Accessing the free expansion of a crystalline colloidal drop by optical experiments.

We study poly-crystalline spherical drops of an aqueous suspension of highly charged colloidal spheres exposed to a colloid-free aqueous environment. Crystal contours were obtained from standard optical imaging. The crystal spheres first expand to nearly four times their initial volume before slowly shrinking due to dilution-induced melting. Exploiting coherent multiple-scattering by (110) Bragg reflecting crystals, time-dependent density profiles were recorded within the drop interior. These show a continuously flattening radial density gradient and a decreasing central density. Expansion curves and density profiles are qualitatively consistent with theoretical expectations based on dynamical density functional theory for the expansion of a spherical crystallite made of charged Brownian spheres. We anticipate that our study opens novel experimental access to density determination in turbid crystals.

Magnetic response of CoFe2O4 nanoparticles confined in a PNIPAM microgel network.

The paper addresses coupling of magnetic nanoparticles (MNPs) with the polymer matrix of temperature-sensitive microgels and their response to magnetic fields. Therefore, CoFe2O4@CA (CA = citric acid) NPs are embedded within N-isopropylacrylamid (NIPAM) based microgels. The volume phase transition (VPT) of the magnetic microgels and the respective pure microgels is studied by dynamic light scattering and electrophoretic mobility measurements. The interaction between MNPs and microgel network is studied via magnetometry and AC-susceptometry using a superconducting quantum interference device (SQUID). The data show a significant change of the magnetic properties by crossing the VPT temperature (VPTT). The change is related to the increased confinement of the MNP due to the shrinking of the microgels. Modifying the microgel with hydrophobic allyl mercaptan (AM) affects the swelling ability and the magnetic response, i.e. the coupling of MNPs with the polymer matrix. Modeling the AC-susceptibility data results in an effective size distribution. This distribution represents the varying degree of constraint in MNP rotation and motion by the microgel network. These findings help to understand the interaction between MNPs and the microgel matrix to design multi responsive systems with tunable particle matrix coupling strength for future applications.

Inner structure and dynamics of microgels with low and medium crosslinker content prepared via surfactant-free precipitation polymerization and continuous monomer feeding approach.

The preparation of poly(N-isopropylacrylamide) microgels via classical precipitation polymerization (batch method) and a continuous monomer feeding approach (feeding method) leads to different internal crosslinker distributions, i.e., from core-shell-like to a more homogeneous one. The internal structure and dynamics of these microgels with low and medium crosslinker concentrations are studied with dynamic light scattering and small-angle neutron scattering in a wide q-range below and above the volume phase transition temperature. The influence of the preparation method, and crosslinker and initiator concentration on the internal structure of the microgels is investigated. In contrast to the classical conception where polymer microgels possess a core-shell structure with the averaged internal polymer density distribution within the core part, a detailed view of the internal inhomogeneities of the PNIPAM microgels and the presence of internal domains even above the volume phase transition temperature, when polymer microgels are in the deswollen state, are presented. The correlation between initiator concentration and the size of internal domains that appear inside the microgel with temperature increase is demonstrated. Moreover, the influence of internal inhomogeneities on the dynamics of the batch- and feeding-microgels studied with neutron spin-echo spectroscopy is reported.

Bridging the gap between two different scaling laws for structuring of liquids under geometrical confinement.

Structural forces are a phenomena obtained in liquids of one-component (e.g. for organic solvents) and two-components (colloidal dispersions), alike. So far, those two systems were discussed separately, using two different scaling laws. In this review article, an attempt is made to bridge the gap between both scaling laws by defining the scaling limit for two-component systems. Colloidal probe atomic force microscopy (CP-AFM) is used to measure structural forces in suspensions of silica nanoparticles (NPs) of three different sizes. In these two-component systems (solid NPs suspended in water), oscillatory behaviour can be obtained in the force vs. separation profiles. The wavelength λ is larger than the actual particle diameter d and rather depends on the particles' volume fraction ϕ following the inverse cubic root law λ∝ϕ-13. It is shown that the real particle diameter d can be determined by a gedankenexperiment by extrapolating the fitted wavelength λ from the structural force measurements at a specific particle concentration to a particle volume fraction ϕ of 52% - the packing factor for simple cubic packing - using the well-known inverse cubic root scaling law. This extrapolation can be interpreted as a transition from a two-component system towards a one-component-like problem. In this case, particles are in contact and the wavelength λ is equal to the particle diameter d, λ = d as for one-component systems. The determined diameters d of the different silica nanoparticles agree well with independent measurements using transmission electron microscopy (TEM), validating the used approach. The proposed method can be extended to numerous dispersions of spherical nano-sized objects, for which structural forces can be measured.

Distribution of CoFe2O4 Nanoparticles Inside PNIPAM-Based Microgels of Different Cross-linker Distributions.

