ABSTRACT
Understanding phenomena such as evaporation and imbibition of picoliter droplets into porous substrates is crucial in printing industry to achieve a higher printing quality and print speed. After printing, the residual pigment must remain fixed at the desired location on a substrate and be of a desired volume to yield a high resolution and vibrantly printed page that has become the expectation of modern printing technology. Current research entails not only chemical composition of the ink but also how this links to the dynamics and interactions that occur between the ink and the substrate at every stage of the printed spot formation, including evaporation, wetting, and imbibition. In this paper, we present an instrument that can print on-demand picoliter volume droplets of ink onto substrates and then immediately record on evolution of the resulting dynamics when these two materials interact. This high-speed laser speckle imaging (HS-LSI) technique has been developed to monitor nanometer displacement of the drying and imbibing ink droplet at a high frame rate, up to 20000 Hz, given the short timescales of these interactions. We present the design of the instrument, discuss the related challenges and the theory underlying the LSI technique, specifically how photons non-evasively probe opaque objects in a multiple scattering regime, and show how this technique can unravel the dynamics of drying and imbibition. We will finish giving a validation on the instrument and an example of its usage.
ABSTRACT
We present the development of a multi-position indentation setup capable of spatially mapping mechanically heterogeneous materials. A detailed description of the indentation instrumentation is first provided, emphasizing force sensitivity, noise reduction, and signal fidelity. We first present indentation experiments on soft hydrogels that are submerged in water and show how the large contributions to the measured force due to the air-water surface tension can be avoided. The displacement field of the indented hydrogel is visualized using fluorescently coated microspheres embedded in the hydrogel, allowing simultaneous mapping of the stress and strain fields for a soft polymer network. We then fabricate a polymer network with patterned elasticity using halftone UV lithography and map the elastic modulus with the multi-position indentation instrument. The applied UV pattern is found back in the measured elastic modulus map, showing the capability of the multi-position indentation setup to map mechanically heterogeneous polymer networks.
ABSTRACT
The assembly of oppositely charged block copolymers, containing small thermoresponsive moieties, was investigated as a function of salt concentration and temperature. Aqueous solutions of poly-[N-isopropylacrylamide]-b-poly[dimethylaminoethyl methacrylate] (NIPAM44-b-DMAEMA216) and PNIPAM-b-poly[acrylic acid]-b-PNIPAM (NIPAM35-b-AA200-b-NIPAM35) were mixed in equal charge stoichiometry, and analysed by light scattering (LS), NMR spectroscopy and small angle X-ray scattering (SAXS). At room temperature, two different micelle morphologies were found at different salt concentrations. At NaCl concentrations below 0.75 M, complex coacervate core micelles (C3M) with a PNIPAM corona were formed as a result of interpolyelectrolyte complexation. At NaCl concentrations exceeding 0.75 M, the C3M micelles inverted into PNIPAM cored micelles (PCM), containing a water soluble polyelectrolyte corona. This behavior is ascribed to the salt concentration dependence of both the lower critical solution temperature (LCST) of PNIPAM, and the complex coacervation. Above 0.75 M NaCl, the PNIPAM blocks are insoluble in water at room temperature, while complexation between the polyelectrolytes is prevented because of charge screening by the salt. Upon increasing the temperature, both types of micelles display a cloud point temperature (T cp), despite the small thermoresponsive blocks, and aggregate into hydrogels. These hydrogels consist of a complexed polyelectrolyte matrix with microphase separated PNIPAM domains. Controlling the morphology and aggregation of temperature sensitive polyelectrolytes can be an important tool for drug delivery systems, or the application and hardening of underwater glues.
ABSTRACT
We study a one-parameter family of quadratic maps, which serves as a template for interior point methods. It is known that such methods can exhibit chaotic behavior, but this has been verified only for particular linear optimization problems. Our results indicate that this chaotic behavior is generic.
ABSTRACT
Light scattering and small-angle neutron scattering experiments were performed on comicelles of several combinations of oppositely charged (block co)polymers in aqueous solutions. Fundamental differences between the internal structure of this novel type of micelle --termed complex coacervate core micelle (C3Ms), polyion complex (PIC) micelle, block ionomer complex (BIC), or interpolyelectrolyte complex (IPEC)-- and its traditional counterpart, i.e., a micelle formed via self-assembly of polymeric amphiphiles, give rise to differences in scaling behaviour. Indeed, the observed dependencies of micellar size and aggregation number on corona block length, N (corona) , are inconsistent with scaling predictions developed for polymeric micelles in the star-like and crew-cut regime. Generic C3M characteristics, such as the relatively high core solvent fraction, the low core-corona interfacial tension, and the high solubility of the coronal chains, are causing the deviations. A recently proposed scaling theory for the cross-over regime, as well as a primitive first-order self-consistent field (SCF) theory for obligatory co-assembly, follow our data more closely.
ABSTRACT
We investigated the thinning of wetting films formed from aqueous solution of non-ionic triblock copolymer Pluronic F127 on the surface of silica using a home-made thin film balance and time-resolved ellipsometry. Imaging ellipsometry was used to visualize the film structures at subsequent stages of their development. The results unambiguously show that the time required for the formation of steady films strongly depends on the electrolyte concentration. When increasing the latter from 10(-4) to 0.1 M, this time typically increases with several orders of magnitude, from a few minutes to several hours. Moreover, for sufficiently large amounts of salt, two characteristic relaxation regimes can be clearly identified. After initial quick thinning, further thinning slows down enormously. These typical kinetic regimes are thought to result from the coupled dependencies of the bulk and interfacial properties of F127 on salt concentration. Possible explanations of the phenomenon are discussed.
