复合无机颜料铜铬黑的制备与性能研究
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摘要
本文采用均匀沉淀法、共沉淀法和溶胶-凝胶法合成了具有优异性能的环保型复合无机颜料铜铬黑,并在溶胶-凝胶法的基础上,研究了离子的掺杂对颜料性能的影响。通过X射线衍射分析、热分析、紫外-可见分光光度计、透射电镜、激光粒度测试仪及着色力等测试对铜铬黑样品进行了表征。
在均匀沉淀法制备铜铬黑颜料中,研究了尿素用量、溶液pH值、表面活性剂以及煅烧温度对颜料制备的影响,并对制得的样品的晶型、形貌、粒径大小及分布、耐热性、着色力进行了测试表征；溶胶-凝胶法除了以上所述,还研究了铜铬比对颜料制备的影响。结果表明：均匀沉淀法能够制得粒径约为50nm的颜料样品,添加了PEG400做分散剂可以显著改善颜料样品的分散性能；而溶胶-凝胶法制得的样品粒径低至30nm；此外,后者的转晶温度较低,两种方法制得的样品都有非常高的热稳定性。
在离子掺杂对铜铬黑颜料性能研究中,一类是发色离子掺杂的研究；另一类是不发色离子的掺杂研究。在发色离子掺杂研究中,选取了Co~(2+)、Ni~(2+)、Fe~(3+)等离子进行研究,着重考察了发色离子掺杂对铜铬黑主色的影响。研究证明：Fe~(3+)掺杂不能有效提高铜铬黑颜料的着色力及色相,而Co~(2+)、Ni~(2+)则可以显著改善颜料的着色力,而且能够获得颜色更加鲜艳的颜料。在不发色离子掺杂研究中,着重研究Zn~(2+)和Mg~(2+)掺杂对铜铬黑样品晶格参数的影响。研究表明：这两种离子对铜铬黑的晶格影响较大,随着掺杂量的增加可以导致样品发生相转变,由四方相转向立方相。
此外,还采用了共沉淀法合成了铜铬黑颜料,该方法的核心是采用碱式铬酸铜铵前驱体热分解的方式合成铜铬黑,只需要500℃即可,并将煅烧之后得到的样品进行酸洗处理,除去产物中的CuO。研究表明：在较低的处理温度下,亚铬酸铜晶体更易以立方晶系存在,但是酸洗也导致晶体发生了相转变,在较高温度煅烧则以稳定的四方相存在,四方晶系亚铬酸铜热稳定性优于立方晶系。
作为一种无毒环保颜料,实验中选择了不同温度煅烧制备的铜铬黑样品进行了六价铬含量的测定。结果表明：铜铬黑样品中六价铬的含量跟晶体的结晶度有很大的关系,当晶体没有转晶完全时,样品中六价铬含量很高；而当晶体转晶完成后,由于铬已经进入到尖晶石的晶格当中,稳定性高,不易被氧化为六价铬。所以六价铬含量随着温度升高下降明显。此外,铜铬比也对六价铬含量影响较大,铬铜比大则样品六价铬含量高。总的来说,铜铬黑中六价铬含量远远低于国际及国家标准,说明铜铬黑是环保无毒的。
In this paper, a composite inorganic environmental protection pigment copper chromite black were prepared by homogeneous precipitation method, co-precipitation method and Sol-Gel method. And on the basis of Sol-Gel method, ions doped samples were studied to show the influence on the copper chromite black pigments. Additionally, copper chromite black pigments were characterized by X-ray diffraction, thermal analysis technology, UV-VIS Spectrophotometer, TEM, laser particle analyzer and coloring power test.
For the copper chromite black pigment samples prepared by homogeneous precipitation method, the additive amount of urea, pH in the solution, surfactant, calcination temperature and other impact factors were studied to show influence on the preparation of pigments, and crystal morphology, particle size and distribution, heat resisting property and coloring power were also discussed. In the Sol-Gel method, except for the factors mentioned above, Cu-Cr ratio was also studied. The results show that copper chromite black pigments with average size of about 50nm were obtained by homogenous precipitation method, and add PEG400 as dispersant can markedly improve the dispersion of pigment samples. But the pigment samples prepared by Sol-Gel method can get even smaller particles with the average size less than 30nm. Besides, samples prepared by the latter can get the crystal transformation temperature lower than the former, and pigment samples synthesized by both methods have high heat resisting property.
