复合型钴蓝颜料的研究

本文采用化学共沉淀法合成复合型钴蓝颜料,确立了合理的制备工艺.采用XRD和DTA-TG分析了颜料的晶体结构和热稳定性.通过光谱反射曲线的分析,探讨了颜料的颜色、结构和发色机理,以及掺杂离子浓度与颜料发色的关系和掺杂离子作用机理.     

钴蓝颜料的研究与开发

笔者对尖晶石型钴蓝颜料的结构和显色机理做了介绍,并对钴蓝颜料的制备方法加以综述。其制备方法主要有固相反应法、液相反应法,其中固相反应法是目前工业生产的常用方法。实验中根据钴蓝颜料的结构与显色机理在配方中引入氧化锌,研究氧化锌对于钴蓝颜料呈色以及烧成温度的影响。最终确定合理配方,节约了氧化钴资源,同时烧成温度也降低了,减少了天然气能量消耗,达到了低碳的目的。     

尖晶石型钴蓝颜料的研究进展

介绍了尖晶石型钴蓝颜料的结构和显色机理,结合纳米材料的制备方法,综述了近年来钴蓝颜料制备方法及工艺,主要有固相反应法、液相反应法、气相法.其中固相反应法生产工艺简单,是目前工业生产常用方法,但制备的颜料粒径、色泽、稳定性等性能不能充分满足市场需求;液相反应法与气相法均可制成高品质的钴蓝颜料,但工艺复杂、成本较高.最后对钴蓝颜料的应用和发展作了简要介绍.     

液相沉淀法制备超微钴蓝颜料

研究了以硝酸铝,硝酸钴等为原料,采用液相沉淀法合成具有尖晶石型结构钴蓝颜料的制备方法。系统讨论了沉淀剂种类(氢氧化钠,氨水,尿素)、反应溶液浓度、洗涤方法、分散剂等工艺因素对合成钴蓝颜料粒度和光学性能的影响。采用SEM、TEM观察了合成颜料的形貌。最终制备出二次粒径中位径d50为670nm,一次粒径在45nm左右的超微钴蓝颜料。     

溶胶凝胶自蔓延燃烧法制备钴蓝颜料

采用溶胶凝胶法制备钴蓝前体干凝胶,经自蔓延燃烧及煅烧制备钴蓝颜料,研究了柠檬酸用量、溶胶反应温度、pH值、金属离子浓度、乙二醇等对凝胶的形成、燃烧特性及对制备的钴蓝颜料晶型结构的影响,以及干凝胶热处理方式和煅烧温度对钴蓝颜料晶型的影响。研究表明:柠檬酸用量、溶胶反应温度、乙二醇对制备的钴蓝晶型结构无影响;提高溶胶反应的温度,增加金属离子的浓度(0.01～0.1mol/L),有利于凝胶的较快形成;Co2+、Al3+总浓度低至0.005mol/L,不能形成完好尖晶石结构;适宜的pH值(约6.5)有利于柠檬酸的电离及与金属离子的络合以及干凝胶的自蔓延燃烧;乙二醇的使用可以改善钴蓝颜料的团聚现象;干凝胶自蔓延燃烧不能形成完好的尖晶石结构,燃烧后再煅烧,有助于改善钴蓝颜料的晶体结构及分散性;干凝胶自蔓延燃烧后再煅烧,随着煅烧温度的提高,制备的钴蓝颜料晶型更加完整,颜色更加鲜亮。     

沉淀法制备草酸钴及其粒度对钴蓝颜料性能的影响

以硫酸钴和草酸为原料,采用直接沉淀法制备超细草酸钴粉体.用激光粒度分析仪和高倍光学显微镜对制备的粉体进行了表征,用紫外分光光度仪对钴蓝颜料进行紫外反射光谱分析.分析了加料方式和Co2浓度对合成草酸钴粒度的影响,以及草酸钴粒度对钴蓝颜料反射率的影响.结果表明采取反加料方式,Co2浓度越低,草酸钴粒度越小,钴蓝颜料的颜色越鲜艳.     

