固相法制备掺杂型高色度Co_(x)M_(1-x)Al_(2)O_(4)/高岭土复合颜料  

Preparation of High-Chroma Co_(x)M_(1-x)Al_(2)O_(4)/Kaolin Composite Pigment via Solid-Phase Method

作　　者：张安杰 陶雯 曾慧崇 王乃迪 牟斌[2] 齐彦兴 李华明 ZHANG Anjie;TAO Wen;ZENG Huichong;WANG Naidi;MU Bin;QI Yanxing;LI Huaming(Northwest Yongxin Coatings Limited Company,Lanzhou 730046,China;Key Laboratory of Clay Mineral Applied Research of Gansu Province,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China;National Engineering Research Center of Fine Petrochemical Intermediates,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China)

机构地区：[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

出　　处：《硅酸盐通报》2021年第9期3081-3089,3104,共10页Bulletin of the Chinese Ceramic Society

基　　金：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)。

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Al_(2)O_(3)和Co_(3)O_(4)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_(x)M_(1-x)Al_(2)O_(4))/高岭土复合颜料(M为Ca^(2+)、Mg^(2+)或Zn^(2+))。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1200℃、研磨时间12 h和n(Co^(2+))/n(M^(2+))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Ca^(2+)后,所制备的Co_(x)M_(1-x)Al_(2)O_(4)复合颜料偏红相,而引入Zn^(2+)后,所制备的Co_(x)Zn_(1-x)Al_(2)O_(4)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Co^(2+)离子半径接近的Mg^(2+)或Zn^(2+),Mg^(2+)或Zn^(2+)可进入CoAl_(2)O_(4)的四面体配位中,部分替代Co^(2+),形成MgAl_(2)O_(4)-CoAl_(2)O_(4)或ZnAl_(2)O_(4)-CoAl_(2)O_(4)的固溶体,而引入离子半径较大的Ca^(2+),形成CaAl_(2)O_(4)和CoAl_(2)O_(4)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。In this study,the low-cost and high-chroma Co_(x)M_(1-x)Al_(2)O_(4)/kaolin(M=Zn^(2+),Ca^(2+)or Mg^(2+))composite pigments were prepared by solid-phase method using kaolin,Co_(3)O_(4),α-Al_(2)O_(3)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 Zn^(2+),Ca^(2+)or Mg^(2+).As the calcining temperature,grinding time and molar ratio of Co^(2+)to M^(2+)are 1200℃,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 Ca^(2+),the obtained composite pigments present the blue color with a red hue,but Co x Zn 1-x Al_(2)O_(4)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 Co^(2+)and Mg^(2+)or Zn^(2+),Mg^(2+)or Zn^(2+)can enter into the tetrahedrally coordinated sites of CoAl_(2)O_(4)to substitute Co^(2+)and form the solid solutions of MgAl_(2)O_(4)-CoAl_(2)O_(4)(or ZnAl_(2)O_(4)-CoAl_(2)O_(4)).However,the ion radius of Ca^(2+)is higher than that of Co^(2+),the introduction of Ca^(2+)led to forming the homogeneous mixtures of CaAl_(2)O_(4)and CoAl_(2)O_(4).Finally,the as-prepared composite pigments are incorporated into organosilicon heat-resistance coating,and the heat-resistance of coating is obviously improved.

关 键 词：复合颜料 钴蓝 高岭土 呈色机理 耐热涂料 

分 类 号：TQ174[化学工程—陶瓷工业]