The volume transition in thermosensitive colloidal core–shell particles is investigated by small-angle x-ray scattering (SAXS), small-angle Neutron scattering (SANS), and dynamic light scattering (DLS). The latex particles are dispersed in water and consist of a solid poly(styrene) core with a diameter of 100 nm. The thermosensitive shell is made up of poly(N-isopropylacrylamide) (PNIPA) chains crosslinked by 2.5 mol % N,N’-methylenbisacrylamide (BIS). Water is a good solvent for PNIPA at room temperature but becomes a poor solvent above 32 °C. The PNIPA network of the shell undergoes a volume transition at this temperature. As a result the diameter of the particle shrinks. The scattering intensities of the particles measured by SAXS and SANS as a function of temperature may be decomposed into a part deriving from the overall structure and a part originating from the fluctuations within the network. The analysis of the overall structure leads to the volume fraction of the swollen network at different temperatures. SANS in conjunction with contrast variation demonstrates that the network is confined in a well-defined shell. SAXS and SANS data therefore allow the phase diagram of the network in the shell of the particles to be derived, i.e., the average volume fraction of the network in the shell can be determined as a function of temperature. DLS corroborates this result but demonstrates that there is a small fraction of chains exceeding the outer radius derived from SAXS and SANS. The static intensity caused by the fluctuations of the network becomes the leading contribution at high scattering angles. SAXS data show that this part can be described by a Lorentzian both below and above the volume transition. The analysis demonstrates that critical fluctuations of the network around the transition temperature are fully suppressed. This finding is explained by the strong steric constraint of the network by its confinement within a shell of colloidal dimension. The swelling and shrinking can only take place along the radial direction and the chains are bound to the solid surface of the cores which remains constant during the transition.

We present an investigation of thermosensitive coreÈshell particles by small-angle neutron scattering (SANS). The particles consist of a solid poly(styrene) core and a shell of crosslinked poly(N-isopropylacrylamide) (PNIPA) chains. These latex particles are dispersed in water and have a diameter of ca. 150 nm. At ambient temperature the PNIPA-network in the shell is swollen but at higher temperature water is expelled and the shell undergoes a continuous volume transition. The radial extension of the shell is investigated as a function of temperature by use of SANS. The analysis by SANS is performed at di †erent contrasts using appropriate mixtures of and It demonstrates that the shell has a well-deÐned compact structure above theO. volume transition. The swelling of the shell upon cooling can be described in terms of an affine expansion of the network. This is followed by a slight decrease of the volume fraction with increasing distance to the surface of the cores. The analysis by SANS demonstrates that the phase behavior of the network in the shell may be undertaken in terms of average volume fractions. It thus supplements the previous analysis by SAXS in a decisive manner.

The flow properties of aqueous suspensions of thermosensitive latex particles are investigated as a function of volume fraction and temperature. The particles consist of a solid poly͑styrene͒ core and a shell composed of crosslinked poly͑N-isopropylacrylamide͒ ͑PNIPA͒ chains. The PNIPA network shrinks with increasing temperature leading to a denser layer of polymeric chains on the surface of the core particles. The shear viscosity obtained from suspensions of these particles at low shear is compared to the viscosity measured in the high-frequency limit. In the limit of dilute suspensions the viscosity is modeled in terms of an effective hydrodynamic radius R H. It is shown that R H of highly swollen particles depends markedly on frequency. The data indicate that the swollen network on the surface of the particles is partially drained at high frequencies. For shrunken networks R H measured in the low and high frequency limit coincides again. The high frequency shear modulus G ϱ Ј measured at high volume fractions demonstrates that the thermosensitive particles may be regarded as soft spheres. The repulsive interaction may be modeled in terms of a power law with an exponent of 9.

We discuss the analysis of the volume transition in thermosensitive colloidal core‐shell particles by synchrotron small‐angle X‐ray scattering. The latex‐particles are dispersed in water and consist of a solid poly(styrene) core (diameter: 107 nm) and a shell of a thermosensitive crosslinked polymer chains. The thermosensitive shell is built up from poly(N‐isopropylacrylamide) chains (PNIPA) crosslinked by N,N'‐methylenbisacrylamide (BIS). The scattering intensities measured as function of temperature may be decomposed into a part deriving from the overall structure and a part originating from the fluctuations within the network. The analysis of the overall structure leads to the volume fraction of the swollen network at different temperatures. The intensity caused by the fluctuations of the network becomes the leading contribution at high scattering angles. It may be described by a Lorentzian below and above the volume transition. The analysis demonstrates that critical fluctuations of the network around the transition temperature are fully suppressed. This finding is explained by the strong steric constraint of the network by its confinement within a shell of colloidal dimensions: i) The swelling and shrinking can only take place along the radial direction, and ii) the chains are bound to the solid surface of the cores which remains constant during the transition.

Summary:We present a survey over recent studies of the volume transition in colloidal core-shell particles composed of a solid poly(styrene) core and a shell of a thermosensitive crosslinked polymer chains. The thermosensitive shell is built up from poly(N-isopropylacrylamide) chains (PNIPA) crosslinked by N,N'-methylenbisacrylamide (BIS). In addition, particles containing acrylic acid (AA) as comonomer have been synthesized and investigated. The volume transition of these particles have been studied by dynamic light scattering (DLS) and by small-angle Xray scattering ( S A X S ) . In all cases analyzed so far the volume transition was found to be continuous. This finding shows that the core-shell microgels behave in a distinctively different manner than ordinary thermosensitive gels: The crosslinked chains in the shell are bound to a solid boundary independent of temperature. The spatial constraint by this boundary decreases the maximum degree of swelling but also prevents a full collapse of the network above the volume transition.