Cu 2+、Tb 3+共掺杂BaZrO3高近红外反射颜料的制备及其性能研究

doi:10.15541/jim20180387

摘要/Abstract

摘要：

环保型高近红外反射颜料可以有效缓解城市“热岛效应”和能源危机, 对推动绿色建筑节能产业发展具有重要的意义。离子掺杂是实现高近红外反射颜料呈色多样性的有效手段, 本研究采用溶胶-凝胶法制备了一系列铜离子和稀土铽离子共掺杂的高近红外反射Ba_1-_xCu_xZr_1-_yTb_yO₃(x=0.15, 0.25, 0.35; y=0, 0.15)无机颜料。利用X射线衍射仪(XRD)、紫外/可见/近红外分光光度计、CIE 1976 L ^*a ^*b ^*色度坐标等对所合成的颜料粉体的晶体结构、反射性能、颜色性能等进行表征。结果表明, 在煅烧温度为1100 ℃时, 所合成的样品均为立方钙钛矿结构; Cu ²⁺、Tb ³⁺共掺杂进入BaZrO₃晶格中, 随着掺杂量的增加, 颜料样品颜色由白色逐渐变为灰色再变为黄色。而且所得颜料在780~2500 nm波长范围内具有较高的近红外太阳光反射率, 其平均反射率(R ^*)可达到 80%左右。因此, 这种Ba_1-_xCu_xZr_1-_yTb_yO₃“冷”颜料粉体在建筑涂料等方面具有广阔的应用前景。

关键词: 溶胶-凝胶法, 共掺杂, 近红外反射, “冷”颜料;

Abstract:

The urban island effect and energy crisis can be relieved usefully by environmentally benign and high near-infrared reflective pigments, which is of great significance to develop of green energy-saving industry. Ions doping is an effective way to achieve the color diversity of high near infrared reflective pigments. In this work, a series of high near-infrared reflection Ba_1-_xCu_xZr_1-_yTb_yO₃ (x=0.15, 0.25, 0.35; y=0, 0.15) inorganic pigment co-doped with Cu ²⁺and rare earth Tb ³⁺was prepared by a Sol-Gel process. Its phase structure, ultraviolet/visible/near-infrared reflectance, and color parameters of the synthesized pigment samples were investigated and characterized by X-ray diffraction (XRD), UV/Vis/NIR spectroscopy, and color CIE-L ^*a ^*b ^* 1976 color scales. The results demonstrate that all synthesized pigments have cubic perovskite structure after calcined at 1100 ℃. The co-doping of Cu ²⁺ and Tb ³⁺ is successfully introduced into the BaZrO₃lattice, and the color increasingly changes from white to gray, and to yellow with the increase of Cu ²⁺and Tb ³⁺concentration. Meanwhile, the obtained pigments possess high near-infrared solar reflectance in the range of 780-2500 nm, the average reflectance is up to 80%. Therefore, these Ba_1-_xCu_xZr_1-_yTb_yO₃cool powdered pigment have great application prospect in the building coatings.

Key words: Sol-Gel, co-doping, near-infrared reflectance, cool pigment

中图分类号:

TQ622

张少丹, 包维维, 马海萍. Cu ²⁺、Tb ³⁺共掺杂BaZrO₃高近红外反射颜料的制备及其性能研究[J]. 无机材料学报, 2019, 34(6): 599-604.

Shao-Dan ZHANG, Wei-Wei BAO, Hai-Ping MA. Near-infrared Reflective Pigments Based on Cu ²⁺ and Tb ³⁺ Codoped BaZrO₃: Preparation and Performance[J]. Journal of Inorganic Materials, 2019, 34(6): 599-604.

