Preparation of Glass Ceramics Containing CaF2 by One-step Method and Analysis of the Fluorescent Probe of Eu3+ Ion†

doi:10.7503/cjcu20160013

Abstract

Abstract:

Transparent glass-ceramics with composition n(SiO₂)∶n(Al₂O₃)∶n(CaO)∶n(CaF₂)∶n(NaF)∶n(B₂O₃)=40∶20∶10∶10∶15∶5 were fabricated via traditional melting technique with one-step method. X-ray diffraction(XRD) results of as-prepared glass-ceramics confirmed the existence of CaF₂ phase. Scanning electron microscopy(SEM) observation showed that the CaF₂ crystalline phase had a size of 200 nm and dispersed in the amorphous phase. The fluorescence intensity of glass ceramics was 1.7 times that of the glass. The emission spectrum showed several luminescence peaks at 590 nm(⁵D₀→⁷F₁), 614 nm(⁵D₀→⁷F₂), 652 nm(⁵D₀→⁷F₃) and 700 nm(⁵D₀→⁷F₄), which are attributed to the Eu³⁺ ion transition. The intensity ratio of ⁵D₀ -⁷F₂ transition to the ⁵D₀ -⁷F₁ transition and Ω₂ of Judd-Ofelt parameters were used to measure the rare earth ion site symmetry. The data revealed that Eu³⁺ ions are embedded into Ca-F environment from Si-O environment during the crystallization process. Therefore Eu³⁺can be applied to investigate the microstructures of glass-ceramic crystal as a fluorescence probe.

Key words: Glass ceramic, Fluorescence probe, Emission spectrum, Local environment

CLC Number:

O614.33

TrendMD:

WANG Caiping, LI Youfen, ZHANG Yidong. Preparation of Glass Ceramics Containing CaF₂ by One-step Method and Analysis of the Fluorescent Probe of Eu³⁺ Ion^†[J]. Chem. J. Chinese Universities, 2016, 37(4): 607.

Figures/Tables 9

Fig.1 XRD patterns of glass and glass ceramicsa. Glass ceramic prepared at 850 ℃; b. glass ceramic prepared at 650 ℃; c. glass; d. standard patterns of CaF2.

Fig.2 SEM images of the glass and glass ceramics prepared at different temperatures (A) Glass; (B) glass ceramics prepared at 650 ℃; (C) glass ceramics prepared at 750 ℃; (D) glass ceramic prepared at 850 ℃. Circled area for EDS sprectrum.

Fig.3 EDS spectrum of glass ceramic prepared at 850 ℃

Table 1 Elementary composition and content of glass ceramics

Element	Actual content(mass ratio, %)	Theoretical content(mass ratio, %)	Atomic content(atomic ratio, %)
C	29.29	25.59	39.64
O	16.38	14.31	16.65
F	25.97	22.69	22.23
Na	3.94	3.44	2.78
Al	8.87	7.75	5.34
Si	6.76	5.90	3.91
K	0.77	0.67	0.32
Ca	22.48	19.64	9.12

Fig.4 Excitation(a, λem=614 nm) and emission (b, λex=614 nm) spectra of glass ceramic prepared at 850 ℃

Fig.5 Emission spectra of glass(a) and glass ceramic(b)

Fig.6 Emission spectra of glass ceramics doped with different concentrations of Eu3+x(Eu3+): a. 0.5%; b. 1.0%; c. 1.5%; d. 2.0%.

Fig.7 Emission spectra of glass ceramics prepared at different temperatures

Table 2 Intensity ratio and J-O intensity parameters of glass ceramics prepared at different temperatures

Temperature/℃(Sample)	I₂/ $I 1 a$	I₄/ $I 1 b$	10²⁰Ω₂/cm²	10²⁰Ω₄/cm²
650	2.650	0.476	3.236	1.792
750	2.694	0.476	3.317	1.793
800	2.715	0.500	3.342	1.883
850	2.769	0.517	3.409	1.947
900	2.687	0.475	3.308	1.789

Table 2 Intensity ratio and J-O intensity parameters of glass ceramics prepared at different temperatures

Temperature/℃(Sample)	I₂/ $I 1 a$	I₄/ $I 1 b$	10²⁰Ω₂/cm²	10²⁰Ω₄/cm²
650	2.650	0.476	3.236	1.792
750	2.694	0.476	3.317	1.793
800	2.715	0.500	3.342	1.883
850	2.769	0.517	3.409	1.947
900	2.687	0.475	3.308	1.789

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Preparation of Glass Ceramics Containing CaF₂ by One-step Method and Analysis of the Fluorescent Probe of Eu³⁺ Ion^†

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