掺锶量对羟基磷灰石形貌及其荧光特性的影响

doi:10.3724/SP.J.1077.2013.12066

摘要/Abstract

摘要：

采用水热合成法制备了一系列具有不同微观形貌和荧光性能的掺锶羟基磷灰石粉末。通过X射线衍射、红外光谱、电子能谱、扫描电镜和荧光光谱表征样品的物相、形貌及荧光性能。结果表明: 所制备的样品形貌为1~ 3 μm的由微小晶粒聚集而成的球形颗粒, 但随着掺锶量的变化, 组成球形颗粒的微小晶粒形貌会出现较大的差异。未掺锶羟基磷灰石晶粒形貌为短棒状, 随着掺锶量的增加, 微小晶粒逐渐变为片状而后转变为长棒状。样品能在紫外光(波长351 nm)激发下发出明亮的蓝色荧光(波长375~500 nm, 最强峰位432 nm), 且荧光强度随掺锶量增加先增强, 而后减弱, 在掺锶量为30mol%时达到最大。

关键词: 锶羟基磷灰石, 发光材料, 水热法

Abstract:

Strontium Hydroxyapatite (Sr_xCa_10-_x(PO₄)₆(OH)₂, x=0, 3, 5, 10) powder with fluorescence property was successfully synthesized by a facile hydrothermal process. X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectra, field emission scanning electron microscope and photoluminescence excitation and emission spectra were employed to analyze phase change, characteristics and fluorescence property of samples. The experimental results indicate that the morphology of samples is spherical particle(D=1~2 μm), and with the amount of strontium changed from 0 to 100mol%, the morphology of spherical particle changes from short nanorods to nanosheets and then long nanorods. The samples show an intense and bright blue emission from 375 nm to 500 nm centered at 432 nm under long-wavelength UV light excitation (351 nm). The PL emission intensity firstly increases and then decreases with increasing the strontium content. When strontium content is 30%, the PL emission intensity reaches the maximum.

Key words: strontium hydroxyapatite, luminescence, hydrothermal

中图分类号:

TQ129

赵欣, 王德平, 邱雯青, 叶松. 掺锶量对羟基磷灰石形貌及其荧光特性的影响[J]. 无机材料学报, 2013, 28(1): 45-50.

ZHAO Xin, WANG De-Ping, QIU Wen-Qing, YE Song. Influence of Strontium on Hydroxyapatite Morphology and Luminescence Characteristics[J]. Journal of Inorganic Materials, 2013, 28(1): 45-50.

图/表 11

Table 1 Formula of strontium hydroxyapatite samples

Sample	Sr(NO₃)₂ /mmol	Ca(NO₃)₂·4H₂O/mmol	χ_Sr=n(Sr)/ n(Ca+Sr)
S1	0	3	0
S2	0.9	2.1	0.3
S3	1.5	1.5	0.5
S4	3	0	1

图1 样品S1、S2、S3和S4的XRD图谱表2 不同样品对应晶相、(211)晶面峰位及晶胞参数

Fig. 1 XRD patterns of samples S1, S2, S3 and S4

Table 2 Crystalline phase, peak position (211) and lattice parameters of different samples

Sample	Product	2θ₍₂₁₁₎	(a=b)/nm	c/nm
S1	Ca₁₀(PO₄)₆(OH)₂	31.54	0.94533	0.69063
S2	Ca₇Sr₃(PO₄)₆(OH)₂	31.40	0.95299	0.70126
S3	Ca₅Sr₅(PO₄)₆(OH)₂	31.22	0.95931	0.70945
S4	Sr₁₀(PO₄)₆(OH)₂	30.40	0.98235	0.72865

图2 样品S1、S2、S3和S4的FT-IR图谱

Fig. 2 FTIR spectra of samples S1, S2, S3 and S4

图3 样品S1 (a)、S2 (b)、S3(c)和S4 (d)的SEM照片

Fig. 3 SEM images of samples (a) S1, (b) S2, (c) S3 and (d) S4

图4 (a)和(b)分别为样品S1、S2、S3和S4的PL激发光谱和PL发射光谱。激发光在波长325~ 375 nm的紫外光范围内, 最大峰值为351 nm。各样品的激发光波长相同, 说明其发光机理相同。各样品的荧光发射波长范围都位于375~500 nm, 最大峰值为432 nm, 呈明亮的蓝色荧光。但随着掺锶量的改变, 各样品的荧光发射强度有较大变化。Xsr由0增加到0.3时, 荧光强度随掺锶量的增加而增强, 且在Xsr为0.3时达到最大值; Xsr由0.3增加到1时, 荧光强度随掺锶量的增加反而减弱, 全锶HAp荧光强度小于不掺锶的HAp。

图4 样品S1、S2、S3和S4的PL激发光谱(a)和PL发射光谱(b)

Fig. 4 Excitation (a) and emission (b) spectra of samples S1, S2, S3 and S4

图5 S1、S2和S3样品的XPS全谱图

Fig. 5 XPS spectra of samples S1, S2 and S3

图6 样品S1、S2和S3在P2p3处的XPS分峰谱图

Fig. 6 XPS deconvulation for P2p3 peaks of samples S1, S2 and S3

Table 3 XPS peak energies of samples S1, S2 and S3

Sample	OKLL-Mg	O1s	Ca2s	Ca2p1/2	Ca2p3/2	C1s	C1s(Ⅲ)	P2s	P2p3	Sr3d
S1	750.20	535.80	443.21	355.40	352.20	289.00	-	195.06	138.00	-
S2	750.20	536.60	444.00	356.00	352.60	289.80	284.54	195.27	140.59	140.59
S3	750.20	535.60	443.82	355.00	351.80	288.00	283.00	194.20	139.00	137.23

图7 样品S1、S2和S3在C1s处的XPS分峰谱

Fig. 7 XPS deconvulation for C1s of samples S1, S2 and S3

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