Jörg Baller

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.

About the Nature of the Structural Glass Transition: An Experimental Approach

The nature of the glassy state and of the glass transition of structural glasses is still a matter of debate. This debate stems predominantly from the kinetic features of the thermal glass transition. However the glass transition has at least two faces: the kinetic one which becomes apparent in the regime of low relaxation frequencies and a static one observed in static or frequency-clamped linear and non-linear susceptibilities. New results concerning the so-called α-relaxation process show that the historical view of an unavoidable cross-over of this relaxation time with the experimental time scale is probably wrong and support instead the existence of an intrinsic glass transition. In order to prove this, three different experimental strategies have been applied: studying the glass transition at extremely long time scales, the investigation of properties which are not sensitive to the kinetics of the glass transition and studying glass transitions which do not depend at all on a forced external time scale.

Strain-induced low-frequency relaxation in colloidal DGEBA/SiO2 suspensions

Diglycidyl ether of bisphenol A (DGEBA) is widely exploited as an epoxy resin in adhesives and coatings. In this paper, it is used as an oligomer matrix for silica-filled nanocomposites. Rheological measurements show that the pure matrix obeys power-law relaxation dynamics in the vicinity of the dynamic glass transition of this low-molecular-weight glass former. In the filled systems, a low-frequency relaxation appears additionally to the structural α-process of the matrix. Considering the nanocomposites as Newtonian hard-sphere suspensions at low angular frequencies (or high temperatures), the modified terminal regime behavior of the matrix can be linked to strain-induced perturbations of the isotropic filler distributions. While in the low-frequency regime hydrodynamic stresses relax instantaneously, the Brownian stress relaxation is viscoelastic and can be evidenced by dynamic rheological measurements. At higher angular frequencies, the α-process of the matrix superimposes on the Brownian stress relaxation. In particular, we were able to depict the low-frequency anomaly for concentrated, semi-dilute, and even for dilute suspensions.

Acoustic profilometry of interphases in epoxy due to segregation and diffusion using Brillouin microscopy

Reactive network forming polymer systems like epoxies are of huge technological interest because of their adhesive properties based on specific interactions with a large variety of materials. These specific interactions alter the morphology of the epoxy within areas determined by the correlation length of these interactions. The changed morphology leads to interphases with altered (mechanical) properties. Besides these surface-induced interphases, bulk interphases do occur due to segregation, crystallization, diffusion, etc. A new experimental technique to characterize such mechanical interphases is µ-Brillouin spectroscopy (µ-BS). With µ-BS, we studied interphases and their formation in epoxies due to segregation of the constituent components and due to selective diffusion of one component. In the latter case, we will demonstrate the influence of changing the boundary conditions of the diffusion process on the shape of the interphase.

Different glassy states, as indicated by a violation of the generalized Cauchy relation

Using Brillouin spectroscopy as a probe for high-frequency clamped acoustic properties, a shear modulus c44? can be measured in addition to the longitudinal modulus c11? already well above the thermal glass transition. On?slow cooling of the liquid through the thermal glass transition temperature Tg, both moduli show a kink-like behaviour and the function c11? = c11?(c44?) follows a generalized Cauchy relation (gCR) defined by the linear relation c11? = 3c44? + constant, which completely hides the glass transition. In this work we show experimentally that on fast cooling this linear transformation becomes violated within the glassy state, but that thermal ageing drives the elastic coefficients towards the gCR, i.e. towards a unique glassy state.

Elastic properties of single-crystalline and consolidated nano-structured yttrium oxide at room temperature

High resolution Brillouin spectroscopy was used to characterize the elastic stiffness properties of consolidated nano-crystalline yttrium oxide as well as of the related single-crystalline state. Defect enriched grain boundaries are discussed as sources for the extremely soft elastic properties of the nano-crystalline state.

On the influence of nano-scaling on the glass transition of molecular liquids

Abstract The nature of the glass transition is still a matter of debate. We used temperature modulated DSC (TMDSC) and Brillouin spectroscopy (BS) to investigate the freezing behaviour of canonical glasses (salol and di-n-butyl-phtalate (DBP)) confined to controlled pore glasses (CPG) with pore diameters between 2.5 and 20 nm. The temperature behaviour of the heat capacity of the composite system deviates from the bulk fluid properties and we interpret the remaining kink-like anomaly at Tg as a static glass transition. In smaller pores Tg is only slightly shifted to lower temperatures. This operative Tg is in good agreement with sound velocity data showing a sharp kink at Tg. The working hypothesis of the existence of a static glass transition is supported by the fact that the α-relaxation process disappears with decreasing pore diameter.

Anomalous glass transition behavior of SBR?Al2O3 nanocomposites at small filler concentrations

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles, the larger is the interface where interactions between polymer molecules and fillers can generate new properties. Using temperature-modulated differential scanning calorimetry and dynamic mechanical analysis, we investigated the properties of pure styrene-butadiene rubber (SBR) and SBR/alumina nanoparticles. Beside a reinforcement effect seen in the complex elastic moduli, small amounts of nanoparticles of about 2 wt% interestingly lead to an acceleration of the relaxation modes responsible for the thermal glass transition. This leads to a minimum in the glass transition temperature as a function of nanoparticle content in the vicinity of this critical concentration. The frequency dependent elastic moduli are used to discuss the possible reduction of the entanglement of rubber molecules as one cause for this unexpected behavior.

Second order elasticity at hypersonic frequencies of reactive polyurethanes as seen by generalized Cauchy relations

The non-equilibrium process of polymerization of reactive polymers can be accompanied by transition phenomena like gelation or the chemical glass transition. The sensitivity of the mechanical properties at hypersonic frequencies-including the generalized Cauchy relation-to these transition phenomena is studied for three different polyurethanes using Brillouin spectroscopy. As for epoxies, the generalized Cauchy relation surprisingly holds true for the non-equilibrium polymerization process and for the temperature dependence of polyurethanes. Neither the sol-gel transition nor the chemical and thermal glass transitions are visible in the representation of the generalized Cauchy relation. Taking into account the new results and combining them with general considerations about the elastic properties of the isotropic state, an improved physical foundation of the generalized Cauchy relation is proposed.

Freezing of nano-scaled fractal molecules: Dendrimers

Abstract Within this paper we present mono-disperse dendrimers as a new class of ideal canonical glass formers where the frustration mechanism originates from the self similar intramolecular order. Because of their fractal intramolecular structure these dendrimers are hardly able to build up a three dimensional translation symmetry necessary to form the crystalline state. Instead they show an unconventional dynamic and static freezing behavior at rather low temperatures. Based on temperature modulated differential scanning calorimetry (TMDSC) and Brillouin spectroscopy (BS) we give further evidences for the existence of an ideal primary glass transition with a thermal glass transition temperature which increases with the generation index of the fractal molecule. However, the primary glass transitions of higher generations do not completely erase the memory of the fractal intramolecular mobility but allow the survival of dynamic processes significant for the freezing of the constituting molecular unit.