凹凸棒石/碱性黄24类玛雅黄颜料的研制

论文总字数：16937字

摘 要

目前玛雅蓝是全世界公认的最早出现的人工合成的有机—无机杂化颜料，它曾广泛的应用于玛雅人的壁画、陶器和雕像中，因其非凡的稳定性受到学者的广泛关注。研究证实玛雅蓝的主要成分是凹凸棒石和靛蓝。受玛雅蓝颜料的启发，多种黏土矿物和染料被用来制备类玛雅蓝颜料。目前该类颜料多通过干法研磨制备，存在色度不均、稳定性不高等问题。凹凸棒石是一种天然硅酸盐黏土矿物，特殊的棒晶结构使其对阳离子染料具有优异的吸附性能。因此，本研究以凹凸棒石为基体，通过湿法吸附阳离子染料碱性黄24得到凹凸棒石/碱性黄24有机-无机杂化颜料。研究发现，凹凸棒石对碱性黄24的饱和吸附量为3%左右，m_dye/m_PAL低于6%时，吸附后上清液中残留染料浓度为3.57 ppm，凹凸棒石对碱性黄24的吸附率达到99.3%以上，电镜显示凹凸棒石吸附碱性黄24后表面由光滑变得粗糙不平，红外谱图揭示凹凸棒石对碱性黄24的吸附过程并非简单的物理吸附，二者之间存在一定的相互作用。对颜料的稳定性测试结果表明，颜料具有较好的耐酸和耐醇性。

关键词：玛雅蓝，凹凸棒石，碱性黄24，吸附，杂化颜料

Abstract: Now the Maya blue is recognized as the world"s earliest synthetic organic-inorganic hybrid pigment which was widely applied in the Maya murals, pottery and sculpture. It received extensive attention of scholars because of its extraordinary stability. Studies have shown that the main ingredients of the Maya blue are palygorskite and indigo. Inspired by the Maya blue pigment, a variety of clay minerals and dyes were used to prepare Maya blue-like pigment. Thus far, these pigments are mainly prepared by dry grinding which leading to uneven chromaticity and low stability of the pigments. Palygorskite is a kind of natural silicate clay mineral which has excellent adsorption properties for cationic dyes. Therefore, this study used palygorskite as the matrix to adsorb a cationic dye-basic yellow 24 via a simple method of wet adsorption to prepare palygorskite/basci yellow 24 organic-inorganic hybrid pigment. The study found that the basic yellow in the palygorskite/basic yellow 24 pigment is up to 3%. The residual dye concentration in the supernatant after adsorption is below 3.57 ppm and the percentage of adsorbed basic yellow 24 is above 99.3% when m_dye/m_PAL is less than 6%. SEM and TEM showed that the surface of the palygorskite crystals in the palygorskite/basic yellow 24 pigment becomes rough compared with that of the pristine palygorskite. FTIR revealed that the adsorption process of basic yellow 24 onto palygorskite involved electrostatic interaction and hydrogen bonding between them. The obtained palygorskite/basic yellow 24 pigment performed excellent acid resistance and alcohol tolerance.

Key words: Maya Blue, Palygorskite, Basic yellow 24, Adsorption , Hybrid pigment

目 录

1 前言 4

2 实验部分 5

2.1 实验材料 5

2.2 制备玛雅黄颜料 6

2.3 稳定性测试 6

2.4 铬酸洗液的配置 7

2.5 仪器及表征 7

3 实验结果与讨论 8

3.1 标准曲线的绘制 8

3.2 凹凸棒石/碱性黄24有机-无机杂化颜料的制备 9

3.3 电镜的测定 11

3.4 红外光谱的测定 11

3.5 颜料稳定性评价 12

结 论 16

参 考 文 献 17

致 谢 20

1 前言

玛雅蓝是一种有机—无机复合颜料，色彩鲜亮，广泛应用于古玛雅文化，如壁画，陶器和雕塑等，有的甚至还被用来治疗疾病^[1-5]。玛雅蓝的最显著的优点是具有优异的稳定性，可防止酸、碱和有机物腐蚀以及生物降解。学者研究发现，玛雅蓝的主要成分是凹凸棒石 (palygorskite，PAL)和靛蓝(indigo)^[6-11]。

凹凸棒石（见图1）又称坡缕石（Palygorskite），是一种具琏层状结构的含水富镁铝硅酸盐粘土矿物，其结构属2：1型粘土矿物。在每个2：1单位结构层中，四面体晶片角顶隔一定距离方向颠倒，形成层链状。在四面体条带间形成与链平行的通道，通道横断面约3.7*6.3A°^[12]。通道中充填沸石水和结晶水，通过适当的热处理可以去除一部分的沸石水和结晶水，从而在保持孔隙结构不变的同时增加凹凸棒石的特定区域面积。同时凹凸棒石对大部份的阳离子、水分子和一定大小的有机分子具有较好的吸附能力，可以直接吸附进孔道中。凹凸棒石的电化学性能也很稳定，电解质不会使其絮凝，凹凸棒石在高温条件下或在盐水中的稳定性能也比较好。因此凹凸棒石的独特的孔隙结构、尺寸和极性可以为小分子提供选择性的通路，使人们通过湿法吸附制备类玛雅蓝颜料成为可能。

图1凹凸棒石晶体结构图

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