Serment Béatrice, Gaudon Manuel, Demourgues Alain, Noël Amélie, Fleury Guillaume, Cloutet Eric, Hadziioannou Georges, Brochon Cyril
CNRS, Univ. Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France.
CNRS, Univ. Bordeaux, Bordeaux INP, LCPO, UMR 5629, F-33615 Pessac, France.
ACS Omega. 2020 Jul 24;5(30):18651-18661. doi: 10.1021/acsomega.0c01289. eCollection 2020 Aug 4.
Cyan Ni AlO single-phase pigments with various Ni/Al atomic ratios (from 1:2 down to 1:4) have been prepared by a sol-gel route (Pechini) followed by postannealing treatments. Nickel aluminates crystallize in the well-known spinel structure (3 space group), where metals are located at two different Wyckoff positions: 16d (octahedron) and 8a (tetrahedron). Based on X-ray diffraction (XRD) Rietveld refinements, Ni cations are shown to be partially located in both tetrahedral and octahedral sites and, in addition, cationic vacancies occupy the Oh environment. In the pure-phase series, Ni/Al = 0.35, 0.40, 0.45, as the Al content increases, the Ni rate in the Td site decreases for Ni/Al = 0.45, thus altering the cyan color; within this series, the most saturated cyan coloration is reached for the highest Al concentration. Inorganic pigment drawbacks are their high density and hydrophilic surface, which induce sedimentation and aggregation in nonpolar media used in electrophoretic inks. Hybrid core-shell particle pigments have been synthesized from cyan pigments using nitroxide-mediated radical polymerization (NMRP) with methyl methacrylate monomer in Isopar G, leading to a dispersion of electrically charged hybrids in apolar media. Surface functionalization of the pigments by -octyltrimethoxysilane (OTS) and -dodecyltrimethoxysilane (DTS) modifiers has been compared. The inorganic pigments are successfully encapsulated by organic shells to allow a strong decrease in their density. Cyan inks, adequate for their use in e-book readers or other electrophoretic displays, taking further advantage of the high contrast ratio and reflectivity of inorganic pigments in regard to organic dyes, have been stabilized.
通过溶胶 - 凝胶法(佩琴尼法)并随后进行退火处理,制备了具有各种镍/铝原子比(从1:2降至1:4)的青色NiAlO单相颜料。铝酸镍以著名的尖晶石结构(3个空间群)结晶,其中金属位于两个不同的Wyckoff位置:16d(八面体)和8a(四面体)。基于X射线衍射(XRD)的Rietveld精修表明,镍阳离子部分位于四面体和八面体位点,此外,阳离子空位占据八面体环境。在纯相系列中,Ni/Al = 0.35、0.40、0.45,随着铝含量的增加,对于Ni/Al = 0.45,四面体位置的镍比率降低,从而改变了青色;在该系列中,铝浓度最高时达到最饱和的青色。无机颜料的缺点是其高密度和亲水性表面,这会在电泳油墨中使用的非极性介质中引起沉降和聚集。使用甲基丙烯酸甲酯单体在异链烷烃G中通过氮氧化物介导的自由基聚合(NMRP)从青色颜料合成了杂化核壳颗粒颜料,从而在非极性介质中产生带电杂化物的分散体。比较了用辛基三甲氧基硅烷(OTS)和十二烷基三甲氧基硅烷(DTS)改性剂对颜料进行的表面功能化。无机颜料成功地被有机壳包裹,使其密度大幅降低。考虑到无机颜料相对于有机染料具有高对比度和反射率的优势,适用于电子书阅读器或其他电泳显示器的青色油墨已经得到了稳定。