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 ▲]

On the elastic nature of the demixing transition of aqueous PNIPAM solutions

in Soft Matter (2012), 8

Mechanical instabilities accompanying the demixing transition of semi-dilute aqueous poly(Nisopropylacrylamide) (PNIPAM) solutions are probed for the first time with Brillouin spectroscopy, densitometry ... [more ▼]

Mechanical instabilities accompanying the demixing transition of semi-dilute aqueous poly(Nisopropylacrylamide) (PNIPAM) solutions are probed for the first time with Brillouin spectroscopy, densitometry and refractometry. The particular role of the elastic moduli and the mass density at this coil-to-globule transition followed by molecular aggregation is investigated. Even though the demixing transition of PNIPAM solutions is denoted as a volume phase transition, it turns out that this transition is governed by the elastic properties, instead of the volume properties. This is consistent with earlier findings made for the demixing transition in chemically cross-linked PNIPAM hydrogels. Above the demixing temperature, Brillouin spectroscopy discriminates compact PNIPAM-rich agglomerates with sizes larger than 200 nm. Interestingly, these agglomerates possess a sharp distribution of elastic moduli, which can be attributed without any doubt to a material with gel-like mechanical consistency. Thus the phase-separated PNIPAM-rich agglomerates are not in the glassy state. [less ▲]

Influence of Nanoparticles on the Coupling Between Optical Dipoles in Epoxy-Silica Nanocomposites During Network Formation

in The Journal of Adhesion (2012), 88(7), 566-588

High-performance refractometry and infrared spectroscopy are combined in order to elucidate the gelation process and the glass transition during the network formation of epoxies and epoxy-based ... [more ▼]

High-performance refractometry and infrared spectroscopy are combined in order to elucidate the gelation process and the glass transition during the network formation of epoxies and epoxy-based nanocomposites. Whereas infrared spectroscopy yields the chemical conversion due to the opening of oxirane rings during the covalent network formation, high-performance refractometry is extremely sensitive to the accompanying changes of the arrangement of the molecular network. In accordance with the Lorentz-Lorenz relationship, the evolution of the refractive index seems to reflect that of the mass density during polymerization of the epoxy-based systems within the limits of a few percent. The slight deviations from the Lorentz-Lorenz relationship, which occur during the gelation of the epoxy-based systems, are attributed to long-ranged dipole-dipole interactions, which respond at optical frequencies. This point of view is supported by the fact that chemically inert silica nanoparticles embedded in the pure epoxy matrix as disturbances for these dipole-dipole interactions are able to diminish or even to suppress totally this excess contribution of the refractive index. [less ▲]

Dissolution, transport and reaction at a DICY/DGEBA interface

in Journal of Adhesion (2012), 88(3), 253-276

The curing of an epoxy consisting of the solid hardener dicyandiamide (DICY) and the resin diglycidyl ether of bisphenol A (DGEBA) is studied in a system consisting of a tablet of DICY embedded in liquid ... [more ▼]

The curing of an epoxy consisting of the solid hardener dicyandiamide (DICY) and the resin diglycidyl ether of bisphenol A (DGEBA) is studied in a system consisting of a tablet of DICY embedded in liquid DGEBA. Dissolution of DICY within the liquid DGEBA in combination with the transport of dissolved DICY from the tablet border into DGEBA and the chemical reaction of both reactants is studied by scanning Brillouin microscopy and infrared spectroscopy. Scanning Brillouin microscopy demonstrates the spatial and temporal evolution of the static and dynamic hypersonic properties in the course of curing in the vicinity of the DICY tablet. Infrared spectroscopy performed on epoxy pieces extracted from the final sample at different distances from the tablet surface give information about the spatial evolution of the curing process. The results achieved by both techniques are finally combined to yield a better understanding of the curing of DICY-based epoxies, which transform upon curing from strongly heterogeneous systems towards increasingly homogeneous systems. Copyright © Taylor & Francis Group, LLC. [less ▲]

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)