The aim of this study is to tailor the inner structure of positively charged poly-( N-isopropylacrylamid- co-allylamine) (P(NIPAM- co-AA)) microgels for a better control of the distribution of negatively charged magnetic cobaltferrite (CoFe2O4@CA) nanoparticles (MNPs) within the microgels. Therefore, two different strategies are followed for the microgel synthesis: the (one pot) batch method which leads to a higher cross-linker density in the microgel core and the feeding method which compensates different reaction kinetics of the cross-linker and the monomers. The latter one is expected to result in a homogeneous cross-linker distribution. Information about the cross-linker distribution is indirectly gained by measuring the elastic modulus via indentation experiments with an atomic force microscope. While the batch method results in a higher elastic modulus in the center of the microgel indicating a core/shell structure, the feeding method leads to a constant elastic modulus over the whole microgel. The loading with MNPs and their distribution are studied with transmission electron microscopy (TEM). The TEM images show a large difference in the MNP distribution which is correlated to the cross-linker distribution of both types of microgels. The batch method microgel has a low MNP concentration in the core. The feeding method microgel shows a much more homogeneous distribution of MNPs across the microgel. The latter one also shows a stronger charge reversal which is a hint for a higher loading of the feeding method microgel. Dynamic light scattering and electrophoretic mobility measurements demonstrate that for both types of microgels, the temperature sensitivity is preserved after loading with MNPs.

A comparison of the network structure and inner dynamics of homogeneously and heterogeneously crosslinked PNIPAM microgels with high crosslinker content.

Poly(N-isopropylacrylamide) microgel particles were prepared via a "classical" surfactant-free precipitation polymerization and a continuous monomer feeding approach. It is anticipated that this yields microgel particles with different internal structures, namely a dense core with a fluffy shell for the classical approach and a more even crosslink distribution in the case of the continuous monomer feeding approach. A thorough structural investigation of the resulting microgels with dynamic light scattering, atomic force microscopy and small angle neutron scattering was conducted and related to neutron spin echo spectroscopy data. In this way a link between structural and dynamic features of the internal polymer network was made.

Combined Cononsolvency and Temperature Effects on Adsorbed PNIPAM Microgels.

The present study addresses the multiresponsive behavior of poly(N-isopropylacrylamide) (PNIPAM) microgels adsorbed to interfaces. The microgels react to changes in temperature by shrinking in aqueous solution above their volume phase transition temperature (VPTT). Additionally, they shrink in mixtures of water and ethanol, although both individual liquids are good solvents for PNIPAM. The combination of this so-called cononsolvency effect and the temperature response of adsorbed microgels is studied by atomic force microscopy (AFM). Adsorbed microgels are of special interest because they are compressed considerably compared to those in bulk solution. It is shown that the impact of adsorption on swelling depends on the specific surface details, as well as the sample preparation. Thereby, the microgels are deposited on two different kinds of surfaces: on gold surface and on polycation (PAH) coating which show different interactions with the microgels in terms of electrostatic interaction and wettability. In addition, the microgels were deposited from different solvent mixtures. This influences the microgel structure and thereby the swelling properties. Nanorheology studies by dynamic AFM measurements lead to surprising results which are explained by the fact that not only polymer density but a subtle interaction between polymer and solvent might dominate the rheological properties. This work supports the view that preferential adsorption of ethanol at PNIPAM drives cononsolvency, while the shrinking at T > VPTT is caused by general breaking of hydrogen bonds between solvents and PNIPAM.

Poly(N-isopropylacrylamide) Microgels under Alcoholic Intoxication: When a LCST Polymer Shows Swelling with Increasing Temperature.

Poly(N-isopropylacrylamide) (PNIPAM) microgel is a smart polymer that shows a volume phase transition temperature (VPTT) at around 32 °C in aqueous solutions, above which it collapses. In this work, combining experiments and molecular simulations, it is shown that PNIPAM microgels do not always exhibit a collapsed structure above the VPTT. Instead, PNIPAM in aqueous alcohol mixtures shows a two-step conformational transition, i.e., a collapse at low temperatures (T < 32 °C) and a reswelling when T > 50 °C. The present analysis indicates that delicate microscopic interaction details, together with the bulk solution properties, play a key role in dictating the reswelling behavior. Even when PNIPAM microgels swell with increasing T, this is not a standard upper critical solution behavior.

Loading of PNIPAM Based Microgels with CoFe2O4 Nanoparticles and Their Magnetic Response in Bulk and at Surfaces.

The present paper addresses the loading of thermoresponsive poly-N-isopropylacrylamide (PNIPAM) based microgel particles with magnetic nanoparticles (MNP: CoFe2O4@PAA (PAA = poly(acrylic acid))) and their response to an external magnetic field. The MNP uptake is analyzed by transmission electron microscopy (TEM). Obviously, the charge combination of MNP and microgels plays an important role for the MNP uptake, but it does not explain the whole uptake process. The MNP uptake results in changes of size and electrophoretic mobility, which is investigated by dynamic light scattering (DLS) and a Zetasizer. The microgels loaded with MNP preserve their thermosensitivity, and they show magnetic separability and are considered as magnetic microgels. After adsorption at a surface the magnetic microgels are studied with a scanning force microscope and indentation experiments. The magnetic microgels show an elongation along the magnetic field parallel to the surface while the height of the microgels (perpendicular to the surface and to the magnetic field) is compressed. This result is in good agreement with simulations of volume change of ferrogels in a magnetic field.