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人工晶体学报 ›› 2022, Vol. 51 ›› Issue (8): 1484-1491.

• 研究论文 • 上一篇    下一篇

金红石型Ti1-2xCrxMoxO2黑色色料制备及其性能研究

陈仁华1, 周小坚2, 张小珍1,2, 卢紫翠2, 刘华锋1, 程兰兰1, 汪永清2   

  1. 1.江西金环颜料有限公司,宜春 336000;
    2.景德镇陶瓷大学材料科学与工程学院,景德镇 333403
  • 收稿日期:2022-05-23 出版日期:2022-08-15 发布日期:2022-09-08
  • 通讯作者: 张小珍,博士,教授。E-mail:zhangxiaozhen@jci.edu.cn
  • 作者简介:陈仁华(1979—),男,湖南省人,高级工程师。E-mail:chenrenhua1979@126.com
  • 基金资助:
    江西省重点研发计划(20192BBE50037,20202BBE53011);江西省研究生创新专项(YC2020-S412)

Preparation and Performance of Rutile Ti1-2xCrxMoxO2 Black Pigments

CHEN Renhua1, ZHOU Xiaojian2, ZHANG Xiaozhen1,2, LU Zicui2, LIU Huafeng1, CHENG Lanlan1, WANG Yongqing2   

  1. 1. Jiangxi Jinhuan Pigments Co., Ltd., Yichun 336000, China;
    2. School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, China
  • Received:2022-05-23 Online:2022-08-15 Published:2022-09-08

摘要: 以TiO2、Cr2O3和MoO3为主要原料,采用固相反应法合成了金红石型Ti1-2xCrxMoxO2(x=0、0.05、0.10、0.15、0.20)色料。研究了Cr/Mo共掺杂量和煅烧温度对Ti1-2xCrxMoxO2色料的晶型结构、呈色性能和微观形貌等的影响。研究结果表明,5%~15%摩尔分数的Cr/Mo等量共掺杂都获得单相金红石型结构黑色色料,均可促进锐钛矿向金红石转变,且Mo掺杂有利于提高Cr在TiO2晶格中的固溶度。随Cr/Mo共掺杂量增加,样品的黑度(L*值)呈先减小后增大的趋势,而红色度(a*值)和黄色度(b*值)都表现出相反的趋势。煅烧温度在950~1 100 ℃时,样品的色度参数变化相对较小。在1 100 ℃煅烧得到的Ti0.70Cr0.15Mo0.15O2色料黑色呈色性能最佳,其L*a*b*值分别为24.41、2.12和-2.53,且在陶瓷釉中表现出良好的呈色性能和化学稳定性。适量Cr/Mo共掺杂使TiO2晶格产生畸变和电荷缺陷,从而吸收绝大部分可见光,是其呈现黑色的主要原因。

关键词: TiO2, 金红石结构, 黑色色料, 固相反应法, 铬钼共掺杂, 呈色性能, 稳定性

Abstract: Rutile Ti1-2xCrxMoxO2 (x=0, 0.05, 0.10, 0.15, 0.20) pigments were synthesized by solid-state reaction method with TiO2, Cr2O3 and MoO3 as the main raw materials. The effects of Cr/Mo co-doping amount and calcination temperature on the phase structure, color performance and microstructure of obtained Ti1-2xCrxMoxO2 pigments were investigated. The results show that the same amount of Cr/Mo co-doping of 5%~15% mole fraction led to single-phase rutile pigments of black color, which can promote the phase transformation from anatase to rutile. Furthermore, the introduction of Mo is beneficial for improving the solid solubility of Cr in TiO2 lattice. With the increase of Cr/Mo co-doping content, the blackness (L* value) of the sample decreases first and then increases, while the redness (a* value) and yellowness (b* value) both show an opposite trend. When the calcination temperature is 950~1 100 ℃, the change of chromatic parameters of the samples is relatively small. The Ti0.70Cr0.15Mo0.15O2 pigment calcined at 1 100 ℃ shows the best color performance of black, and its L*, a* and b* values are 24.41, 2.12 and -2.53, respectively. The obtained rutile pigments also have good color performance and chemical stability in ceramic glaze. The main mechanism to produce black color could be attributed to the lattice distortion of rutile TiO2 and charge defects caused by appropriate Cr/Mo co-doping, thus absorbing most visible light.

Key words: TiO2, rutile structure, black pigment, solid-state reaction method, chromium and molybdenum co-doping, color performance, stability

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