77 research outputs found
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
Anomalous small-angle X-ray scattering: analyzing correlations and fluctuations in polyelectrolytes
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
Observation of the Volume Transition in Thermosensitive Core−Shell Latex Particles by Small-Angle X-ray Scattering
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