Zhuang Guanzheng, Jaber Maguy, Rodrigues Francisco, Rigaud Baptiste, Walter Philippe, Zhang Zepeng
Sorbonne Université, Laboratoire d'Archéologie Moléculaire et Structurale (LAMS), CNRS UMR 8220, Case Courrier 225, UPMC 4 Pl. Jussieu, 75005 Paris Cedex 05, France; Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Xueyuan Road, Haidian District, Beijing 100083, PR China.
Sorbonne Université, Laboratoire d'Archéologie Moléculaire et Structurale (LAMS), CNRS UMR 8220, Case Courrier 225, UPMC 4 Pl. Jussieu, 75005 Paris Cedex 05, France.
J Colloid Interface Sci. 2019 Sep 15;552:204-217. doi: 10.1016/j.jcis.2019.04.072. Epub 2019 Apr 24.
Covering with polyorganosilane (POS) was proved as an effective way to enhance the chemical and thermal stability of clay/dye hybrid pigments. But the photostability and interactions with clay minerals, dyes and POS layer has never been reported. In order to investigate above issues, new organic-inorganic hybrid pigments based on halloysite (Hal) and indigo (In) were prepared by grinding method. X-ray diffraction, transmission electron microscopy, thermogravimetry, Fourier transform infrared spectroscopy were applied to characterize the structure of In-Hal (without POS layer) and In-Hal-POS (with POS layer) pigments. Solid state nuclear magnetic resonance (NMR) was employed to reveal the interactions between Hal, In and POS. Reflection spectra and CIE 1976 color space system were used to evaluate the color parameters and color changes of pigments. Thermal stability, chemical resistance to ethanol, 1 mol·L HCl and 1 mol⋅L NaOH, and light fastness to visible light were tested. Indigo molecules dispersed on the surface of Hal nanotubes. POS layer homogeneously covered on the surface of hybrid pigments, without changing the crystal structure and morphology of Hal. Covering with POS layer seldomly affect the color of hybrid pigments. However, In-Hal-POS exhibited better stability than In-Hal, due to hydrophobic surface which can prevent indigo molecules from chemical reactions and degradation. A new route was proposed to prepare organic-inorganic hybrid pigments, ignoring the interaction between dye molecules and substrates.
事实证明，用聚有机硅烷（POS）包覆是提高粘土/染料混合颜料化学稳定性和热稳定性的有效方法。但光稳定性以及与粘土矿物、染料和POS层之间的相互作用尚未见报道。为了研究上述问题，通过研磨法制备了基于埃洛石（Hal）和靛蓝（In）的新型有机-无机混合颜料。采用X射线衍射、透射电子显微镜、热重分析、傅里叶变换红外光谱对In-Hal（无POS层）和In-Hal-POS（有POS层）颜料的结构进行了表征。利用固态核磁共振（NMR）揭示了Hal、In和POS之间的相互作用。利用反射光谱和CIE 1976颜色空间系统评估了颜料的颜色参数和颜色变化。测试了热稳定性、对乙醇、1 mol·L HCl和1 mol⋅L NaOH的耐化学性以及对可见光的耐光性。靛蓝分子分散在Hal纳米管表面。POS层均匀覆盖在混合颜料表面，未改变Hal的晶体结构和形态。包覆POS层对混合颜料的颜色影响很小。然而，In-Hal-POS由于其疏水表面可防止靛蓝分子发生化学反应和降解，因此表现出比In-Hal更好的稳定性。提出了一种制备有机-无机混合颜料的新途径，忽略了染料分子与底物之间的相互作用。
