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The search for alternative routes of organic thin film formation is stimulated by the outstanding properties of these films in such fields as nonlinear optics, photonic data processing and molecular electronics. The formation of highly ordered multilayer structures by thermal vacuum deposition (VD) of organic compounds is an essential step toward the application of supramolecular organic architectures in technical systems. The VD of an amphiphilic substituted 2,5- diphenylene-1,3,4-oxadiazole 1 onto silicon substrates at defined temperature was used for the formation of ultrathin films. The structural data obtained for the VD-films of oxadiazole 1 by means of X-ray reflectivity, X-ray grazing incidence diffraction and atomic force microscopy (AFM) investigations indicate the formation of well ordered oxadiazole multilayers. The structure of the VD-multilayers is compared with that of Langmuir-Blodgett (LB) films and thermally treated LB-multilayers prepared from the same compound.
New amphiphilic compounds 1-9 that feature a construction with dendronized hydrophilic and hydrophobic segment groups connected to a specific aromatic or aliphatic spacer unit have been synthesized, following a modular building block strategy. The hydrophilic dendrons are typically branched elements with peripheral carboxylic groups, unlike the hydrophobic dendrons that contain peripheral alkyl chains as part of respective amide functions. The hydrophilic dendrons are in different generations of branching, while the hydrophobic dendrons are all in the first generation of branching (three terminal branching), but differ in the length of the alkyl chains, thus giving rise to designed structure and amphiphilic properties in the new compounds. The resulting surfactants are capable of forming well-defined Langmuir films of remarkable stability when spread from a solution onto an aqueous subphase. Nevertheless, specific packing behaviour and orientation of the amphiphilic molecules were found, depending on the molecular structure, as determined using analysis of the surface pressure-area (pi-A) isotherms. Langmuir-Blodgett transfer of the first monolayer from a pure water subphase to a clean silicon wafer proved possible for the amphiphiles of peripheral alkyl chain length C-12, while the amphiphiles with the longer alkyl chains failed, possibly due to the more rigid monolayers they form, impeding the transfer.
The pendant drop technique was used to determine p/A isotherms of docosanic acid spread on the drop surface of an aqueous polymer solution. Two water soluble polymers were used, poly(dimethyl-diallyl-ammoniumchloride) and sodium poly(styrene sulfonate-b-ethylethylene). By fast changes of the drop volume, the monolayers were compressed and dilated. The stress relaxation was monitored and surface rheological dilation parameters were obtained. It is shown that the fatty acid monolayer can be mechanically stabilized by both interacting anionic and cationic polymers. In the case of the anionic polymer, the interaction becomes more pronounced in the presence of salts in the subphase (counterions). Brewster angle microscopy shows that the typical tilt-orientation of crystalline domains of the fatty acid monolayers transforms into a more uniform and fluid-like structure caused by the polymer/monolayer interaction. The surface rheological behavior is dramatically influenced by the polymer binding. The interaction results in surface dilational viscoelastic properties and show that there is a strong resistance against expansion of the complex fatty acid/polymer layer.
This paper describes the formation and structure investigation of Langmuir monolayers and Langmuir-Blodgett multilayers formed from amphiphilic derivatives of 2,5-diphenyl-1,3,4-oxadiazole. The 2,5-diphenyl-1,3,4-oxadiazole group as a functional unit with interesting physical and chemical properties is maintained, while the head group, the length of the alkyl chain and the structure of the coupling unit between aromatic and aliphatic part of these linear short-chain amphiphiles is systematically varied in order to explore the influence of this change on the film forming properties and the stability of Langmuir and Langmuir-Blodgett films. Molecular mechanics simulations are shown by these systematic variations to be suitable for the prediction of optimal chemical structures allowing for a stable stratified molecular packing. The combination of a detailed structure investigation of the multilayers based on scanning force microscopy and X-ray data with molecular mechanics simulations yields an insight into the packing of the molecules and the intermolecular interactions.
Study of gas transport through composite membranes with a stabilised Langmuir-Blodgett skin layer
(1995)
The Langmuir-Blodgett (LB-) technique is used to deposit molecular reinforced separation layers on porous polymer substrates resulting in composite membranes for gas separation. The adsorption of a polycation to the arachidic acid Langmuir layer and the subsequent transfer of the highly ordered and stabilised monolayer onto a polypropylene membrane (Cellgard 2400) yields a laminated separation layer combining the advantageous high degree of order of fatty acid films and the stability of thin polymeric films. X-ray reflectivity data of these films confirm the transfer of the assembled polymer layer together with the fatty acid monolayer and the formation of ordered Y-type LB-films. SFM pictures show a dense film without pinholes completely covering the porous support. Gas permeation measurements are used to study the transport process of different gases through the composite membrane.
The thermal treatment of Y-type Langmuir-Blodgett (LB) films formed from the amphiphilic derivative of 2,5- diphenyl-1,3,4-oxadiazole 1 results in changes of the molecular packing. These changes have been analysed by a combination of X-ray specular reflectivity data, X-ray grazing incidence diffraction data and scanning force microscopy images, On the basis of these experimental data we have simulated possible supramolecular structures, These simulations provide insight into the intermolecular interactions giving rise to the observed structural transitions. The crystalline structure induced by thermal treatment of the LB films is characterized by a uniaxial texture, which is correlated with the dipping direction during deposition of the LB film.
Langmuir floating layers of two phthalocyanine derivatives, ytterbium bisphthalocyanine and tetra-tert-butyl nickel phthalocyanine, were investigated by means of compression isotherms, surface potential kinetics and Brewster angle microscopy (BAM) in order to study the influence of peripheral substituents on the structure and stability of these films and on their suitability for a subsequent transfer onto solid substrates. Specific substitutions that may lead to amphiphilic molecular units seem to play a key role in the development of well organised thin films prepared with this technique.
Langmuir-Blodgett films of bolaamphiphiles with reactive head groups can be used for the surface modification of composite membranes for gas separation processes. The scope of our investigations was to get a detailed insight in the monolayer behaviour and LB film structure of previously synthesized bisaroyl azide bolaamphiphiles. The layers have been analyses by means of surface potential measurements and Brewster angle microscopy. Furthermore parameters for a successful LB Film deposition were found. As expected for a molecule with two hydrophilic ends the transfer ratio on upstroke was close to one and on downstroke no transfer occurred. The multilayer structure was analysed by scanning force microscopy and X-ray reflectivity measurements. The SFM images revealed a periodic in plane structure on molecular level. Based on a combination of the X-ray data with results of other methods two possible models of the multilayer structure are presented