脉冲激光喷涂一步合成黑色二氧化钛复合涂层

doi:10.15541/jim20180163

无机材料学报 ›› 2019, Vol. 34 ›› Issue (1): 109-113.DOI: 10.15541/jim20180163

所属专题： MAX相和MXene材料

脉冲激光喷涂一步合成黑色二氧化钛复合涂层

张立宪¹, 梁砚琴¹, 王绍丹¹, 卢红¹, 刘爱峰², 魏强^1,3

1. 天津大学材料科学与工程学院, 天津市材料复合与功能化重点实验室, 天津 300350;
2. 天津中医院大学第一附属医院, 天津 300193;
3. 河北工业大学机械工程学院, 天津 300130

收稿日期:2018-04-16 修回日期:2018-06-13 出版日期:2019-01-21 网络出版日期:2018-12-17
作者简介:张立宪(1992-),男,硕士研究生. E-mail: naturematerials@163.com
基金资助:
天津市应用基础与前沿技术研究计划重点项目(15JCZDJC38200);国家自然科学基金(81673994, 51573137);Tianjin Research Program of Application Foundation and Advanced Technology (15JCZDJC38200);National Natural Science Foundation of China (81673994, 51573137)

One-step Synthesis of Black TiO₂ Composite Coating on Glass by Pulsed Laser Spraying

ZHANG Li-Xian¹, LIANG Yan-Qin¹, WANG Shao-Dan¹, LU Hong¹, LIU Ai-Feng², WEI Qiang^1,3

1. Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China;
2. First Teaching Hospital of Tianjin University of Traditional Chinese Medicine, Tianjin 300193, China;
3. School of Mechanical Engineering, Hebei University of Technology, Tianjin 300130, China

Received:2018-04-16 Revised:2018-06-13 Published:2019-01-21 Online:2018-12-17
About author:ZHANG Li-Xian. E-mail: naturematerials@163.com

摘要/Abstract

摘要：

为实现黑色纳米TiO₂有效负载, 提高实际应用能力, 本研究提出了脉冲激光溅射喷涂的方法。在石英玻璃基底上一步制备了非晶分子筛和金红石型TiO₂纳米晶的黑色复合涂层, 表征了复合涂层表面形貌, 测定了复合涂层粉末的光谱吸收性能、物相结构、化学价态以及光催化性能。研究结果表明: 涂层为2~5 μm球体堆积成的多孔结构, 在整个可见光区具有较强的吸收能力。脉冲激光溅射喷涂过程中, 分子筛高温熔融急冷转变为非晶态结构, TiO₂则由锐钛矿型转变为金红石型; 其中Ti⁴⁺离子部分被还原为Ti³⁺离子, 缩小了禁带宽度。脉冲激光溅射喷涂技术实现了黑色纳米TiO₂快速负载, 且在全光谱和可见光条件下仍表现出良好的光催化能力。

关键词: 纳秒脉冲激光, 溅射喷涂, 黑色TiO₂, 纳米材料负载

Abstract:

To achieve effective load of black TiO₂ nanoparticles and improve the practical application ability, the pulsed laser spraying was proposed. The composite coating was prepared on quartz glass substrate, which consisted of amorphous molecular sieve and rutile TiO₂ nanocrystals. The surface morphology of the composite coating was characterized, and a series of test about composite coating powder was conducted including absorption properties, phase structure, chemical valence, and photocatalytic properties. The results show that the coating is porous structure packed with 2-5 μm ball and has strong absorptive capacity in the visible region. In the process of pulsed laser sputtering, the molecular sieve changed to amorphous structure, and TiO₂ changed from anatase to rutile type. Ti⁴⁺ ion was reduced to Ti³⁺ion, which resulted in reduced band-gap. The pulsed laser spraying technology achieves the fast load of the black nano TiO₂, which still has good photocatalytic ability under the full spectrum and visible light conditions.

Key words: nanosecond pulsed laser, sputtering spraying, black TiO₂, nanomaterial load.

中图分类号:

TQ134

张立宪, 梁砚琴, 王绍丹, 卢红, 刘爱峰, 魏强. 脉冲激光喷涂一步合成黑色二氧化钛复合涂层[J]. 无机材料学报, 2019, 34(1): 109-113.

ZHANG Li-Xian, LIANG Yan-Qin, WANG Shao-Dan, LU Hong, LIU Ai-Feng, WEI Qiang. One-step Synthesis of Black TiO₂ Composite Coating on Glass by Pulsed Laser Spraying[J]. Journal of Inorganic Materials, 2019, 34(1): 109-113.

图/表 9

图1 激光溅射喷涂实验装置示意图

Fig. 1 Schematic diagram of experimental device for laser spraying deposition

图2 压片靶材与激光溅射沉积涂层的宏观照片

Fig. 2 Macroscopical photographs of tableting target and deposition coating after laser sputtering

图3 涂层SEM形貌与能谱扫描能谱图

Fig. 3 SEM images and EDS scanning mapping (a) Surface morphology of coating; (b) Ball structure on coating surface; (c) Cross section of coating; (d) Map of Ti element distribution

图4 原始TiO2、TiO2和13X分子筛混合物涂层的UV-Vis 吸收光谱图

Fig. 4 UV-Vis absorption spectra of raw TiO2, TiO2 and 13X molecular sieves, composite coatings

图5 激光溅射前后粉末的XRD图谱

Fig. 5 XRD analysis of coated powder before and after pulsed laser ablation (a) XRD analysis of pressed powder after 700℃ and 1 h heat treatment; (b) XRD analysis of composite coating powder prepared by laser sputtering

图6 涂层粉末的TEM照片

Fig. 6 TEM analysis of coated powder

图7 XPS测试谱图

Fig. 7 XPS analysis spectra (a) Survey scan of raw TiO2; (b) Survey scan of composite coating; (c) Ti high-resolutionXPS spectra of the raw TiO2; (d) Ti high-resolution XPS spectra of composite coating

图8 黑色复合涂层的顺磁共振分析结果

Fig. 8 ESR analysis of black composite coatings

图9 不同光照条件下复合涂层的光催化效率曲线

Fig. 9 Photocatalytic efficiency of composite coatings under different illumination conditions

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脉冲激光喷涂一步合成黑色二氧化钛复合涂层

One-step Synthesis of Black TiO₂ Composite Coating on Glass by Pulsed Laser Spraying

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脉冲激光喷涂一步合成黑色二氧化钛复合涂层

One-step Synthesis of Black TiO2 Composite Coating on Glass by Pulsed Laser Spraying

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One-step Synthesis of Black TiO₂ Composite Coating on Glass by Pulsed Laser Spraying