Molecular versus macroscopic perspective on the demixing transition of aqueous PNIPAM solutions by studying the dual character of the refractive index

in Soft Matter (2014), 10(37), 7297-7305

The phase separation of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions is known to strongly affect their volume expansion behaviour and the elastic moduli, as the latter are strongly coupled to ... [more ▼]

The phase separation of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions is known to strongly affect their volume expansion behaviour and the elastic moduli, as the latter are strongly coupled to the macroscopic order parameter. On the molecular scale, considerable changes in H-bonding and hydrophobic interactions, as well as in the structure govern the demixing process. However, the relationship between the molecular and macroscopic order parameters is unclear for such complex phase-separating solutions. We contribute to the clarification of this problem by relating optical to volumetric properties across the demixing transition of dilute to concentrated aqueous PNIPAM solutions. Far from the demixing temperature, the temperature dependence of the refractive index is predominantly determined by thermal expansion. In the course of phase separation, the refractive index is dominated by the anomalous behaviour of the specific refractivity, which reflects the spatio-temporally averaged changes in molecular interactions and the structural reorganization of the demixing solutions. Moreover, the presence of relaxation processes is studied by the complex expansion coefficient using the novel technique of temperature modulated optical refractometry. [less ▲]

Kinetic processes at the demixing transition of PNIPAM solutions

in Soft Matter (2013), 9

Kinetic processes, which are joined with mass transport, are studied in the vicinity of the sharp LCST-type demixing transition of semi-dilute aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions ... [more ▼]

Kinetic processes, which are joined with mass transport, are studied in the vicinity of the sharp LCST-type demixing transition of semi-dilute aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions. These processes are slow as compared to the highly cooperative collapse of individual polymer chains. Purely elastic properties, that are particularly sensitive to this phase transition, are addressed depending on the temperature, space and time by Brillouin spectroscopy. Above the demixing temperature Tc, we discriminate between kinetics related to the phase separation into PNIPAM-rich and PNIPAM-poor domains and kinetics connected to the impact of gravitation on the on-going phase separation. Using shallow temperature jumps of 0.3 C, the growth of compact PNIPAM-rich agglomerates with identical gel-like mechanical consistency is provoked independently of temperature and position within the sample above Tc. Astonishingly, the transition temperature does not vary while heating or cooling the solutions across the phase transition, although the elastic properties depend strongly on space and time during the equilibration of PNIPAM concentration gradients following the re-entrance into the lowtemperature phase. [less ▲]

Immense elastic nonlinearities at the demixing transition of aqueous PNIPAM solutions

in Soft Matter (2013), 9

Elastic nonlinearities are particularly relevant for soft materials because of their inherently small linear elasticity. Nonlinear elastic properties may even take over the leading role for the ... [more ▼]

Elastic nonlinearities are particularly relevant for soft materials because of their inherently small linear elasticity. Nonlinear elastic properties may even take over the leading role for the transformation at mechanical instabilities accompanying many phase transitions in soft matter. Because of inherent experimental difficulties, only little is known about third order (nonlinear) elastic constants within liquids, gels and polymers. Here we show that a key concept to access third order elasticity in soft materials is the determination of mode Gr¨uneisen parameters. We report the first direct observation of third order elastic constants across mechanical instabilities accompanying the liquid–liquid demixing transition of semi-dilute aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions. Immense elastic nonlinearities, leading to a strong strain-softening in the phase-separating PNIPAM solutions, are observed. Molecular mechanisms, which may be responsible for these immense elastic nonlinearities, are discussed. The importance of third order elastic constants in comparison to second order (linear) elastic constants in the demixing PNIPAM solutions evidences the need to focus more on the general role played by nonlinear elasticity at phase transitions within synthetic and biological liquids and gels. [less ▲]

Competition Between Chemical Network Formation and Physical Adsorption and Desorption Processes in a Silica-Filled Silicone Rubber: Calorimetry versus Refractometry Studies

in Journal of Adhesion (2012), 88(7), 649-663

Calorimetry and high-performance refractometry are applied to study the network formation and accompanying morphological changes in reactive polydimethylsiloxane systems filled with silica nanoparticles ... [more ▼]

Calorimetry and high-performance refractometry are applied to study the network formation and accompanying morphological changes in reactive polydimethylsiloxane systems filled with silica nanoparticles. Both methods give insight into the structure formation during the polymerization of silica-filled silicone nanocomposites in an impressively complementary way. It will be shown that the specific heat flow as determined by calorimetry does not allow for estimating the chemical conversion whereas the refractive index does, which results from the different perspectives of both techniques on the relevant polymerization, adsorption, and desorption processes occurring in the nanocomposites. Finally, the interphase formation in the polymeric matrix in the vicinity of the nanoparticles and the network formation within the silicone rubber are demonstrated to be strongly correlated processes. [less ▲]

