Publikationen

We report on a friction study at the nanometer scale using atomic force microscopy under electrochemical control. Friction arises from the interaction between two surfaces functionalized with cyclodextrin molecules. The interaction is mediated by connector molecules with (ferrocenylmethyl)ammonium end groups forming supramolecular complexes with the cyclodextrin molecules. With ferrocene connector molecules in solution, the friction increases by a factor of up to 12 compared to control experiments without connector molecules. The electrochemical oxidation of ferrocene to ferrocenium causes a decrease in friction owing to the lower stability of ferrocenium-cyclodextrin complex. Upon switching between oxidative and reduction potentials, a change in friction by a factor of 1.2-1.8 is observed. Isothermal titration calorimetry reveals fast dissociation and rebinding kinetics and thus an equilibrium regime for the friction experiments.

We combine non-contact atomic force microscopy (AFM) imaging and AFM indentation in ultra-high vacuum to quantitatively and reproducibly determine the hardness and deformation mechanisms of Pt(111) and a Pt57.5Cu14.7Ni5.3P22.5 metallic glass with unprecedented spatial resolution. Our results on plastic deformation mechanisms of crystalline Pt(111) are consistent with the discrete mechanisms established for larger scales: Plasticity is mediated by dislocation gliding and no rate dependence is observed. For the metallic glass we have discovered that plastic deformation at the nanometer scale is not discrete but continuous and localized around the indenter, and does not exhibit rate dependence. This contrasts with the observation of serrated, rate-dependent flow of metallic glasses at larger scales. Our results reveal a lower size limit for metallic glasses below which shear transformation mechanisms are not activated by indentation. In the case of metallic glass, we conclude that the energy stored in the stressed volume during nanometer-scale indentation is insufficient to account for the interfacial energy of a shear band in the glassy matrix.

Thermoplastic nanocomposites used for vibration welding are compounded on a twin-screw extruder by dilution of a concentrate masterbatch containing 14 vol% of filler. They are butt welded under different weld pressures by a linear vibration welding machine. By means of a quick ramp-down technology, this machine enables a very short vibration damping time of about 40 ms. The influence of different damping time on the weld strength of various materials is investigated. The experimental results are compared also with the results of simulation. In the case of nano-silica filled polypropylene, no impact of the damping time on the weld quality is detected and the possible reasons for this observation are explained.

Polyoxymethylene nanocomposites containing different contents of carbon nanotubes were produced by a two-step melt compounding process using a twin-screw extruder. The dispersion quality, thermal and mechanical properties, and the creep as well as the tribological behaviors of the nanocomposites were investigated. Morphological investigations show that the masterbatch dilution process significantly improves the dispersion quality of carbon nanotubes within polyoxymethylene matrix, and as a consequence, enhanced mechanical properties and creep resistance are gained. Furthermore, to predict the long-term property based on the short-term experimental data, the time-temperature superposition principle and Findley model were used. Master curves with extended time scale are constructed using time-temperature superposition principle to horizontally shift the short-term experimental data. The simulated results confirm the reinforced creep resistance by incorporation of the carbon nanotubes into the polymer matrix even at extended long time scale. By contrast, the tribological performance of polyoxymethylene was remarkably impaired after adding carbon nanotubes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42639.

Although the research and development of nanocomposites for almost a decade focused on structural properties, these properties remained until today far below
expectations, which were forecast at the beginning of the new millennium. However, even if it is well known that the processing history has a major impact on the structure and properties of final components, this aspect was not subject of intensive research in the past. The talk focuses on the role of the manufacturing sequence on the morphology and properties of polypropylene based nanocomposites. In general it can be stated that the incorporation of nano-sized TiO2-fillers improves the some mechanical properties of the resulting nanocomposites as long as the production enables a good dispersion and distribution of the nanofiller agglomerates. However, with increasing filler loading, the morphology of injection molded parts changes: The size of the spherulites and the degree of crystallinity decreases while the crystallization/solidification proceeds faster. Simultaneously a slight improvement in the mechanical performance up to a certain filler loading can be found. However, improved mechanical properties of the nanocomposites in the final component cannot be exploited if its production in a subsequent welding step is required. The reason for the decrease in the mechanical properties is the decrease in the viscosity by the addition of the fillers, and thereby caused extreme flow processes and subsequent orientation of the fillers as well as the weakening of the filler/matrix-interphase in the welding zone. In summary, it
can be observed that nanocomposites increasingly offer great opportunities for applications where single-component materials reach their limits. The key to success is the processing. Therefore it is of crucial importance that the total manufacturing history is understood and controlled. Only then it is possible to sustainably exploit the potential of polymer nanocomposites in the application.

Severe plastic deformation (strains > 100%) has been shown to create significant grain refinement in polycrystalline materials, leading to a nanometric equiaxed crystalline structure for such metals as aluminum, copper and nickel alloys. This process, termed continuous dynamic recrystallization, is governed by evolution of the dislocation structure, which creates new grain boundaries from dislocation walls. In the proposed model, plasticity occurs which firstly involves dislocation multiplication, leading to strain hardening limited by dynamic recovery. After a critical dislocation density is reached new grain boundaries are formed by condensation of walls of dislocations, creating a new stable configuration that is favored due to a reduction of the system free energy. This evolution of the microstructure continues to develop, with a consequent progressive decrease in the average grain diameter. The proposed model provides a quantitative prediction of the evolution of the average grain size, as well as the dislocation density, during continued plastic strain. The model can be calibrated by use of results from any experiment that involves large plastic deformation of metals, subject to negligible annealing effects. In this paper, the model has been calibrated, and consequently validated, through experiments on machining of Al 6061-T6.

