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61.
Oscillatory interaction between two like‐charged nanoparticles induced by polyelectrolyte brush–solvent interface 下载免费PDF全文
We use two‐dimensional (2D) self‐consistent field theory to study the effective interactions between two like‐charged cylindrical nanoparticles mediated by an oppositely weakly charged polyelectrolyte brush in a solvent solution. In a poor solvent, where a sharp brush–solvent interface forms, an oscillatory interaction is observed when two nanoparticles are both located at the brush–solvent interface. This oscillatory interaction depends on the penetration depths of the particles and their geometric orientations with respect to the substrate. When the particles are both immersed in the brush and/or the particles are oriented vertically or diagonally with large angles to the substrate, the oscillatory behavior disappears. We interpret our findings by analyzing in detail the contributions to the free energy from electrostatic interaction, nonelectrostatic interaction, and entropies, separately. Briefly, the deformations of the interface and the ion layers formed in the vicinity of the interface are responsible for this oscillatory behavior. In a good solvent, where the narrow brush–solvent interface vanishes, the effective particle–particle interactions behave like that for both particles immersed into the brush with poor solvent. They are found to be repulsive. The influences of the particle size, grafting density, and amount of charges and ions are also briefly discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1458–1468 相似文献
62.
Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing 下载免费PDF全文
Judith Wollbrett‐Blitz Sébastien Joannès Rémi Bruant Christophe Le Clerc Marc Romero De La Osa Anthony Bunsell Alba Marcellan 《Journal of Polymer Science.Polymer Physics》2016,54(3):374-384
The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384 相似文献
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Jennifer T. Duong Mark J. Bailey Teresa E. Pick Patrick M. McBride Evelyn L. Rosen Raffaella Buonsanti Delia J. Milliron Brett A. Helms 《Journal of polymer science. Part A, Polymer chemistry》2012,50(18):3719-3727
Water‐dispersible, polymer‐wrapped nanocrystals are highly sought after for use in biology and chemistry, from nanomedicine to catalysis. The hydrophobicity of their native ligand shell, however, is a significant barrier to their aqueous transfer as single particles. Ligand exchange with hydrophilic small molecules or, alternatively, wrapping over native ligands with amphiphilic polymers is widely employed for aqueous transfer; however, purification can be quite cumbersome. We report here a general two‐step method whereby reactive stripping of native ligands is first carried out using trialkyloxonium salts to reveal a bare nanocrystal surface. This is followed by chemically directed immobilization of a hydrophilic polymer coating. Polyacrylic acids, with side‐chain grafts or functional end groups, were found to be extremely versatile in this regard. The resulting polymer‐wrapped nanocrystal dispersions retained much of the compact size of their bare nanocrystal precursors, highlighting the unique role of monomer side‐chain functionality to serve as effective, conformal ligation motifs. As such, they are well poised for applications where tailored chemical functionality at the nanocrystal's periphery or improved access to their surfaces is desirable. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
65.
Abstract This review aims to provide a critical overview of automated flow injection and sequential injection liquid-liquid extraction for preconcentration and/or separation of ultra-trace metal and metalloid species hyphenated with atomic spectrometric detection systems, including some new trends and applications in the subbranches of cloud point extraction (CPE), wetting film extraction (WFE), supported liquid membrane extraction (SLME), extraction chromatography (EChr), and liquid-phase microextraction (LPME) techniques. The analytical performance of flow-injection/sequential injection liquid-liquid extraction methods is markedly affected by the components of the flow network such as segmentor, extraction coil, and phase separator. Thus, an overall presentation of system components along with some novel strategies for interface with atomic spectrometers is discussed and exemplified with selected applications. 相似文献
66.
《Journal of computational chemistry》2017,38(10):659-668
We report an enhanced sampling technique that allows to reach the multi‐nanosecond timescale in quantum mechanics/molecular mechanics molecular dynamics simulations. The proposed technique, called horsetail sampling, is a specific type of multiple molecular dynamics approach exhibiting high parallel efficiency. It couples a main simulation with a large number of shorter trajectories launched on independent processors at periodic time intervals. The technique is applied to study hydrogen peroxide at the water liquid–vapor interface, a system of considerable atmospheric relevance. A total simulation time of a little more than 6 ns has been attained for a total CPU time of 5.1 years representing only about 20 days of wall‐clock time. The discussion of the results highlights the strong influence of the solvation effects at the interface on the structure and the electronic properties of the solute. © 2017 Wiley Periodicals, Inc. 相似文献
67.
《Journal of Polymer Science.Polymer Physics》2018,56(13):999-1011
The aggregation behavior of P3HT is investigated at the interface of orthogonal solvents for P3HT. The changeable characteristics of P3HT aggregate dispersions, for example, extent of aggregation and intrachain order, are studied by varying (1) the interfacial area, (2) the poor solvent used to induce aggregation – dichloromethane (DCM), hexane (HEX), and acetonitrile (AcN) – and (3) the relative composition of the good solvent, chloroform (CF), and poor solvents. The results are compared to those observed using rapid injection of the solvent. Miscibility gap values (Δδ) provide a reasonable justification of the assembly behavior of P3HT in the solvent mixtures in terms of the kinetics of polymer aggregation and the kinetics of solvent mixing at the interface. Atomic force microscopy (AFM) is used to analyze the morphology of films processed from dispersions with disparate characteristics, but having the same solvent composition, for example, 70:30 CF:HEX or 60:40 CF:DCM. Based on the disparity of the kinetics and miscibility gap values, the prevalence of specific structural motifs in the films, for example, spheroids (globules) and fibers, is effectively rationalized in terms of the structural attributes of the aggregates in the liquid phase rather than the evaporation rate (boiling point) differences of the solvents in the mixture. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 999–1011 相似文献
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Over the last years, aqueous two-phase systems (ATPS) regained an increasing interest due to their potential in the downstream processing of biomolecules. After many years with only a few articles published, a lot of effort and work has been put into studying these systems for the partitioning of a range of compounds including proteins, organic low-molecular weight molecules or metal ions. Although several research and review articles appeared, a background review on ATPS partitioning fundamentals is needed. In this article, partitioning theories and main effects of several important factors for partitioning, such as molecular weight of the polymer, effect of added salts, pH, electrical charges, and temperature on phase diagrams, tie-line lengths, interfacial tension and settling time of the two aqueous phases are extensively reviewed. The trend in ATPS research is given compiling the recent 2008–2013 research articles published in the field. 相似文献
70.
《Journal of Polymer Science.Polymer Physics》2018,56(5):402-413
Surface welding effect of covalent adaptable network (CAN) polymers enables self‐healing, reprocessing and recycling of thermosets, but little is known about their welding behaviors during repeated welding‐peeling cycles. In this article, we study the cyclic welding effect of an epoxy based thermal‐sensitive CAN. Surface roughness is generated by rubbing the sample on sandpapers with different grid sizes. The welding‐peeling cycles are repeated on the same pair of samples for five times, with roughness amplitude and interfacial fracture energy measured in each cycle. It is shown that the roughness gradually decreases during the repeated welding cycles, especially when a long welding time or high welding pressure is applied. Even though lower roughness amplitude promotes the contact area, the interfacial fracture energy reduces due to the increased BER activation energy after long‐time heating. A multiscale constitutive model is adopted, where we incorporate an explicit expression of interfacial contact area as a function of root‐mean‐square roughness parameter. The model is able to capture the evolving interfacial fracture energy during repeated welding cycles by using the measured roughness parameter, network modulus and BER activation energy. The study provides theoretical basis for the design and applications of CANs involving cyclic welding‐peeling operations. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 402–413. 相似文献