In the research on the ions doping based on the copper chromite black pigments; two kinds of ions were studied. The first kind is chromophoric ions; the other is colourless ions. In chromophoric ions doping research, Fe3+, Co2+and Ni2+were taken into account and the roles these ions playing in the pigment samples were mainly discussed. The results show that Fe3+impacts bad on the coloring power of the pigments while Co2+and Ni2+have opposite effects. They can improve the coloring power significantly and also obtain chromatic color. As far as colourless ions are concerned, Zn2+and Mg2+were chosen to study the influence on the microstructure such as lattice parameters. Research has shown that both ions have relatively big influence on the lattice parameters of the copper chromite black pigment samples. With the increase amount of doped ions, phase transition was happened on the pigment samples. The tetragonal copper chromite turned to cubic phase.
In addition, copper chromite black pigments also prepared by co-precipitation method, the core of this method is preparing ammonium hydroxide copper chromite first and then put it into muffle furnace to calcinate. By this means, with the temperature of 500℃is enough. After calcination, the samples were washed by hot dilute hydrochloric acid and then washed by hot distilled water. In consequence, copper chromite crystal exists in cubic phase at lower temperature while exists in tetragonal phase at higher temperatures. But after washed by acid, the cubic phase turned to tetragonal phase. And experiment shows that cubic phase samples have bad heat resisting property.
As a kind of non-toxic and environmental protection pigment, hexavalent chromium content of the pigment samples calcinated at different temperatures were characterized. Results show that hexavalent chromium content has a great relationship with the crystallinity of the pigment samples. When the crystallinity is lower, the hexavalent chromium content is higher. But when the copper chromite crystal formed completely, chromium ions were inserted into spinel lattices, so the samples were very stable that trivalent chromic ions were hard to be oxidized to hexavalent valence. Besides, Cu-Cr ratio also plays a great important role in the hexavalent chromium content. If total chromium is far beyond theoretical content, it is easier to be oxidized to hexavalent valence. But, by and large, hexavalent chromium content is far less than any national and international standards; this proves copper chromite black pigment to be a kind of non-toxic and environmental protection pigment.
在均匀沉淀法制备铜铬黑颜料中,研究了尿素用量、溶液pH值、表面活性剂以及煅烧温度对颜料制备的影响,并对制得的样品的晶型、形貌、粒径大小及分布、耐热性、着色力进行了测试表征；溶胶-凝胶法除了以上所述,还研究了铜铬比对颜料制备的影响。结果表明：均匀沉淀法能够制得粒径约为50nm的颜料样品,添加了PEG400做分散剂可以显著改善颜料样品的分散性能；而溶胶-凝胶法制得的样品粒径低至30nm；此外,后者的转晶温度较低,两种方法制得的样品都有非常高的热稳定性。
在离子掺杂对铜铬黑颜料性能研究中,一类是发色离子掺杂的研究；另一类是不发色离子的掺杂研究。在发色离子掺杂研究中,选取了Co~(2+)、Ni~(2+)、Fe~(3+)等离子进行研究,着重考察了发色离子掺杂对铜铬黑主色的影响。研究证明：Fe~(3+)掺杂不能有效提高铜铬黑颜料的着色力及色相,而Co~(2+)、Ni~(2+)则可以显著改善颜料的着色力,而且能够获得颜色更加鲜艳的颜料。在不发色离子掺杂研究中,着重研究Zn~(2+)和Mg~(2+)掺杂对铜铬黑样品晶格参数的影响。研究表明：这两种离子对铜铬黑的晶格影响较大,随着掺杂量的增加可以导致样品发生相转变,由四方相转向立方相。
此外,还采用了共沉淀法合成了铜铬黑颜料,该方法的核心是采用碱式铬酸铜铵前驱体热分解的方式合成铜铬黑,只需要500℃即可,并将煅烧之后得到的样品进行酸洗处理,除去产物中的CuO。研究表明：在较低的处理温度下,亚铬酸铜晶体更易以立方晶系存在,但是酸洗也导致晶体发生了相转变,在较高温度煅烧则以稳定的四方相存在,四方晶系亚铬酸铜热稳定性优于立方晶系。
作为一种无毒环保颜料,实验中选择了不同温度煅烧制备的铜铬黑样品进行了六价铬含量的测定。结果表明：铜铬黑样品中六价铬的含量跟晶体的结晶度有很大的关系,当晶体没有转晶完全时,样品中六价铬含量很高；而当晶体转晶完成后,由于铬已经进入到尖晶石的晶格当中,稳定性高,不易被氧化为六价铬。所以六价铬含量随着温度升高下降明显。此外,铜铬比也对六价铬含量影响较大,铬铜比大则样品六价铬含量高。总的来说,铜铬黑中六价铬含量远远低于国际及国家标准,说明铜铬黑是环保无毒的。
In this paper, a composite inorganic environmental protection pigment copper chromite black were prepared by homogeneous precipitation method, co-precipitation method and Sol-Gel method. And on the basis of Sol-Gel method, ions doped samples were studied to show the influence on the copper chromite black pigments. Additionally, copper chromite black pigments were characterized by X-ray diffraction, thermal analysis technology, UV-VIS Spectrophotometer, TEM, laser particle analyzer and coloring power test.