Heterogeneous Transport Processes and Unexpected Structure Formation in Layered Epoxy and Epoxy-Alumina Nanocomposite Systems

in Journal of Adhesion (2011), 87(11), 1073-1098

Static and dynamic hypersonic properties are probed to reveal the subtle interplay between demixing, matter transport, chemical network formation, polymer network swelling, and network damage in the ... [more ▼]

Static and dynamic hypersonic properties are probed to reveal the subtle interplay between demixing, matter transport, chemical network formation, polymer network swelling, and network damage in the vicinity of the interface between the reactants of amine-curing epoxies. An innovative time- and space-resolved acoustic microscopy, called scanning Brillouin microscopy, gives access to these competing transport and structure formation processes in epoxy systems consisting of either pure resin, alumina nanoparticles-filled resin, or various epoxy resin-hardener mixtures topped by a layer of pure hardener. Static and dynamic hypersonic properties are probed to reveal the subtle interplay between demixing, matter transport, chemical network formation, polymer network swelling, and network damage in the vicinity of the interface between the reactants of amine-curing epoxies. An innovative time- and space-resolved acoustic microscopy, called scanning Brillouin microscopy, gives access to these competing transport and structure formation processes in epoxy systems consisting of either pure resin, alumina nanoparticles-filled resin, or various epoxy resin-hardener mixtures topped by a layer of pure hardener. [less ▲]

Functional nano fillers in epoxy-dicyandiamide adhesives for prolonged shelf life and efficient cure

in e-Polymers (2011), (10), 1-15

Shelf life at room temperature and curing behaviour at elevated temperature are studied for hot-curing accelerated epoxies (EP, diglycidylether of bisphenol A plus dicyandiamide (Dicy)) by FTIR ... [more ▼]

Shelf life at room temperature and curing behaviour at elevated temperature are studied for hot-curing accelerated epoxies (EP, diglycidylether of bisphenol A plus dicyandiamide (Dicy)) by FTIR-spectroscopy and modulated DSC. The accelerator is added either directly or with nano-zeolite filler to the EP. Due to the immobilization of the accelerator in the pores of the nano-zeolite, the shelf life of this EP is 5 times longer than for the EP containing free accelerator. While the free accelerator acts during the whole heating step to curing temperature, the nano-zeolite does not release the accelerator before ca. 100 °C. As monitored by light microscopy, the released accelerator not only supports the curing but also stimulates the dissolution of the solid Dicy. As the result, network formation at 170 °C finishes within less than 25 minutes for the nano-filled EP. [less ▲]

Shelf Life and Controlled Cure of Epoxies by Loaded Zeolite

in Composite Interfaces (2010)

Epoxy formulations based on the multi-functional amine hardener, dicyandiamide (Dicy), regularly contain a free accelerator for reducing the curing temperature and the time needed to complete the network ... [more ▼]

Epoxy formulations based on the multi-functional amine hardener, dicyandiamide (Dicy), regularly contain a free accelerator for reducing the curing temperature and the time needed to complete the network formation. Unfortunately, all accelerators reduce the shelf life of these adhesives at 25◦C. In order to solve this problem, accelerator-loaded zeolites fillers were developed, optimised with respect to host–guest interactions and characterised by Fraunhofer IFAM (Bremen, Germany) with regard to the release and curing behaviour in epoxy adhesive formulations. They are added to an epoxy adhesive (diglycidylether of bisphenol A (EP) and dicyandiamide (Dicy), mass ratio 100:6.7), stored at 25◦C in regular air or cured (heated with β = 10 K/min to 170◦C subsequent isothermal curing for 45 min). That shelf life and curing behaviour are investigated by FT-IR spectroscopy and modulated DSC. Compared to the EP containing free accelerator, the zeolite-filled EP possesses a threefold increase in shelf life at 25◦C due to the immobilization of the accelerator in the pores of the zeolites. While the free accelerator acts steadily during heating, it is shown that the loaded zeolite releases the accelerator at about 76◦C. Surprisingly, the released accelerator is not only involved in the chemical formation of the epoxy network but it accelerates the dissolution of Dicy considerably. As the result, network formation at 170◦C finishes after not more than 19 min and the starting temperature for curing could be reduced to 140◦C. [less ▲]