亚微米-微米级异晶包裹型锆基色料在非水溶剂系统中的制备研究

Zircon-based heteromorphic (ZBHM) pigments are naturally endowed with series of outstanding properties, such as superior stabilities, strong tinting strength, plenteous tones and decent coloration, which make these pigments function vitally in the industries of various color decoration applications. To date, there still exist some problems for further investigation for ZBHM pigments, which usually can be listed as low encapsulation efficiency of the encapsulating ZrSiO4 body to the coloring particles, fluctuating coloration effect in different batches and relevant coloring dependence on the raw materials caused by the low efficiency, and insufficient stability at high temperature, etc. In response to the current situation, we plan to employ CdSxSe1-x, Fe2O3 and carbon black as three optional coloring materials for 200 nm–2 m submicron-micron ZBHM pigments engendered with high encapsulation efficiency. They will be fabricated through dedicate soft-chemistry control of the solvent-coloring colloid-reactant system and by the solvothermal route with quasi-homogeneous precursor mixtures of the Zr-Si colloids and superfine coloring cores that have been prefabricated (for CdSxSe1-x, Fe2O3) or well-dispersed (for carbon black), while the parallel groups will be fabricated by calcination of the dry gel from the precursor mixtures at medium or high temperature. Strong-polar aprotic organic solvents will be applied as the primary liquid reaction systems during the liquid reaction process. Further explorations will be accordingly enhanced for the encapsulation mechanism and encapsulation efficiency calcinations from the previous modeling for zircon-based pigments. It can be expected that the current work will be instrumental to succedent researches, industrial production and extension to non-aforementioned coloring materials for other heteromorphic pigments.

异晶包裹型锆基色料具有稳定性好、着色力强、色调丰富等一系列优点，在目前的陶瓷、玻璃等与色彩装饰相关的应用中发挥着重要作用。目前该类色料在应用与研究中存在着包裹体ZrSiO4对色剂粒子的包裹率低、呈色多变、对原材料的依赖性较强与高温稳定性有待提升等主要问题。针对这一现状，本研究拟在强极性、非质子型有机溶剂系统下实现异晶包裹型锆基色料的制备。在非水溶剂系统下，通过对“溶剂-包裹体-色剂胶粒”这一系统的软化学控制，实现大红CdSxSe1-x、铁红Fe2O3与炭黑色剂的超细化制备或者分散，并与形成ZrSiO4的前驱体在液相条件下混合均化，经过后续溶剂热反应或者固相烧成处理，以期获得尺度在200 nm -2 um亚微米-微米级高包裹率的锆基色料。在此基础上，进一步探讨锆基异晶色料的包裹机理，完善该类色料的异晶包裹率计算模型，从而为锆基色料的后续研究、生产应用以及对其他异晶色料的研究提供有益借鉴。

异晶包裹型锆基色料具有稳定性好、着色力强、色调丰富等一系列优点，在目前的陶瓷、玻璃等与色彩装饰相关的应用中发挥着重要作用。本研究力图解决该类色料在应用中存在着包裹体ZrSiO4在结晶过程中形貌难控，对色剂粒子的包裹率低，色料呈色多变、对原材料的依赖性较强与高温稳定性有待提升等现实问题。在为期三年的研究中，我们从基础上探讨了控制ZrSiO4结晶的Zr-OH-F-R四元体系，揭示了高酸度值与适宜的氟化物矿化剂对ZrSiO4结晶的重要影响，首次制备出约1.0 um超细单分散球形硅酸锆粉体材料。该类粉体具有类似于Zr1–xSiO4[(OH)1–y·Ry]4x的结构组成，发现结晶过程中羟基或氟优先取代Zr而非Si；这一发现不同于前人在弱酸或者碱性条件（通常pH>1）下制备的产物ZrSi1–xO4[(OH)·F]4x，羟基或氟优先取代Si而非Zr。该球形单分散超细硅酸锆粉体具有出色的隔热与光反射特性，可以作为良好的保温隔热、能量屏蔽备选材料。在“水-非水”溶剂系统中开展了一系列色剂分散工作，通过精细调控，制备了400-600 nm范围亚微米级超细CdSxSe1-x@ZrSiO4红色色料，明显优于行业产品的呈色性能；对于3-10 μm常规尺度微米级大红色料，本研究采用硫源络合的方法，提升了色料的包裹率于现在水平的2-4倍。基于上述研究，我们完善了硅酸锆粉体的成核与生长过程控制机理，并发现了硅酸锆材料的完全消解方法。基于以成果，我们提出了锆基主体多元材料的包裹率（或组分含量）的准确测定方法。对于本工作中的超细CdSxSe1-x@ZrSiO4红色色料与高包裹率的大红色料两部分研究成果，我们正与企业合作努力推向产业化应用。