稀土黄色颜料研究进展

稀土黄色颜料是新型的环境友好型无机颜料,具有广阔的应用前景。这里对稀土黄色颜料的制备方法,以及其组成、掺杂离子、矿化剂和灼烧温度对黄色颜料晶体结构和呈色机理影响进行了综述性介绍。     

两种钴蓝颜料在聚烯烃色母粒中的应用研究

通过X射线光电子能谱仪、X射线衍射仪及扫描电镜对钴蓝颜料元素种类及含量、结晶性能、颜料粒子形貌及分布的研究,了解两种钴蓝颜料的微观差异;将两种钴蓝颜料应用于色母粒,采用积分球式测色仪、显微镜和熔体流动速率仪,分析了色母粒及其着色制品的着色力、分散性能、遮盖性能及色母粒的加工流动性能差异。结果表明,恰当的钴铝含量可以使钴蓝颜料在制品中有良好的着色效果;颜料表面元素中碳含量高有利于颜料在塑料中的分散,制备的色母粒加工流动性能更好;原生粒子小的钴蓝颜料充分分散后其着色效果比原生粒子大的更好;而对于40%钴蓝颜料含量的色母粒,采用5%的蜡作为分散剂,可以达到很好的分散效果。     

熔盐法合成钴蓝颜料及其性能研究

采用熔盐法下制备了尖晶石结构的钴蓝颜料。研究了烧成温度、熔盐量与反应原料的配比、保温时间等工艺参数对样品的发色、相结构、相貌的影响。     

钴蓝颜料在外墙乳胶漆中的应用研究

分别通过 X射线光电子能谱仪（ EDS）、 X射线衍射仪（ XRD）、红外光谱（ FT-IR）及透射电镜（ TEM）对国内外钴蓝颜料元素成分及含量、结构、结晶性能、颜料粒子形貌及粒径分布进行了对比分析,将所选择的钴蓝颜料添加到外墙乳胶漆中,考察了不同微观形貌的钴蓝颜料对外墙乳胶漆的着色力、黏度、粒径、相容性的影响。结果表明：钴蓝颜料的初始粒径对其着色性能影响较大,初始粒径越小,其着色力越高;此外,钴蓝纳米粒子的粒径分布越窄,其在外墙乳胶漆中的分散能力越优异,同时提高了老化性能、耐候性能, 600 h不起泡、变色 ≤1级,在耐候要求年限较高的户外涂层中可以选择搭配钴蓝颜料着色代替酞青蓝,以达到涂层保光保色性要求。     

黑色陶瓷色料的研究现状与展望

分析了黑色陶瓷色料的现状,重点阐述了尖晶石型钴黑和无钴黑的发色机理,以及其固相法和液相法制备工艺;并对包裹黑、功能黑色色料进行了简单分析,提出了一些研究改进的思路及经验.     

Solid-state synthesis and characterization of cobalt blue core-shell pigment particles

Cobalt blue is one of the most chemically and thermally stable blue pigments. However, cobalt is scarce and expensive. To minimize the use of cobalt and reduce production costs and toxicity, cobalt blue core-shell pigments were synthesized by a solid-state method, which is cheaper than a liquid-phase reaction. Small cobalt hydroxide particles and large α-alumina particles, in various ratios, were used as the starting materials. The dry mixed powders were calcined at 1200°C for 2 hours. Elemental mappings of the surfaces and cross sections of the synthesized particles showed that the cobalt blue had a core-shell structure. X-ray diffraction patterns showed that the synthesized cobalt blue consisted of an α-alumina core and a cobalt aluminate shell. The color tone of the synthesized cobalt blue was evaluated from the lightness (L*) and chroma (C*) values. The color tone of the cobalt blue synthesized in this study was almost same as those of commercially available samples although the cobalt molar fraction was lower than the stoichiometric ratio (Co/(Co + Al) = 0.33, Co/Al = 0.5) which was calculated from the chemical reaction formula.     

Synthesis and color properties of the TiO2@CoAl2O4 blue pigments with low cobalt content applied in ceramic glaze

The TiO₂@CoAl₂O₄ complex blue pigments with low cobalt content were synthesized through calcinations of the precursor obtained from coprecipitating Co²⁺ and Al³⁺ to form Co‐Al LDHs (layered double hydroxides) on the surface of TiO₂ particles. The structure and the properties of the synthesized pigments were characterized by XRD, SEM, TEM, UV‐Vis spectroscopy, XPS, and colorimeter. The precursors of the blue TiO₂@CoAl₂O₄ complex pigments were consisted of LDHs shell layer encapsulated TiO₂ microsphere. After calcinations at 1100°C, the LDHs shell layer were absolutely transformed to the spinel CoAl₂O₄, and the pigments presented a core‐shell structure and uniform sphere morphology (the diameter of microsphere was about 780 nm). The absorption bands at around 547, 584, and 624 nm in the Uv‐Vis absorption spectra of the TiO₂@CoAl₂O₄ complex pigments were corresponded to the characteristic absorption bands of the spinel CoAl₂O₄, revealed the pigments with a bright blue hue. In addition, as the mass ratio of CoAl₂O₄/TiO₂ increased to 0.4, the blue component of the pigments reached to 27.89 and slight color variation with the increase in the CoAl₂O₄ content in a range, possessed low cobalt content and exhibited a stabile performance in commercial low‐temperature ceramic glazes. The XGT results showed that the TiO₂@CoAl₂O₄ complex pigments with low cobalt content presented bright color in ceramic glaze. Especially, the synthesized pigments reduced the usage and toxicity of cobalt, which were efficiency for economy and environmental protection.     