Scanning Brillouin Microscopy: Acoustic Microscopy at Gigahertz Frequencies

in Archives des Sciences Naturelles, Physiques et Mathématiques (2012), NS 46(Special volume (invited Review Article)),

Structural properties of poly(N-isopropyl acrylamide)-based systems

Poster (2011, October 10)

Structural properties of poly(N-isopropyl acrylamide)-based systems

Poster (2011, June 01)

On the interplay between matter transport and structure formation at epoxy-hardener interfaces visualized by scanning Brillouin microscopy

in Soft Matter (2011), 7(1), 118-124

Structural developments are investigated in network-forming reactive polymers by time- and 10 space-resolved scanning Brillouin microscopy. Hypersonic properties are probed to reveal the subtle interplay ... [more ▼]

Structural developments are investigated in network-forming reactive polymers by time- and 10 space-resolved scanning Brillouin microscopy. Hypersonic properties are probed to reveal the subtle interplay between molecular transport, dissolution, polymerization and network defects in the vicinity of the interface between reactants, which are either pure epoxy resin or various epoxy resin-hardener mixtures, topped by a layer of pure hardener. The trans-interfacial polymerization produces heterogeneous epoxy structures of either gelatinous or glassy nature. Interestingly, the 15 hardener can easily penetrate and swell these networks and epoxy network fragments can be transported over several millimeters by convective flow. The observed features may be used to form interpenetrating networks during self-healing procedures. [less ▲]

Trans-Interfacial Polymerization and Matter Transport Processes in Epoxy-Alumina Nanocomposites Visualized By Scanning Brillouin Microscopy

in Journal of Physical Chemistry B (2010), 114(25), 8396-8404

The structural developments in the vicinity of the interface between the reactants of an epoxy are investigated using time- and space-resolved scanning Brillouin microscopy. The hypersonic profile across ... [more ▼]

The structural developments in the vicinity of the interface between the reactants of an epoxy are investigated using time- and space-resolved scanning Brillouin microscopy. The hypersonic profile across the phase boundary evolves with strong spatial asymmetry and exhibits erratic behavior within the resin-rich region, which is attributed to a complex interplay between matter transport, dissolution, polymerization, and molecular unravelling process. The presence of alumina nanoparticles in the resin changes the character of these matter transport and reaction processes significantly. On the one hand, the nanoparticles act as transport barriers, hindering the mixing of the reactive components; on the other hand they seem to have a catalytic influence on the epoxy polymerization under certain circumstances. Their transport against gravity is tentatively attributed to gradients in surface tension. [less ▲]

Nichtgleichgewichtsphänomene, Strukturbildung und Grenzflächeneinflüsse in netzwerkbildenden Systemen aus optischer und akustischer Sicht.

Doctoral thesis (2009)

Isostructural phase transitions occurring under non-equilibrium conditions are investigated using technologically relevant epoxies. The evolution of the hypersonic and optical properties during the ... [more ▼]

Isostructural phase transitions occurring under non-equilibrium conditions are investigated using technologically relevant epoxies. The evolution of the hypersonic and optical properties during the genesis of the polymeric network leads to deeper insight into the chemically induced sol-gel transition and glass transition, as demonstrated e.g. by the elastic anharmonicity and the generalised Cauchy relation. During gelation the refractive index versus chemical conversion behaves in an unexpected manner, indicating that in addition to the mass density an excess polarisability seems to contribute to the optical polarisability. The clarification of the isostructural phase transitions is impeded by the demixing tendency of the epoxy components which leads to different types of epoxy inhomogeneities on the nano- to mesoscopic scale. Taking benefit from a sample arrangement where both epoxy components are layered, the spatio-temporal evolution of acoustic properties gives supplementary information about trans-interfacial transport and structure formation processes. Of special technological relevance, but also of fundamental interest, is the influence of nanoscopic disturbances placed into the epoxy matrix. So-called interphases surrounding the nanoparticles modify and complicate the epoxy network formation, leading to long-lived metastable morphologies and properties. The role of the mixing sequence of the epoxy resin, the hardener and the nanoparticles for the polymerised epoxy state and the transient states during network formation, as well as the isostructural phase transitions is further elucidated. [less ▲]