固相法制备掺杂型高色度CoxM1-xAl2O4/高岭土复合颜料

硅酸盐通报 ›› 2021, Vol. 40 ›› Issue (9): 3081-3089.

固相法制备掺杂型高色度Co_xM_1-xAl₂O₄/高岭土复合颜料

张安杰^1,2,3, 陶雯¹, 曾慧崇¹, 王乃迪¹, 牟斌², 齐彦兴³, 李华明¹

1.西北永新涂料有限公司,兰州 730046;
2.中国科学院兰州化学物理研究所,甘肃省黏土矿物应用研究重点实验室,兰州 730000;
3.中国科学院兰州化学物理研究所,精细石油化工中间体国家工程研究中心,兰州 730000

收稿日期:2021-03-26 修回日期:2021-06-04 出版日期:2021-09-15 发布日期:2021-10-08
通讯作者: 牟斌,博士,研究员。E-mail:mubin@licp.cas.cn
作者简介:张安杰(1984—),男,博士,高工。主要从事新材料、涂料的研发工作。E-mail:anjie422@163.com
基金资助:
中国博士后科学基金面上项目(2019M663958XB);兰州市城关区人才创新创业类项目(2020RCCX0007)

Preparation of High-Chroma Co_xM_1-xAl₂O₄/Kaolin Composite Pigment via Solid-Phase Method

ZHANG Anjie^1,2,3, TAO Wen¹, ZENG Huichong¹, WANG Naidi¹, MU Bin², QI Yanxing³, LI Huaming¹

1. Northwest Yongxin Coatings Limited Company, Lanzhou 730046, China;
2. Key Laboratory of Clay Mineral Applied Research of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China;
3. National Engineering Research Center of Fine Petrochemical Intermediates, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China

Received:2021-03-26 Revised:2021-06-04 Online:2021-09-15 Published:2021-10-08

摘要/Abstract

摘要： 为了制备低成本、高色度的钴蓝颜料,本文以高岭土为载体,以Al₂O₃和Co₃O₄为主要原料,通过引入ZnO、CaO及MgO不同金属氧化物,采用固相法制备了高色度(Co_xM_1-xAl₂O₄)/高岭土复合颜料(M为Ca²⁺、Mg²⁺或Zn²⁺)。系统考察了研磨时间、煅烧温度、煅烧时间和不同金属氧化物掺量对复合颜料呈色性能的影响规律。研究表明,在煅烧温度1 200 ℃、研磨时间12 h和n(Co²⁺)/n(M²⁺)为3:2时,制得的复合颜料具有最好的呈色性能(L^*=53.68,a^*=7.58,b^*=-62.89)。同时,引入不同的金属元素,可实现对复合颜料颜色的调控,引入Ca²⁺后,所制备的Co_xCa_1-xAl₂O₄复合颜料偏红相,而引入Zn²⁺后,所制备的Co_xZn_1-xAl₂O₄复合颜料偏绿相。通过相关表征,提出了复合颜料的呈色机理,在颜料制备过程中,引入与Co²⁺离子半径接近的Mg²⁺或Zn²⁺,Mg²⁺或Zn²⁺可进入CoAl₂O₄的四面体配位中,部分替代Co²⁺,形成MgAl₂O₄-CoAl₂O₄或ZnAl₂O₄-CoAl₂O₄的固溶体,而引入离子半径较大的Ca²⁺,形成CaAl₂O₄和CoAl₂O₄的均相混合物。最后,将制得复合颜料应用到有机硅耐热涂料中,可以明显提高有机硅涂料的热稳定性。

关键词: 复合颜料, 钴蓝, 高岭土, 呈色机理, 耐热涂料

Abstract: In this study, the low-cost and high-chroma Co_xM_1-xAl₂O₄/kaolin (M=Zn²⁺, Ca²⁺ or Mg²⁺) composite pigments were prepared by solid-phase method using kaolin, Co₃O₄, α-Al₂O₃ and metal oxides (ZnO, CaO or MgO) as raw materials. The effect of preparation conditions on the color properties of composite pigments was systematically investigated, including calcining temperature, grinding time, the added amounts and the types of different metal ions of Zn²⁺, Ca²⁺ or Mg²⁺. As the calcining temperature, grinding time and molar ratio of Co²⁺ to M²⁺ are 1 200 ℃, 12 h and 3:2, respectively, the as-prepared composite pigments present the best color performance (L^*=53.68, a^*=7.58, b^*=-62.89). Furthermore, the color of composite pigments can be facilely adjusted by incorporating different metal elements. After incorporation of Ca²⁺, the obtained composite pigments present the blue color with a red hue, but Co_xZn_1-xAl₂O₄ composite pigments are blue with a green hue. Based on the relevant characterizations, the possible coloring mechanism was proposed. Due to the similar ion radius of the tetrahedrally coordinated Co²⁺ and Mg²⁺ or Zn²⁺, Mg²⁺ or Zn²⁺ can enter into the tetrahedrally coordinated sites of CoAl₂O₄ to substitute Co²⁺and form the solid solutions ofMgAl₂O₄-CoAl₂O₄ (or ZnAl₂O₄-CoAl₂O₄). However, the ion radius of Ca²⁺ is higher than that of Co²⁺, the introduction of Ca²⁺ led to forming the homogeneous mixtures of CaAl₂O₄ and CoAl₂O₄. Finally, the as-prepared composite pigments are incorporated into organosilicon heat-resistance coating, and the heat-resistance of coating is obviously improved.

Key words: composite pigment, CoAl₂O₄, kaolin, coloring mechanism, heat-resistance coating

中图分类号:

TQ174

张安杰, 陶雯, 曾慧崇, 王乃迪, 牟斌, 齐彦兴, 李华明. 固相法制备掺杂型高色度Co_xM_1-xAl₂O₄/高岭土复合颜料[J]. 硅酸盐通报, 2021, 40(9): 3081-3089.

