Immersion of oxidized aluminum substrates in ethanol solutions of poly(acrylic acid) (PAA), followed by extensive solvent immersion, results in tenaciously chemisorbed, nanometer scale, controllable thickness films for a wide range of solution concentrations and molecular weights. Atomic force microscope images reveal isolated polymer globules from adsorption in low-concentration solutions with crossover to conformal, highly uniform, nanometer-thickness films at higher concentrations, an indication that the chemisorbing chains start to overlap and trap underlying segments to form planar chemisorbed films only two or three chains in thickness. Quantitative IR reflection spectroscopy in combination with chemical derivitization on a standard set of 1.0(±0.2) nm thick films reveals a film structure with 5.5(±1) chemisorbed -CO(-)(2) groups/nm(2) and 6.3 unattached -CO(2)H groups/nm(2), with up to ~3.6/nm(2) available for chemical derivitization, a comparable number to typical self-assembled monolayer coverages of ~4-5 molecules/nm(2). Thermal treatment of the ~1 nm chemisorbed films, at even extreme temperatures of ~150 °C, results in almost no anhydride formation via adjacent -CO(2)H condensation, in strong contrast to bulk PAA, a clear indication that the films have a frozen glass structure with effectively no segment and side group mobility. Overall, these results demonstrate that these limiting thickness nanometer films provide a model surface for understanding the behavior of strongly bound polymer chains at substrates and show potential as a path to creating highly stable, chemically functionalized inorganic substrates with highly variable surface properties. 相似文献
The joint-scalar probability density function (PDF) approach provides a comprehensive framework for large eddy simulation (LES) based combustion modeling. However, currently available stochastic approaches for solving the high-dimensional PDF transport equation can be error prone and numerically unstable in highly compressible shock-containing flows. In this work, a novel Eulerian approach called the direct quadrature method of moments (DQMOM) is developed for evolving the PDF-based supersonic combustion model. The DQMOM technique uses a set of scalar transport equations with specific source terms to recover the PDF. The new technique is coupled to a compressible LES solver through the energy equation. The DQMOM approach is then used to simulate two practical flow configurations: a supersonic reacting jet and a cavity-stabilized supersonic combustor. Comparisons with experimental data demonstrate the predictive accuracy of the method. 相似文献
We describe a robust method for both encapsulating and stabilizing photo‐sensitive antioxidants in polymer microcapsules prepared by a water‐in‐oil‐in‐water double emulsification and evaporation technique, in which a volatile solvent from the oil layer consisting of poly(methyl methacrylate) and methylene chloride is gradually removed. Using poly(ethylene glycol) (PEG) in this study, we demonstrate that control over its molecular weight allows to tune the phase property of the capsule wall; introducing PEG with high molecular weight results in increased heterogeneity. The heterogeneity of the capsule walls displays an ability to effectively block sunlight, which is essential for improving the molecular stability of photo‐sensitive antioxidants. In this study, we experimentally confirm this by observing natural sunlight‐driven molecular decomposition of a model antioxidant, riboflavin‐5′‐phosphate, in poly (methyl methacrylate) microcapsules.
An exchange of hydrogen-bond and coordinate covalent-bond (dative-bond) interactions is found to play a critical role in the self-assembly of NH3 molecules on the Si(001) surface. An NH3 molecule in the height of approximately 3-10 A above the surface is attracted toward the preadsorbed NH2 moiety through the long-range H-bond interaction. Within approximately 3 A, the H-bond interaction becomes repulsive, and instead the dative bond with the buckled-down Si atom governs the adsorption process. The interplay of the two interactions induces the clustering and the zigzag feature of the dissociatively adsorbed NH3 molecules on the Si(001) surface. 相似文献