STUDY ON THE CLAY INTERLAMELLA REACTION FOR HIGHLY ORIENTATED MOLECULAR STRUCTURE

高度定向分子结构的粘土层间反应研究

• 批准号: 05453124
• 负责人: ENDO Tadashi
• 金额: $ 4.74万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453124/
• 关键词: CLAY-ORGANIC COMPOSITE; LANGMUIR-BLODGETT FILM; ALKYLAMINE; SMECTITE CLAY; INTERCALATION REACTION; MONOLAYER FILM; MULTILAYER FILM; SILICATE LAYERED STRUCTURE; AGGLOMERATION; ULTIMATE ORIENTATED MOLECULE; 高配向性組織; ナノコンポジット

Intercalation reaction has been extensively studied with a number of different approaches, experimentally as well as theoretically. Among inorganic materials, swelling clays were fairly profitable for understanding the interface characteristics between organic and inorganic materials, since the swelling clay as host allowed to confine various kinds of organic molecules as guest in its gallery. Numerical studies have been therefore focused on a well-orientated sequence of the functional organic molecules in the interlayrs of clay. On the other hand, the recent interests in Langmuir-Brodgett (LB) mono-and multilayr assemblies have originated from their potential use as ultrathin organic films with special and purposefully designed properties in microlithography, electro-optics, biochemical sensing, and tribology. For all these and other applications the careful control of the molecular structure and the microscopic order of the thin films-both lateral and traversal-are required.In this p … More aper we report on a new approach to fabricate the clay unit layrs/organic molecules multilayrs films using a conventional LB technique. It will be demonstrated that there is no other homogenized preparation techniques to from inorganic and organic composites in the nano-scale with a wide variety of possibilities for influencing ordered states and thus adjusting their properties. This is due to the fact that the organic ions or molecules are initially organized on a clay surface where the environmental parameters can be readily changed and in a wide range, comparing with the intercalation reaction.The surface pressure-area, pi-A isotherms were measured at 16ﾟC for the fabrication of the monolayrs of nanodeylamine on distillled water and aqueous solutions contained various quantities of hectorite clay (referred to as HT-C_<19>). By using the horizontal lifting method on the hydrophillic surface of glass substrate, the deposition of a suitable monolayr was observed. The extrapolated surface area per molecule was estimated to be 21-22A_2. Nine times this value (189A^2) was almost equivalent to 7 times the hexagonal block area, involving 6-member rings of SiO_4 tetrahedrons on the silica sheet (189.7 A^2). By assuming that a functional headgroup of nanodecylamine was ionized as +1, it was plausible that 9 molecules was sufficiently covered with the 7 mean-charges of clay sheets for keeping the electroneutrality.At lower quantity of clays, the monolayr of composites never be statified. This implied that the built-up of monolayrs was apparently conducted by the electrostatic interaction between cationic amine and anionic clay. In contrast, at larger quantity of clay, the condensation of LB film was observed on the water subphase as the deposition progressed. The observation implied that the collapse of monolayr or the crystallization of nanodecylamine itself occurred.According to the powder X-ray diffraction patterns of multilayr NaHT-C_<19> composites, the well-stratification of LB film was performed under a surface pressure of 20 to 35 dyn/cm at pH=5.80. The basal spacing of LB films was estimated to be 61-62 A,which corresponded to the bilayrs of alkylamines (Y-type).According to the chemical analysis and the consumed area of LB trough, the accumulative proportion in multilayred LB films was estimated. The accumulative proportion is scarcely changed between swelling clays, but steeply shifted from theoretical one with increasing the pH.The FTIR-RAS spectra of 15 layred hectorite-nanodecylamine films and nanodecylamine LB multilayred film demonstrated that the nu (CH_2) bands at 2917 and 2850 cm^<-1> are enhanced in intensity and width. These changes indicate conformational disordering of the-CH_2-chains with an accompanying transition dipole component perpendicular to the clay surface. A relative intensity changes of the delta (CH_2) band at 1467 cm^<-1> probably arises from the same origin.The temperature dependence of d_< (002) > peak intensity for montmorillonite-nanodecylamine indicated that Na^+-hectorite nanodecylamine and nanodecylamine LB films. On heating above 48ﾟC of melting temperature, nanodecylalkylamine LB film collapses. However, the geometrical arrangement of alkylamine molecules is changed stepwise in the composite LB film having the basal spacings of 61.5 A to 38.6 A,as being of an intercalated clay compound.Our results are explained by models which links particular chain orientations on the clay surface to the surface binding geometry of the terminal amine group and the lateral interlocking geometry of the zigzag hydrocarbon skeleton. Less

