前驱溶液的pH值对制备Ca2Zn4Ti16O38 ∶ Pr3+,Na+ 发光粉物相、形貌和发光性质的影响

周 文; 余丽萍; 廉世勋; 祁 媛; 朱爱玲; 荣春英

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前驱溶液的pH值对制备Ca₂Zn₄Ti₁₆O₃₈ ∶ Pr³⁺,Na⁺ 发光粉物相、形貌和发光性质的影响

论文 | 更新时间：2020-08-12

- 前驱溶液的pH值对制备Ca₂Zn₄Ti₁₆O₃₈ ∶ Pr³⁺,Na⁺ 发光粉物相、形貌和发光性质的影响
- Influence of pH Value in Precursor Solution on the Component, Morphology and Photoluminescence of Ca₂Zn₄Ti₁₆O₃₈ ∶ Pr³⁺, Na⁺ Phosphor
- 发光学报 2010年31卷第5期页码：712-718
- 作者机构：
  
  湖南师范大学化学化工学院资源精细化与先进材料湖南省高校重点实验室, 湖南长沙 410081
- 作者简介：
- 基金信息：
  
  国家自然科学基金(50772035,20971042)();湖南省教育厅重点项目(10A070)();长沙市科技计划重点项目(K0902014-11)();湖南师范大学
- DOI：
  中图分类号： O482.31
- 纸质出版日期：2010-9-21，
  
  网络出版日期：2010-9-21，
  
  收稿日期：2009-7-16，
  
  修回日期：2009-9-27，
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周文, 余丽萍, 廉世勋, 祁媛, 朱爱玲, 荣春英. 前驱溶液的pH值对制备Ca2Zn4Ti16O38 ∶ Pr3+,Na+ 发光粉物相、形貌和发光性质的影响[J]. 发光学报, 2010,31(5): 712-718

ZHOU Wen, YU Li-ping, LIAN Shi-xun, QI Yuan, ZHU Ai-ling, RONG Chun-ying. Influence of pH Value in Precursor Solution on the Component, Morphology and Photoluminescence of Ca2Zn4Ti16O38 ∶ Pr3+, Na+ Phosphor[J]. 发光学报, 2010,31(5): 712-718
周文, 余丽萍, 廉世勋, 祁媛, 朱爱玲, 荣春英. 前驱溶液的pH值对制备Ca2Zn4Ti16O38 ∶ Pr3+,Na+ 发光粉物相、形貌和发光性质的影响[J]. 发光学报, 2010,31(5): 712-718 DOI：

ZHOU Wen, YU Li-ping, LIAN Shi-xun, QI Yuan, ZHU Ai-ling, RONG Chun-ying. Influence of pH Value in Precursor Solution on the Component, Morphology and Photoluminescence of Ca2Zn4Ti16O38 ∶ Pr3+, Na+ Phosphor[J]. 发光学报, 2010,31(5): 712-718 DOI：

摘要

以钛酸丁酯、醋酸钙、醋酸锌、柠檬酸和乙二醇为原料

采用溶胶-凝胶法制备Ca

∶ Pr

发光粉。研究了前驱溶液的pH值对溶胶-凝胶转变过程、发光粉物相组成、样品形貌和发光性质的影响。通过热重-差热分析(TG/DTA)、X射线衍射(XRD)分析、扫描电子显微镜(SEM)对前驱物分解、发光粉物相和颗粒大小进行了研究。采用荧光光谱对材料的光谱性质进行了表征。研究发现前驱溶液pH 3时

所得发光粉样品为蓬松的、颗粒均匀的单相Ca

粉末

红色余辉时间较长;随着pH值增大

逐渐有杂质相TiO

、CaTiO

和Zn

TiO

生成

并且样品颗粒逐渐变大

颗粒团聚呈现不规则形状

余辉时间变短。结果表明

只有在pH 3条件下以溶胶-凝胶法制备Ca

∶ Pr

发光粉下才能获得被日光有效激发

并呈现余辉衰减慢的红色长余辉(644 nm)发光。

Abstract

The phosphor Ca

∶ Pr

has received increasing interest owing to its high chemical stability

broad red emission and special long afterglow properties. However

the sintering temperature for obtaining pure Ca

∶ Pr

is confirmed to be 950 ℃ and the sintering period is 21 h for sol-gel synthesis of this phosphor. So

optimization of synthesis conditions of Ca

must be carried out.It is most important to get uniform and transparent gel in the sol-gel process. The results show that the mixture solution is clarification when pH 3 (adjusted by HNO

solution).While increasing the pH value (adjusted by ammonia solution) the mixture solution begin to come forth muddy. After dried in 150 ℃

the exrogel shows yellow color under pH 3 and others present black. After further heated at 400 ℃ for 2 h

a dark dry gel is obtained and ground in an agate mortar to black powder serving as the precursor for the present work. The final phosphor powder is obtained after reheated at 900 ℃ for 8 h. Crystalline phases

morphology and photoluminescence properties have been characterized by using powder X-ray diffractometry (XRD)

scanning electron microscopy (SEM) and fluorescence spectrophotometer

respectively. XRD patterns show that the synthesized Ca

powders possess well structure when pH 3. Extra-resultants such as CaTiO

TiO

and TiO

appeared when pH 5.The SEM results showed that the samples obtained at pH 3 are fleecy and uniform. With the increasing pH value

particles gradually become larger

the reunion and sinter phenomenon become seriousevident.TG-DAT curves reveal the different various trends for the precursors of pH=3 and pH=9. The electrical alkoxy-OR of Ti (OC

)

make metal ions Ti

highly vulnerable by nucleophilic attack. Ti (OC

)

easily hydrolyzes or polymerizes no matter what in acid or alkaline conditions. When pH3

speeds up the hydrolysis of Ti (OC

)

and to replace the form of coordination of tetrabutyl titanate alkoxy

direct bonding with titanium ion formed by hydrolysis of Ti (OH)

x(AC)

y(with

x+y

=4). However

when pH=9

a large number of OH

ions exists in Ti (OC

)

hydrolysis and produces Ti(OH)

or TiO(OH)

and that the other cations Ca

and Pr

from Ca(OH)

Zn(OH)

and Pr(OH)

will not mixe with each other effectively and will not form other phases. Thereby

keeping the pH 3 is necessary for cations to uniformly mix to inhibit Ti (OC

) directly hydrolyzed to form Ti (OH)

precipitation. Excitation and emission spectra indicate that the phosphors exhibit the highest excitation bands in the visible region in the ranges of 450~495 nm originated from 4f4f transition

as well as red emitting of Pr

at 613 nm(

)and 644 nm (

) when pH3

which result in

upon excitation with 475 nm

the red emission at 644 nm decays slower than that of pH 5. This fact suggests that Ca

∶ Pr

obtained via acid sol-gel process (pH 3) gives the good red long afterglow under visible light irradiation.

关键词

Ca2Zn4Ti16O38 ∶ Pr3+溶胶-凝胶法pH值红色发光粉长余辉

Keywords

Ca2Zn4Ti16O38 ∶ Pr3+sol-gel methodpH valuered phosphorlong afterglow

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