Spatial inhomogeneity, interfaces and complex vitrification kinetics in a network forming nanocomposite.

A detailed calorimetric study on an epoxy-based nanocomposite system was performed employing bisphenol A diglycidyl ether (DGEBA) cured with diethylenetriamine (DETA) as the polymer matrix and a taurine-modified MgAL layered double hydroxide (T-LDH) as the nanofiller. The -NH2 group of taurine can react with DGEBA improving the interaction of the polymer with the filler. The combined X-ray scattering and electron microscopy data showed that the nanocomposite has a partially exfoliated morphology. Calorimetric studies were performed using conventional DSC, temperature modulated DSC (TMDSC) and fast scanning calorimetry (FSC) in the temperature modulated approach (TMFSC) to investigate the vitrification and molecular mobility dependent on the filler concentration. First, TMDSC and NMR were used to estimate the amount of the rigid amorphous fraction which consists of immobilized polymer segments at the nanoparticle surface. It was found to be 40 wt% for the highest filler concentration, indicating that the interface dominates the overall macroscopic properties and behavior of the material to a great extent. Second, the relaxation rates of the α-relaxation obtained by TMDSC and TMFSC were compared with the thermal and dielectric relaxation rates measured by static FSC. The investigation revealed that the system shows two distinct α-relaxation processes. Furthermore, two separate vitrification mechanisms were also found for a bulk network-former without geometrical confinement as also confirmed by NMR. This was discussed in terms of the intrinsic spatial heterogeneity on a molecular scale, which becomes more pronounced with increasing nanofiller content.

Concept of a Novel Glass Ionomer Restorative Material with Improved Mechanical Properties.

The objective of this study was to transfer the concept of ductile particle reinforcement to restorative dentistry and to introduce an innovative glass ionomer material that is based on the dispersion of PEG-PU micelles. It was hypothesized that reinforcing a conventional glass ionomer in this way increases the flexural strength and fracture toughness of the material. Flexural strength and fracture toughness tests were performed with the novel reinforced and a control glass ionomer material (DMG, Hamburg, Germany) to investigate the influence of the dispersed micelles on the mechanical performance. Transmission electron microscopy was used to identify the dispersed micelles. Fracture toughness and flexural strength were measured in a 3-point-bending setup using a universal testing machine. Before performing both tests, the specimens were stored in water at 37 °C for 23 h. The fracture toughness (MPa∙m0.5) of the novel glass ionomer material (median: 0.92, IQR: 0.89-0.94) was significantly higher than that of the control material (0.77, 0.75-0.86, p = 0.0078). Significant differences were also found in the flexural strength (MPa) between the reinforced (49.7, 45.2-57.8) and control material (41.8, 40.6-43.5, p = 0.0011). Reinforcing a conventional glass ionomer with PEG-PU micelles improved the mechanical properties and may expand clinical applicability of this material class in restorative dentistry.

Common Origin of Filler Network Related Contributions to Reinforcement and Dissipation in Rubber Composites.

A comparative study focusing on the visco-elastic properties of two series of carbon black filled composites with natural rubber (NR) and its blends with butadiene rubber (NR-BR) as matrices is reported. Strain sweeps at different temperatures are performed. Filler network-related contributions to reinforcement (ΔG') are quantified by the classical Kraus equation while a modified Kraus equation is used to quantify different contributions to dissipation (ΔGD″, ΔGF″). Results indicate that the filler network is visco-elastic in nature and that it is causing a major part of the composite dissipation at small and intermediate strain amplitudes. The temperature dependence of filler network-related reinforcement and dissipation contributions is found to depend significantly on the rubber matrix composition. We propose that this is due to differences in the chemical composition of the glassy rubber bridges connecting filler particles since the filler network topology is seemingly not significantly influenced by the rubber matrix for a given filler content. The underlying physical picture explains effects in both dissipation and reinforcement. It predicts that these glassy rubber bridges will soften sequentially at temperatures much higher than the bulk Tg of the corresponding rubber. This is hypothetically due to rubber-filler interactions at interfaces resulting in an increased packing density in the glassy rubber related to the reduction of free volume. From a general perspective, this study provides deeper insights towards the molecular origin of reinforcement and dissipation in rubber composites.

Calorimetric and Dielectric Investigations of Epoxy-Based Nanocomposites with Halloysite Nanotubes as Nanofillers.

Epoxy nanocomposites are promising materials for industrial applications (i.e., aerospace, marine and automotive industry) due to their extraordinary mechanical and thermal properties. Here, the effect of hollow halloysite nanotubes (HNT) on an epoxy matrix (Ep) was the focus of the study. The structure and molecular mobility of the nanocomposites were investigated using a combination of X-ray scattering, calorimetry (differential (DSC) and fast scanning calorimetry (FSC)) and dielectric spectroscopy. Additionally, the effect of surface modification of HNT (polydopamine (PDA) and Fe(OH)3 nanodots) was considered. For Ep/HNT, the glass transition temperature (Tg) was decreased due to a nanoparticle-related decrease of the crosslinking density. For the modified system, Ep/m-HNT, the surface modification resulted in enhanced filler-matrix interactions leading to higher Tg values than the pure epoxy in some cases. For Ep/m-HNT, the amount of interface formed between the nanoparticles and the matrix ranged from 5% to 15%. Through BDS measurements, localized fluctuations were detected as a ß- and γ-relaxation, related to rotational fluctuations of phenyl rings and local reorientations of unreacted components. A combination of calorimetry and dielectric spectroscopy revealed a dynamic and structural heterogeneity of the matrix, as confirmed by two glassy dynamics in both systems, related to regions with different crosslinking densities.

From the surface to the bulk: A comparison of methods for the microanalysis of an immiscible polymer blend.

In this study, the morphology of an immiscible polymer blend system at various regions of interests was analyzed using different microanalytical methods with varying surface sensitivities. As a model immiscible polymer blend, a HDPE/PP (80/20 wt%) polymer film was used. The blend film was subjected to polarized light microscopy (PLM), scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM) and time of flight secondary ion mass spectrometry (ToF-SIMS). The obtained results were compared regarding the sensitivities, informational values and overall applicability of the analytical methods. It was evaluated which methods can be applied for a fast analysis of the morphology (surface and bulk) of the immiscible polymer blend with low preparation efforts, which is especially important for the analysis of new materials, for example materials manufactured via recycling. It was demonstrated that PLM, as well as SEM on wet-etched material, provide sufficient information to evaluate the bulk morphology. Additionally, the presented study shows the advantage of applying ToF-SIMS imaging for the characterization of the surface of immiscible polymer blend. As expected, the domain distribution of HDPE and PP varied between the bulk and the surface of the films. The proposed procedures can be taken as a guideline for other investigations concerning the morphology of heterogeneous polyolefin systems.