanoparticles Gd2O3:Tb3\ Na2CO3 and S in 1200°C. According to the PDF, the products has pure hexagonal structure. TEM photo show the nanoparitcles are sphere, having uniform diameter size of 10~20nm. And Because of high temperature calcinations, the nanoparticles conglomerate to form micron balls, whose diameter size are 0.2-0.5um. Compared with the microemulsion, the products prepared by oxalate deposition are anomaly micron flake. In addition, the emission spectra of nanosized Gd2O2S:Tb + are different to the micron materials. The intensity of the major emission peaks is enhanced obviously. And blue-shift are happened in the transition from 5D4 to 7F6.
引文
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