铜离子掺杂Y2Ba2O5高近红外反射颜料的制备和光学性能研究

doi:10.15541/jim20150562

摘要/Abstract

摘要：

采用溶胶-凝胶法制备一系列环境友好型绿色近红外反射纳米颜料, 结构通式为Y₂Ba_(2-_x₎Cu_xO₅(x=0、0.25、0.50、0.75和1.0), 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、UV-vis-NIR分光光度仪和高精度分光测色仪对制备颜料的结构、形貌和光学性能进行了表征。研究结果表明, 铜离子掺杂进入Y₂Ba₂O₅晶格中, Y₂Ba₂O₅晶粒尺寸由62.1 nm降低至54.7 nm。Cu²⁺取代Y₂Ba₂O₅中的部分Ba²⁺, 粉末颜色由白色变为绿色(a*=-21.61), 禁带宽度由2.30 eV 减少到2.04 eV; 粉末呈现不规则球形结构, 粒径分布在150~300 nm范围内。掺杂Cu²⁺使粉末的近红外反射率降低, 但Cu²⁺掺杂量为x=0.50时仍然表现出较高的近红外反射率(68.80%)和太阳光反射率(45.95%)。因此, Y₂Ba_(2-_x₎Cu_xO₅系列高近红外反射绿色粉末作为“冷”颜料在建筑涂料方面具有巨大的应用潜能。

关键词: 溶胶-凝胶, 绿色颜料, 近红外反射率, 禁带宽度

Abstract:

A series of environmentally benign near-infrared reflective green nano-pigments were synthesized via Sol-Gel method with a general formula of Y₂Ba_(2-_x₎Cu_xO₅(x=0, 0.25, 0.50, 0.75 and 1.0). The crystal structure, morphology and optical properties of the synthesized pigments were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-Vis-NIR diffuse reflectance spectra, and high accuracy spectrophotometer. Analysis results demonstrated that Cu ion was successfully introduced into the Y₂Ba₂O₅lattice of which grain size decreased from 62.1 nm to 54.7 nm. The systematic substitution of Cu²⁺for Ba²⁺in Y₂Ba₂O₅ changed color from white to green (a*=-21.61) and decreased band gap from 2.30 eV to 2.04 eV. These pigment samples revealed the uniform spherical-like morphology with an average size of 150-300 nm. When Cu²⁺ was introduced, the infrared reflectance of pigment sample was decreased. However, the pigment still displayed high near infrared reflectance (68.80%) and solar reflectance (45.95%), while the doping of Cu²⁺ up to x=0.50. Therefore, such green high near-infrared reflectance from these Y₂Ba₍₂_-x₎Cu_xO₅ powders have great potential in serving as cool pigments for building coatings.

Key words: Sol-Gel, green pigment, near-infrared reflectance, band gap

中图分类号:

TQ174

姜峻, 姚伯龙, 高旭瑞, 王利魁, 李洪萍, 邓丽朵. 铜离子掺杂Y₂Ba₂O₅高近红外反射颜料的制备和光学性能研究[J]. 无机材料学报, 2016, 31(6): 641-646.

JIANG Jun, YAO Bo-Long, GAO Xv-Rui, WANG Li-Kui, LI Hong-Ping, DENG Li-Duo. Synthesis and Optical Properties of Copper Doped Y₂Ba₂O₅Pigments with High Near-infrared Reflectance[J]. Journal of Inorganic Materials, 2016, 31(6): 641-646.

图/表 10

图1 Y2Ba(2-x)CuxO5(x=0~1.0)粉末的XRD图谱(a)及其2θ在28.0º~31.3º范围内的放大图谱(b)

Fig. 1 Powder X-ray diffraction patterns of Y2Ba(2-x)CuxO5(x=0-1.0) (a) and the expanded XRD patterns in the 2θ range of 28.0°-31.3° (b)

表1 Y2Ba(2-x)CuxO5(x=0~1.0)粉末的晶胞参数和晶粒尺寸

Table 1 Lattice parameters and crystallite size of the Y2Ba(2-x)CuxO5(x=0-1.0) powder

Pigment composition Y₂Ba_(2-_x)Cu_xO₅	Lattice parameter/nm			Crystallite size /nm
Pigment composition Y₂Ba_(2-_x)Cu_xO₅	a	b	c	Crystallite size /nm
x=0	0.4377 1.2210 1.2201 1.2183 1.2176	0.4377	1.1852	62.1 61.0 59.8 56.5 54.7
x=0.25		0.5602	0.7121
x=0.50		0.5629	0.7124
x=0.75		0.5642	0.7129
x=1.0		0.5655	0.7130

图2 绿色颜料Y2Ba(2-x)CuxO5(x=0~1.0)的拉曼光谱

Fig. 2 Raman spectra of Y2Ba(2-x)CuxO5(x=0-1.0) green pigments

图3 Y2Ba2O5(A)、Y2Ba1.5Cu0.5O5(B)和Y2BaCuO5(C)的FESEM照片

Fig. 3 FESEM images of Y2Ba2O5 (A), Y2Ba1.5Cu0.5O5 (B) and Y2BaCuO5 (C)

图4 粉末颜料Y2Ba(2-x)CuxO5(x=0~1.0)的数码照片

Fig. 4 Photographs of Y2Ba(2-x)CuxO5(x=0-1.0) powder pigments

表2 粉末颜料Y2Ba(2-x)CuxO5(x=0~1.0)色度坐标和禁带宽度

Table 2 Color coordinates and band gap of the Y2Ba(2-x)CuxO5(x=0-1.0) powder pigments

Pigment Y₂Ba_(2-_x₎Cu_xO₅	Color coordinates				Band gap /eV
Pigment Y₂Ba_(2-_x₎Cu_xO₅	L*	a*	b*	C*	Band gap /eV
x=0	90.83	-1.76	12.68	12.76	2.30 2.16 2.08 2.04 2.04
x=0.25	58.13	-13.83	11.37	17.90
x=0.50	56.40	-17.09	10.29	19.95
x=0.75	54.03	-18.67	11.53	21.94
x=1.0	51.86	-21.61	4.50	22.07

图5 粉末颜料Y2Ba(2-x)CuxO5 (x= 0~1.0)的紫外-可见漫反射光谱图

Fig. 5 UV-Vis diffuse reflectance spectra of Y2Ba(2-x)CuxO5 (x= 0-1.0) powder pigments

表3 粉末颜料Y2Ba(2-x)CuxO5(x=0~1.0)近红外反射率和太阳光反射率

Table 3 Values of NIR reflectance and solar reflectance of Y2Ba(2-x)CuxO5(x=0-1.0) powder pigments

Pigment Y₂Ba_(2-_x₎Cu_xO₅	x=0	x=0.25	x=0.50	x=0.75	x=1.0
NIR reflectance/%	85.87	70.53	68.80	67.32	56.38
Solar reflectance, R*/%	63.78	47.49	45.95	42.07	38.83

图6 粉末颜料Y2Ba(2-x)CuxO5(x =0~1.0)近红外反射光谱图

Fig. 6 NIR reflectance spectra of Y2Ba(2-x)CuxO5 (x=0-1.0) powder pigments

图7 粉末颜料Y2Ba(2-x)CuxO5(x =0~1.0)近红外太阳光反射谱图

Fig. 7 NIR solar reflectance spectra of Y2Ba(2-x)CuxO5 (x= 0-1.0) powder pigments

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铜离子掺杂Y₂Ba₂O₅高近红外反射颜料的制备和光学性能研究

Synthesis and Optical Properties of Copper Doped Y₂Ba₂O₅Pigments with High Near-infrared Reflectance

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