Monolayer and multilayer compact film formations on different substrates by physical deposition

Dissipative particle dynamics simulations are applied to investigate the monolayer and multilayer film formations on different solid substrates by physical deposition. The influences of the polymer concentration, the polymer chain length, the solvent quality, and the interactions between the polymer solution and the solid substrate surface on the film formation dynamics and the mechanism are studied in detail. The results are analyzed in terms of the thickness and the shape of the deposited film, the kinetics of phase separation in the polymer solution, and the contact angle formed between the polymer aggregations and the substrate surface. Moreover, we suggest two strategies, designing a deposition process analogous to “chemical titration” and physically blocking interlayer diffusion by a simple crosslinked network barrier, to deposit the compact monolayer and multilayer films with better quality, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 353–365, 2009     

Effects of molecular mass and surface treatment on adsorbed poly(methyl methacrylate) on silica

The behavior of relatively monodisperse adsorbed poly(methyl methacrylate) (PMMA) samples, from 19 to 587 kDa on silica, was studied using modulated differential scanning calorimetry and FTIR. On untreated Cab? O? Sil silica, the glass transition temperatures (T_gs) were higher (by around 30 °C), and the transitions were significantly broader (by a factor of 5–6) than those for the corresponding bulk samples. While the T_gs for the bulk polymers showed the expected dependence on molecular mass, the polymers on untreated silica showed little dependence, i.e., at the same adsorbed amounts, the glass transitions were very similar. The FTIR spectra of the adsorbed PMMA (on untreated silica) showed the presence of at least two resonances, one for the bound (hydrogen bonded to surface silanols) and another for free carbonyls. Fitting of the spectra allowed the estimation of the bound fractions of carbonyls that were dependent on the adsorbed amount, but not molecular mass. On Cab? O? Sil treated with hexamethyldisilizane (HMDS), the adsorbed PMMA exhibited glass transition behavior with little molecular‐mass dependence; the T_gs for the different PMMA samples were very similar to those of the high‐molecular mass bulk polymer, but with additional broadening of about a factor of 2. FTIR spectra for the PMMA samples on the treated silica did not show significant amounts of any of the hydrogen‐bonded carbonyl groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 649–658, 2008     

Secondary adsorption of nitrobenzene and m-nitrophenol by hexadecyltrimethylammonium-montmorillonite thermo-XRD-analysis

In the present research we studied the effect of the solvent used, whether it was polar water or a non-polar organic solvent (n-hexane or n-hexadecane), on the basal-spacing and bulk structure of the sorbate-sorbent complexes obtained by the secondary adsorption of nitrobenzene and m-nitrophenol by two types of organo-montmorillonites. X-ray measured basal spacings before and after thermal treatments up to 360°C. The organo-clays were synthesized, with 41 and 90% replacement of the exchangeable Na⁺ by hexadecyltrimethylammonium (HDTMA), with mono-and bilayers of HDTMA cations in the interlayer space, labelled OC-41 and OC-90, respectively. After heating at 360°C both organo-clays showed spacing at 1.25–1.28 nm, due to the presence of interlayer-charcoal, indicating that in the preheated organo-clays the HDTMA was located in the interlayer. The thermo-XRD-analysis of Na-clay complexes showed that from organic solvents both sorbates were adsorbed on the external surface but from water they were intercalated. m-Nitrophenol complexes of both organo-clays obtained in aqueous suspensions contain water molecules. Spacings of nitrobenzene complexes of OC-41 and OC-90 and those of nitrophenol complexes of OC-41 showed that the adsorbed molecules were imbedded in cavities in the HDTMA layers. Adsorption of m-nitrophenol by OC-90 from water and n-hexane resulted in an increase of basal spacing (0.21 and 0.29 nm, respectively) suggesting the existence of a layer of nitrophenol molecules sandwiched between two parallel HDTMA layers.     

Dynamic electrochemical impedance spectroscopy of the adsorption and relaxation of polyaniline chains during potentiodynamic redox transformations

A new approach to an equivalent circuit analysis of impedance spectra of a conducting polyaniline (PAni) layer is presented. Film properties are often modeled by constant-phase elements (CPE), which are closer to experimental results than capacitors. We want to take an insight into the CPE. We propose a novel equivalent circuit based on the Frumkin-Melik-Gaikazyan adsorption model, as we suppose that the PAni layer molecules may behave like other adsorbing and relaxing organic compounds. Measurements are performed using recently developed experimental technique—dynamic electrochemical impedance spectroscopy. Obtained spectra are analyzed using the proposed equivalent circuits. Characteristics of several parameters are analyzed and discussed. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 9, pp. 1111–1119. The text was submitted by the authors in English.     

Effect of amino and polysiloxane groups on the chemical adsorption of polymers containing thiophosphate at the oil/metal interface under extreme pressure

Copolymers that separately contained thiophosphate–polysiloxane, thiophosphate–amino, and thiophosphate–polysiloxane–amino groups were synthesized and characterized. The performances of these synthesized copolymers on metal surfaces under a high load and rotary velocity were examined by the measurement of the oil temperature, frictional coefficient, and electrical contact resistance between two metal surfaces. The configuration of the adsorption layer was studied with energy‐dispersive spectrometry (EDS) and scanning electron microscopy (SEM). Copolymers that contained amino–thiophosphate groups reduced the frictional coefficient between two metal surfaces and markedly limit the increase in the oil temperature. Notably, a higher content of polysiloxane groups in the copolymer corresponded to an increased operating time to establish the adsorption layer on the metal surface. However, a higher content of amino groups reduced the time required for the layer to form. The adsorption layers that formed on the metal surfaces were investigated by EDS as phosphides produced by a chemical reaction of the thiophosphate‐containing copolymer with the metal surface. These adsorption layers on the metal surface were directly observed with SEM. The layer that formed on the metal surface of copolymers containing less polysiloxane and more amino groups was the thickest layer for all the synthesized copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1795–1803, 2002     

阿达玛变换成像光谱术的研究

本文论述了阿达玛变换成像光谱仪的基本原理,探讨了工作模式和若干设计问题,利用自行研制的实验装置,在可见波段获得了各种透明字形的成像光谱图。采用对称π变换和快速δ阿达玛变换,改善了实验数据的处理方法。     

The Possible Coupling of LNG Regasification Process with the TSA Method of Oxygen Separation from Atmospheric Air

Liquefied Natural Gas (LNG) must be vaporized before it is used in the combustion process. In most regasification terminals, energy that was previously expended to liquefy natural gas is dissipated in the environment. The paper proposes the use of the thermal effect of LNG regasification for the atmospheric air separation as a possible solution to the LNG exergy recovery problem. The presented idea is based on the coupling of the LNG regasification unit with an oxygen generator based on the Temperature Swing Adsorption (TSA) process. Theoretical analysis has revealed that it is thermodynamically justified to use the LNG enthalpy of vaporization for cooling of the TSA adsorption bed for increasing its adsorptive capacity. It has been shown that 1 kg of LNG carries enough exergy for separating up to approximately 100 g of oxygen using the TSA method. Although the paper suggests using the enthalpy of LNG vaporization for atmospheric air separation, similar processes for other gas mixture separations using the TSA method can be applied.