插层反应已被广泛研究了许多不同的方法，实验以及理论。在无机材料中，膨胀粘土对于理解有机和无机材料之间的界面特性是相当有益的，因为作为主体的膨胀粘土允许将各种有机分子作为客体限制在其画廊中。因此，数值研究一直集中在一个良好的定向序列的功能有机分子的粘土夹层。另一方面，最近的兴趣在LB的单层和多层组件已经起源于它们的潜在用途作为有机薄膜具有特殊的和有目的地设计的性能在微光刻，电光，生物化学传感，和摩擦学。对于所有这些和其他应用，需要仔细控制薄膜的分子结构和微观顺序（横向和横向）。 ...更多信息 本文报道了一种利用传统LB技术制备粘土/有机分子多层膜的新方法。它将被证明，有没有其他均匀的制备技术，以形成无机和有机复合材料在纳米尺度上具有各种各样的可能性，影响有序状态，从而调整其性能。这是由于有机离子或分子最初是在粘土表面上组织的，与插层反应相比，粘土表面的环境参数可以容易地在宽范围内改变。在16 ℃下测量π-Δ等温线，用于在蒸馏水和含有不同量的锂蒙脱石粘土（称为HT-1）的水溶液上制造纳米脱胺的单层。C_<19>）。用水平提拉法在玻璃基片的玻璃表面上沉积了合适的单层膜。外推的每分子表面积估计为21-22A_2。这个值的9倍（189A^2）几乎相当于六方块面积的7倍，包括二氧化硅片上SiO_4四面体的6元环（189.7 A^2）。假设纳米癸胺的一个官能团被电离为+1，则9个分子被粘土层的7个平均电荷充分覆盖以保持电中性，在较低的粘土含量下，复合材料的单层结构不会分层。这表明单分子膜的形成是通过阳离子胺与阴离子粘土之间的静电相互作用进行的。相比之下，在更大量的粘土，LB膜的冷凝观察到的水亚相的沉积进展。根据多层NaHT-C_2复合物的粉末X射线衍射图<19>，在pH=5.80、表面压力为20 ~ 35 dyn/cm的条件下，LB膜的分层较好。根据化学分析和LB槽的消耗面积估算了多层LB膜中的累积比例。15层锂蒙脱石-纳米癸胺膜和纳米癸胺LB多层膜的FTIR-RAS光谱表明，nu（CH_2）在2917和2850 cm ~ 2处的吸收<-1>峰强度和宽度均有所增强。这些变化表明-CH_2-链的构象无序，并伴随着垂直于粘土表面的跃迁偶极分量。δ（CH_2）峰在1467 cm ↑ [2]处的相对强度变化<-1>可能源于相同的原因.蒙脱石-纳米癸胺的d_&lt;（002）&gt;峰强度随温度的变化表明Na^+-锂蒙脱石纳米癸胺和纳米癸胺LB膜.在加热到高于48 ° C的熔融温度时，纳米癸基烷基胺LB膜塌陷。然而，烷基胺分子的几何排列是逐步改变的复合LB膜具有的基础间距为61.5 A至38.6 A，作为一个插层粘土compound.Our的结果解释的模型，链接特定的链取向粘土表面的表面结合几何形状的末端胺基和锯齿形的烃骨架的横向联锁几何形状。少

项目成果

Yoshifumi Uchita, Tadashi Endo, Hirotsugu Takizawa and Masahiko Shimada: ""Synthesis of High Orientated Clay-organic Composites Using Langmuir-Blodgett Technique"" J.Jpn. Soc. Powder and Powder Metallurgy. 41. 1185 (1994)

Yoshifumi Uchita、Tadashi Endo、Hirotsugu Takizawa 和 Masahiko Shimada：“使用 Langmuir-Blodgett 技术合成高取向粘土有机复合材料”J.Jpn。

Tadashi Endo: "clay-organic nanocomposites in Langmuir-Blodgett multilayer Films" Langmuir. in press. (1995)

Tadashi Endo：“Langmuir-Blodgett 多层薄膜中的粘土有机纳米复合材料”Langmuir。

TADASHI ENDO,YOSHIFUMI UCHITA,and MASAHIKO SHIMADA: ""CLAY-ORGANIC NANOCOMPOSITES IN LANGMUIR-BRODGETT MULTILAYER FILMS"" Proc. of 1994 Fall Meeting of MRS. (in press).

TADASHI ENDO、Yoshifumi UCITA 和 MASAHIKO SHIMADA：“朗缪尔-布罗德杰特多层薄膜中的粘土有机纳米复合材料”Proc。

Tadashi Endo: "Clay-organic nanocomposites in Langmuir-Brodgett multilayer Films" Langmuir. (in press). (1995)

Tadashi Endo：“Langmuir-Brodgett 多层薄膜中的粘土有机纳米复合材料”Langmuir。

内田淑文ら: "Langmuir-Blodgett法による高配向粘土-有機物複合体の合成" 粉体および粉末冶金. 41. 1185-1188 (1994)

Yoshifumi Uchida 等人：“通过 Langmuir-Blodgett 方法合成高度定向的粘土有机复合材料”粉末和粉末冶金。 41. 1185-1188 (1994)