For the copper chromite black pigment samples prepared by homogeneous precipitation method, the additive amount of urea, pH in the solution, surfactant, calcination temperature and other impact factors were studied to show influence on the preparation of pigments, and crystal morphology, particle size and distribution, heat resisting property and coloring power were also discussed. In the Sol-Gel method, except for the factors mentioned above, Cu-Cr ratio was also studied. The results show that copper chromite black pigments with average size of about 50nm were obtained by homogenous precipitation method, and add PEG400 as dispersant can markedly improve the dispersion of pigment samples. But the pigment samples prepared by Sol-Gel method can get even smaller particles with the average size less than 30nm. Besides, samples prepared by the latter can get the crystal transformation temperature lower than the former, and pigment samples synthesized by both methods have high heat resisting property.
In the research on the ions doping based on the copper chromite black pigments; two kinds of ions were studied. The first kind is chromophoric ions; the other is colourless ions. In chromophoric ions doping research, Fe3+, Co2+and Ni2+were taken into account and the roles these ions playing in the pigment samples were mainly discussed. The results show that Fe3+impacts bad on the coloring power of the pigments while Co2+and Ni2+have opposite effects. They can improve the coloring power significantly and also obtain chromatic color. As far as colourless ions are concerned, Zn2+and Mg2+were chosen to study the influence on the microstructure such as lattice parameters. Research has shown that both ions have relatively big influence on the lattice parameters of the copper chromite black pigment samples. With the increase amount of doped ions, phase transition was happened on the pigment samples. The tetragonal copper chromite turned to cubic phase.
In addition, copper chromite black pigments also prepared by co-precipitation method, the core of this method is preparing ammonium hydroxide copper chromite first and then put it into muffle furnace to calcinate. By this means, with the temperature of 500℃is enough. After calcination, the samples were washed by hot dilute hydrochloric acid and then washed by hot distilled water. In consequence, copper chromite crystal exists in cubic phase at lower temperature while exists in tetragonal phase at higher temperatures. But after washed by acid, the cubic phase turned to tetragonal phase. And experiment shows that cubic phase samples have bad heat resisting property.
As a kind of non-toxic and environmental protection pigment, hexavalent chromium content of the pigment samples calcinated at different temperatures were characterized. Results show that hexavalent chromium content has a great relationship with the crystallinity of the pigment samples. When the crystallinity is lower, the hexavalent chromium content is higher. But when the copper chromite crystal formed completely, chromium ions were inserted into spinel lattices, so the samples were very stable that trivalent chromic ions were hard to be oxidized to hexavalent valence. Besides, Cu-Cr ratio also plays a great important role in the hexavalent chromium content. If total chromium is far beyond theoretical content, it is easier to be oxidized to hexavalent valence. But, by and large, hexavalent chromium content is far less than any national and international standards; this proves copper chromite black pigment to be a kind of non-toxic and environmental protection pigment.
引文
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