A general asymptotic plane strain crack tip stress field is constructed for linear versions of neo-Hookean materials, which spans a wide variety of special cases including incompressible Mooney elastomers, the compressible Blatz-Ko elastomer, several cases of the Ogden constitutive law and a new result for a compressible linear neo-Hookean material. The nominal stress field has dominant terms that have a square root singularity with respect to the distance of material points from the crack tip in the undeformed reference configuration. At second order, there is a uniform tension parallel to the crack. The associated displacement field in plane strain at leading order has dependence proportional to the square root of the same coordinate. The relationship between the amplitude of the crack tip singularity (a stress intensity factor) and the plane strain energy release rate is outlined for the general linear material, with simplified relationships presented for notable special cases.

The phase field description for crack growth and fracture is an attractive alternative to numerical methods based on discrete representations of cracks, since the phase field methodology avoids the numerically challenging monitoring of the discontinuities introduced by the crack. In particular, for the simulation of complex crack growth topologies and application to coupled systems, e.g. with thermal or electrical fields, the phase field method has shown promise. However, an accurate prediction of the crack growth initiation is mandatory for a reliable simulation of crack trajectories both in terms of load history and the path followed through the material. In this work, we therefore investigate predictions of crack growth derived from the phase field method and compare them with established relations from fracture mechanics. To implement the phase field method for crack growth, a parallelized finite element method computer code using adaptive mesh refinement is developed and implemented. Results from it are presented. For these results, pre-existing cracks are introduced into the finite element model in two ways, including their representation as discrete discontinuities and as heterogeneities in the phase field order parameter.

While silica nanoparticles have enabled numerous industrial and medical applications, their toxicological safety requires further evaluation. Macrophages are the major cell population responsible for nanoparticle clearance in vivo. The prevailing macrophage phenotype largely depends on the local immune status of the host. Whereas M1-polarized macrophages are considered as pro-inflammatory macrophages involved in host defense, M2 macrophages exhibit anti-inflammatory and wound-healing properties, but also promote tumor growth. We employed different models of M1 and M2 polarization: granulocyte-macrophage colony-stimulating factor/lipopolysaccharide (LPS)/interferon (IFN)-γ was used to generate primary human M1 cells and macrophage colony-stimulating factor (M-CSF)/interleukin (IL)-10 to differentiate M2 monocyte-derived macrophages (MDM). PMA-differentiated THP-1 cells were polarized towards an M1 type by LPS/IFN-γ and towards M2 by IL-10. Uptake of fluorescent silica nanoparticles (Ø26 and 41 nm) and microparticles (Ø1.75 μm) was quantified. At the concentration used (50 μg/ml), silica nanoparticles did not influence cell viability as assessed by MTT assay. Nanoparticle uptake was enhanced in M2-polarized primary human MDM compared with M1 cells, as shown by flow cytometric and microscopic approaches. In contrast, the uptake of microparticles did not differ between M1 and M2 phenotypes. M2 polarization was also associated with increased nanoparticle uptake in the macrophage-like THP-1 cell line. In accordance, in vivo polarized M2-like primary human tumor-associated macrophages obtained from lung tumors took up more nanoparticles than M1-like alveolar macrophages isolated from the surrounding lung tissue. In summary, our data indicate that the M2 polarization of macrophages promotes nanoparticle internalization. Therefore, the phenotypical differences between macrophage subsets should be taken into consideration in future investigations on nanosafety, but might also open up therapeutic perspectives allowing to specifically target M2 polarized macrophages.

Background: Exposure of the airways to carbonaceous nanoparticles can contribute to the development of immune diseases both via the aggravation of the allergic immune response in sensitized individuals and by adjuvant mechanisms during the sensitization against allergens. The cellular and molecular mechanisms involved in these adverse pathways are not completely understood. We recently described that the reduction of carbon nanoparticle-induced lung inflammation by the application of the compatible solute ectoine reduced the aggravation of the allergic response in an animal system. In the current study we investigated the influence of carbon nanoparticles on the sensitization of animals to ovalbumin via the airways. Ectoine was used as a preventive strategy against nanoparticle-induced neutrophilic lung inflammation. Methods: Balb/c mice were repetitively exposed to the antigen ovalbumin after induction of airway inflammation by carbon nanoparticles, either in the presence or in the absence of ectoine. Allergic sensitization was monitored by measurement of immunoglobulin levels and immune responses in lung and lung draining lymph nodes after challenge. Furthermore the role of dendritic cells in the effect of carbon nanoparticles was studied in vivo in the lymph nodes but also in vitro using bone marrow derived dendritic cells. Results: Animals exposed to antigen in the presence of carbon nanoparticles showed increased effects with respect to ovalbumin sensitization, to the allergic airway inflammation after challenge, and to the specific T(H)2 response in the lymph nodes. The presence of ectoine during the sensitization significantly reduced these parameters. The number of antigen-loaded dendritic cells in the draining lymph nodes was identified as a possible cause for the adjuvant effect of the nanoparticles. In vitro assays indicate that the direct interaction of the particles with dendritic cells is not able to trigger CCR7 expression, while this endpoint is achieved by lung lavage fluid from nanoparticle-exposed animals. Conclusions: Using the intervention strategy of applying ectoine into the airways of animals we were able to demonstrate the relevance of neutrophilic lung inflammation for the adjuvant effect of carbon nanoparticles on allergic sensitization.