ZHANG Anjie, TAO Wen, ZENG Huichong, WANG Naidi, MU Bin, QI Yanxing, LI Huaming. Preparation of High-Chroma Co_xM_1-xAl₂O₄/Kaolin Composite Pigment via Solid-Phase Method[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(9): 3081-3089.

参考文献

[1] ZHENG W, ZOU J. Synthesis and characterization of blue TiO₂/CoAl₂O₄ complex pigments with good colour and enhanced near-infrared reflectance properties[J]. RSC Advances, 2015, 5(107): 87932-87939.
[2] ZHANG A J, MU B, HUI A P, et al. A facile approach to fabricate bright blue heat-resisting paint with self-cleaning ability based on CoAl₂O₄/kaolin hybrid pigment[J]. Applied Clay Science, 2018, 160: 153-161.
[3] SUGUNA S, SHANKAR S, JAGANATHAN S K, et al. Novel synthesis and characterization studies of spinel Ni_xCo_1-xAl₂O₄ (x=0.0 to 1.0) nano-catalysts for the catalytic oxidation of benzyl alcohol[J]. Journal of Nanoscience and Nanotechnology, 2018, 18(2): 1019-1026.
[4] 张安杰.环保型钴蓝/黏土矿物杂化颜料的制备及应用研究[D].北京:中国科学院大学,2018.
ZHANG A J. Preparation and application of environmentally friendly cobalt blue/clay mineral hybrid pigments[D]. Beijing: University of Chinese Academy of Sciences, 2018 (in Chinese).
[5] HE X, WANG F, LIU H, et al. Synthesis and color properties of the TiO₂@CoAl₂O₄ blue pigments with low cobalt content applied in ceramic glaze[J]. Journal of the American Ceramic Society, 2018, 101(6):2578-2588.
[6] PENG X J, ZHANG Q, CHENG J S, et al. Preparation and characterization of a stable nano-sized Zn_xCo_1-xAl₂O₄ ink for glass decoration by ink-jet printing[J]. Glass Physics and Chemistry, 2017, 43(3): 246-256.
[7] ZHOU N Y, LI Y, ZHANG Y, et al. Synthesis and characterization of Co_1-xCa_xAl₂O₄ composite blue nano-pigments by the polyacrylamide gel method[J]. Dyes and Pigments, 2018, 148: 25-30.
[8] MU B, WANG Q, WANG A Q. Effect of different clay minerals and calcination temperature on the morphology and color of clay/CoAl₂O₄ hybrid pigments[J]. RSC Advances, 2015, 5(124): 102674-102681.
[9] ZHANG A J, MU B, LI H M, et al. Cobalt blue hybrid pigment doped with magnesium derived from sepiolite[J]. Applied Clay Science, 2018, 157: 111-120.
[10] ZHANG A J, MU B, WANG X W, et al. Formation and coloring mechanism of typical aluminosilicate clay minerals for CoAl₂O₄ hybrid pigment preparation[J]. Frontiers in Chemistry, 2018, 6: 125.
[11] ZHANG A J, MU B, WANG X W, et al. CoAl₂O₄/kaoline hybrid pigment prepared via solid-phase method for anticorrosion application[J]. Frontiers in Chemistry, 2018, 6: 586.
[12] ZHANG A J, WANG N D, MU B, et al. Amino-acid-assisted preparation of CoAl₂O₄/kaolin hybrid pigments[J]. Applied Clay Science, 2020, 191: 105611.
[13] ZHANG A J, MU B, WANG X W, et al. Microwave hydrothermal assisted preparation of CoAl₂O₄/kaolin hybrid pigments for reinforcement coloring and mechanical property of acrylonitrile butadiene styrene[J]. Applied Clay Science, 2019, 175: 67-75.
[14] RAN S S, WANG L J, ZHANG Y D, et al. Reinforcement of bone China by the addition of sepiolite nano-fibers[J]. Ceramics International, 2016, 42(12): 13485-13490.
[15] SHANG K, LIAO W, WANG J, et al. Nonflammable alginate nanocomposite aerogels prepared by a simple freeze-drying and post-cross-linking method[J]. ACS Applied Materials & Interfaces, 2016, 8(1): 643-650.
[16] GÜLGÜN M A, NGUYEN M H, KRIVEN W M. Polymerized organic-inorganic synthesis of mixed oxides[J]. Journal of the American Ceramic Society, 2004, 82(3): 556-560.
[17] FREEDA M, SUBASH T D. Optical characterization of dysporsium doped calcium aluminate nanophosphor (CaAl₂O₄: Dy) by sol-gel method[J]. Materials Today: Proceedings, 2017, 4(2): 4290-4301.
[18] ZHANG A J, MU B, LUO Z H, et al. Bright blue halloysite/CoAl₂O₄ hybrid pigments: preparation, characterization and application in water-based painting[J]. Dyes and Pigments, 2017, 139: 473-481.
[19] MINDRU I, MARINESCU G, GINGASU D, et al. Blue CoAl₂O₄ spinel via complexation method[J]. Materials Chemistry and Physics, 2010, 122(2/3): 491-497.
[20] OUAHDI N, GUILLEMET S, DEMAI J J, et al. Investigation of the reactivity of AlCl₃ and CoCl₂ toward molten alkali-metal nitrates in order to synthesize CoAl₂O₄[J]. Materials Letters, 2005, 59(2/3): 334-340.

固相法制备掺杂型高色度Co_xM_1-xAl₂O₄/高岭土复合颜料

Preparation of High-Chroma Co_xM_1-xAl₂O₄/Kaolin Composite Pigment via Solid-Phase Method

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