Roland Sanctuary

Evidence for low temperature phase transition in Rb2ZnCl4 from dielectric constant and birefringence measurements

Temperature dependences of the dielectric constants ϵi and of the birefringences Δni for light propagation directions along all the three crystallographic axes (i = a, b, c) have been measured between 5 and 350 K. The optical measurements clearly reveal a new phase transition at TL = 75 K, below which the crystal structure is transformed from the ferroelectric Pna21 phase into an unknown low temperature phase, possibly the monoclinic space group P1121. Small peaks in the dielectric constants ϵa and ϵb have been observed at this transition temperature.

GRADIENT OF THE MECHANICAL MODULUS IN GLASS–EPOXY–METAL JOINTS AS MEASURED BY BRILLOUIN MICROSCOPY

The newly developed Brillouin microscopy is used for the first time to measure in situ the longitudinal elastic stiffness coefficient in the GHz-range inside of glass–epoxy–metal joints as a function of distance from the substrates. Interphases with a local variation of mechanical properties are quantitatively characterized. These interphases possess unexpected widths of tens to hundreds of microns. Inside the interphases, the spatial variation of the longitudinal stiffness coefficient depends on the type of substrate, on the curing conditions for the epoxy and probably on the distribution of internal stresses. The obtained spatial mechanical profiles provide valuable insight into the morphology-driven mechanics of the interphase, but additional information is needed for a full understanding of their physical and chemical origin. The presented results prove the sensitivity of the Brillouin microscopy; the elastic stiffness coefficients are detected with an accuracy in the subpercentage range. The spatial resolution is better than 10 µm.

Influence of Al(2)O(3) nanoparticles on the isothermal cure of an epoxy resin.

The influence of Al(2)O(3) nanoparticles on the curing of an epoxy thermoset based on diglycidyl ether of bisphenol A was investigated using temperature-modulated differential scanning calorimetry (TMDSC) and rheology. Diethylene triamine was used as a hardener. TMDSC not only allows for a systematic study of the kinetics of cure but simultaneously gives access to the evolution of the specific heat capacities of the thermosets. The technique thus provides insight into the glass transition behaviour of the nanocomposites and hence makes it possible to shed some light on the interaction between the nanoparticles and the polymer matrix. The Al(2)O(3) fillers are shown to accelerate the growth of macromolecules upon isothermal curing. Several mechanisms which possibly could be responsible for the acceleration are described. As a result of the faster network growth chemical vitrification occurs at earlier times in the filled thermosets and the specific reaction heat decreases with increasing nanoparticle concentration. Rheologic measurements of the zero-shear viscosity confirm the faster growth of the macromolecules in the presence of the nanoparticles.

Imaging of microwave-induced acoustic fields in LiNbO3 by high-performance Brillouin microscopy

High performance Brillouin microscopy (BM) has been used to characterize the spatial distribution of piezoelectrically induced acoustic fields excited at microwave frequencies in a LiNbO3 single crystal. It is demonstrated that under suitable conditions BM is able to detect microwave-induced bulk as well as surface acoustic waves. Brillouin spectroscopy is able to probe sound wave intensities of induced phonons, which are as small as those of thermal phonons.

Immense elastic nonlinearities at the demixing transition of aqueous PNIPAM solutions

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 Gruneisen 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.

The generalized Cauchy relation: a probe for local structure in materials with isotropic symmetry

The elastic properties of the isotropic state of condensed matter are given by the elastic constants ell and c44. In the liquid state the static shear stiffness c44 vanishes whereas at sufficient high probe frequencies a dynamic shear stiffness may appear. In that latter case the question about the existence of a Cauchy relation appears. It will be shown that a pure Cauchy relation can appear only under special conditions which are rarely fulfilled. For all investigated materials, including ceramics, liquids and glasses, a linear relation between ell and c44 called generalized Cauchy relation is observed, which, surprisingly, follows a linear transformation

Acoustic profilometry within polymers as performed by Brillouin microscopy

Using high performance Brillouin spectroscopy we present a new technique, which enables us to perform acoustic microscopy with a spatial resolution of about 1 µm. This technique, called Brillouin microscopy, is tested on several bulk- and film-like polymer samples.

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

Structural developments are investigated in network-forming reactive polymers by time- and 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 hardener can easily penetrate and swell these networks and epoxy network fragments can be transported over several millimetres by convective flow. The observed features may be used to form interpenetrating networks during self-healing procedures.

Phase Instability and Molecular Kinetics Provoked by Repeated Crossing of the Demixing Transition of PNIPAM Solutions

The demixing process of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions can occur either via a nucleation and growth process or via spinodal decomposition. The ensuing self-assembly, leading to heterogeneous morphologies within the PNIPAM solution, is codetermined by kinetic processes caused by molecular transport. By subjecting PNIPAM solutions to cyclic changes in temperature leading to repeated crossing of the demixing transition, we are able to assess the importance of kinetics as well as of overheating and supercooling of the phase transition within the metastable range delimited by the binodal and spinodal lines. First indications about the location of these stability limits for the low- and high-temperature phases, separated by about 1.6 K, could be gained by detailed kinetic studies of the refractive index. These investigations are made possible due to the novel technique of temperature-modulated optical refractometry.

Kinetic processes at the demixing transition of PNIPAM solutions

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 low-temperature phase.