Modeling of Intermediate Structures and Chain Conformation in Silica-Latex Nanocomposites Observed by SANS During Annealing

The evolution of the polymer structure during nanocomposite formation and annealing of silica-latex nanocomposites is studied using contrast-variation small angle neutron scattering. The experimental system is made of silica nanoparticles (Rsi \approx 8 nm) and a mixture of purpose-synthesized hydrogenated and deuterated nanolatex (Rlatex \approx 12.5 nm). The progressive disappearance of the latex beads by chain interdiffusion and release in the nanocomposites is analyzed quantitatively with a model for the scattered intensity of hairy latex beads and an RPA description of the free chains. In silica-free matrices and nanocomposites of low silica content (7%v), the annealing procedure over weeks at up to Tg + 85 K results in a molecular dispersion of chains, the radius of gyration of which is reported. At higher silica content (20%v), chain interdiffusion seems to be slowed down on time-scales of weeks, reaching a molecular dispersion only at the strongest annealing. Chain radii of gyration are found to be unaffected by the presence of the silica filler

Coupling of Rotational Motion with Shape Fluctuations of Core-shell Microgels Having Tunable Softness

The influence of shape fluctuations on deformable thermosensitive microgels in aqueous solution is investigated by dynamic light scattering (DLS) and depolarized dynamic light scattering (DDLS). The systems under study consist of a solid core of polystyrene and a thermosensitive shell of cross-linked poly(N-isopropylacrylamide) (PNIPA) without and with embedded palladium nanoparticles. PNIPA is soluble in water, but has a lower critical solution temperature at 32 C (LCST). Below the LCST the PNIPA shell is swollen. Here we find that besides translational and rotational diffusion, the particles exhibit additional dynamics resulting from shape fluctuations. This leads to a pronounced apparent increase of the rotational diffusion coefficient. Above the transition temperature the shell collapses and provides a rather tight envelope of the core. In this state the dynamics of the shell is frozen and the core-shell particles behave like hard spheres. A simple physical model is presented to capture and explain the essentials of the coupling of rotational motion and shape fluctuations.Comment: 9 pages, 7 figure

Use of anomalous small-angle X-ray scattering for the investigation of highly charged colloids

We present a study of the radial structure of a spherical polyelectrolyte brushes by anomalous small-angle X-ray scattering. The spherical polyelectrolyte brushes consist of a solid poly( styrene) core of ca : 100 nm diameter onto which long linear chains of poly( acrylic acid) (PAA) are densely grafted. A sufficiently high pH, these polyelectrolyte chains are fully charged. Rubidium ions are used as counterions because their adsorption edge (15 199.6 eV) can be conventiently reached by synchrotron radiation. By performing small-angle X-ray scattering studies at different energies of the incident radiation, the contribution of the Rb+ counterions can be analyzed separately. The scattering contribution of the counterions can be derived and compared to the scattering intensity of the entire particle. The distributions of the macro-ion and of the counterions are shown to be very similiar. This shows that the counterions must be confined within the brush

Microstructure formation in dip-coated particulate films

The microstructure-dependence of dip-coated particulate thin films on the stability of an aqueous silica sol used as coating bath is studied. Different stability conditions are adjusted in the sol by changing electrolyte concentration and pH value. Care was taken to avoid pronounced aggregation of the particles before the coating process. The characterization of the stability behavior gives clear evidence of a non-DLVO contribution at low pH values that is attributed to hydration forces. Structural evolution of the particulate network during film formation is studied using a dialysis accumulation procedure. The viscosity of the accumulated sol is measured as a function of shear rate and related to the drying characteristic of the coating process. Atomic force microscopy (AFM), small-angle X-ray scattering (SAXS) and N2 sorption are used to obtain information on the surface and volume structure of the dip-coated films. The structure of coatings is found to distinctly vary with stability parameters. This is attributed to changing interactions during the first drying stage. Finally, the influence of coating structures on the light transmission properties is determined. A comparison between the extinction of the uncoated and the coated substrate revealed a difference of up to +/-50% in dependence on the microstructure