X‐ray absorption spectroscopy study of synthetic cobalt blue pigments similar to Kangxi blue and white porcelain

A series of cobalt blue pigments, which were synthesized based on the chemical compositions of the blue pigments in Kangxi blue and white porcelain, were investigated by Co, Mn, and Fe K‐edge and L_2,3‐edge X‐ray absorption spectroscopy to determine the oxidation states and species of the elements and to discern their impact on the blue color. The results reveal that Co is bivalent and mainly located at tetrahedral sites, which is the main parameter controlling the blue color. Mn is mainly present as Mn²⁺, or Co_xZn_1‐xAl₂O₄ and Fe is mainly present as Fe³⁺. In particular, Fe³⁺ substitutes the Al in CoAl₂O₄ and occupies octahedral sites with a high Mn content. All the synthetic cobalt blue pigments can form a solid solution with various end‐members or an intermediate solution spinel. The spectroscopic determination of the oxidation states and speciation of Co, Mn, and Fe furthers understanding of the coloration of blue pigments in blue and white porcelain.     

预涂钴离子的二氧化钛薄膜制备和性能

采用溶胶-凝胶法在玻璃表面预涂一层Co离子TiO2薄膜.研究了Co离子掺杂对样品相结构、晶粒尺寸和光催化降解亚甲基蓝活性的影响.实验结果表明,钴的掺杂对二氧化钛的相变有很大的抑制作用,并使其光谱响应范围向可见光区拓展.与未掺杂的二氧化钛相比较,经钻掺杂的二氧化钛具有更高的催化性能.     

Provenance of the cobalt pigment used for Jingdezhen minyao blue-and-white porcelain in the early Qing dynasty

The earliest cobalt application to porcelains can be traced back to the Tang dynasty (618–907). The production of the widely recognised blue-and-white porcelains in Jingdezhen did not mature until the late Yuan dynasty. According to historical texts, imported cobalt pigments were applied to blue-and-white porcelains in Jingdezhen kilns from the Yuan dynasty (1271–1368), and native Chinese cobalt pigments replaced imported sources in the Ming dynasty (1368–1644). As such, scholars have focused intensive studies on the sources of these blue pigments used in the Yuan and Ming dynasties. In this study, fifteen fragments of blue-and-white porcelain excavated from Jingdezhen minyao sites were selected to investigate the provenance of the cobalt pigment used in the Reigns of Kangxi (1662–1722), Yongzheng (1723–1735) and Qianlong (1735–1795). The results suggests that the cobalt rich materials correlate more closely to the Yunnan asbolites, rather than the widely-accepted Zhejiang asbolites mentioned in the historical texts and publications.     

耐酸陶瓷釉上钴蓝颜料的研究

采用固相法合成尖晶石型CoAl<,2>O<,4>和硅锌矿型(Co,Zn)<,2>,SiO<,4>钴蓝色料,比较了它们的呈色及耐酸性.引入SiO<,2>和MgO对Co<,2>O<,3>-AI<,2>O<,3>系统进行改性,并以细磨CoAl<,2>O<,4>为晶核,考察其对颜料呈色及耐酸性的影响,研制出呈色鲜艳、色饱和度较...     

陶瓷釉上钴蓝颜料用耐酸无铅熔剂的研究

采用固相法合成了硅锌矿型钴蓝色料,然后选取耐酸性较强的无铅熔剂与色料按照一定比例混合,在一定温度下彩烤得到钴蓝颜料.通过单因素试验、正交试验对熔剂配方进行优化,制得呈色鲜艳、耐酸性良好的釉上钴蓝颜料.XRD分析结果表明:彩烤后颜料中存在(Co,Zn)2SiO4和ZrSiO4晶相.