图/表 8

表1 Ba1-xCuxZr1-yTbyO3颜料样品符号和组成说明

Table 1 Symbols and compositions of Ba1-xCuxZr1-yTbyO3 pigments samples

Ref.	Composition
BZ	BaZrO₃
BC 015	Ba_0.85Cu_0.15ZrO₃
BC 025	Ba_0.75Cu_0.25ZrO₃
BC 035	Ba_0.65Cu_0.35ZrO₃
BC 015 T	Ba_0.85Cu_0.15Zr_0.85Tb_0.15O₃
BC 025 T	Ba_0.75Cu_0.25Zr_0.85Tb_0.15O₃
BC 035 T	Ba_0.65Cu_0.35Zr_0.85Tb_0.15O₃

图1 不同煅烧温度下BaZrO3颜料的XRD图谱

Fig. 1 XRD patterns of BaZrO3 pigment calcined at different temperature

图2 Ba1-xCuxZr1-yTbyO3系列颜料样品的XRD谱图

Fig. 2 XRD patterns of Ba1-xCuxZr1-yTbyO3 pigments

表2 Ba1-xCuxZr1-yTbyO3系列颜料的晶胞参数

Table 2 Cell parameters of the cubic cell of Ba1-xCuxZr1-yTbyO3 pigments

Ref.	(hkl)	(110)	(111)	(211)	(220)	(310)	Average/nm	Volume/nm³
BZ	a=b=c/nm	0.41915	0.41889	0.41908	0.41907	0.41917	0.41907	0.07360
BC 015	a=b=c/nm	0.41705	0.41916	0.41909	0.41880	0.41926	0.41867	0.07339
BC 025	a=b=c/nm	0.41814	0.41811	0.41846	0.41870	0.41885	0.41845	0.07327
BC 035	a=b=c/nm	0.41703	0.41819	0.41849	0.41929	0.41885	0.41837	0.07323
BC 015 T	a=b=c/nm	0.42057	0.41943	0.41925	0.41938	0.41937	0.41960	0.07388
BC 025 T	a=b=c/nm	0.41945	0.41930	0.41922	0.41926	0.41937	0.41932	0.07373
BC 035 T	a=b=c/nm	0.41925	0.41922	0.41917	0.41884	0.41908	0.41911	0.07362

图3 Ba1-xCuxZr1-yTbyO3系列颜料的紫外-可见漫反射光谱图

Fig. 3 UV-Vis diffuse reflectance spectra of Ba1-xCuxZr1-yTbyO3 pigments

表3 粉体颜料Ba1-xCuxZr1-yTbyO3 (x=0.15, 0.25, 0.35; y=0, 0.15)的色度坐标和禁带宽度

Table 3 Color coordinates of the Ba1-xCuxZr1-yTbyO3 (x=0.15, 0.25, 0.35; y=0, 0.15) powdered pigments and band gap values

Pigment composition	Color coordinates				Band gap/eV
Pigment composition	L^*	a^*	b^*	c^*	Band gap/eV
BZ	95.51	-0.21	0.91	0.93	2.71
BC 015	72.94	0.22	1.18	1.20	2.54
BC 025	64.87	0.56	0.94	1.09	2.53
BC 035	81.78	-0.39	-0.82	0.91	3.25
BC 015 T	73.30	6.28	26.02	26.77	2.59
BC 025 T	76.07	5.08	26.03	26.52	2.64
BC 035 T	80.04	1.33	19.03	19.08	2.70

图4 粉体颜料Ba1-xCuxZr1-yTbyO3的近红外反射光谱图(a)和近红外太阳光反射谱图(b)

Fig. 4 NIR reflectance (a) and NIR solar reflectance (b) of Ba1-xCuxZr1-yTbyO3 powdered pigments

表4 粉体颜料Ba1-xCuxZr1-yTbyO3 (x=0.15, 0.25, 0.35; y=0, 0.15)的近红外太阳光反射率

Table 4 NIR solar reflectance of Ba1-xCuxZr1-yTbyO3 (x=0.15, 0.25, 0.35; y=0, 0.15) powdered pigments

Pigment composition	BZ	BC 015	BC 025	BC 035	BC 015 T	BC 025 T	BC 035 T
NIR solar reflectance	86.8%	74.8%	68.8%	72.5%	79.8%	80.1%	77.2%

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Cu ²⁺、Tb ³⁺共掺杂BaZrO₃高近红外反射颜料的制备及其性能研究

Near-infrared Reflective Pigments Based on Cu ²⁺ and Tb ³⁺ Codoped BaZrO₃: Preparation and Performance

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