6 Materialchemie
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- 2019 (28) (entfernen)
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- Broadband dielectric spectroscopy (4)
- Discotic Liquid Crystals (3)
- Epoxy (3)
- Microplastics (3)
- Nanocomposites (3)
- Simulation (3)
- Specific heat spectroscopy (3)
- Boehmite (2)
- Flash DSC (2)
- Interphase (2)
Organisationseinheit der BAM
- 6.6 Physik und chemische Analytik der Polymere (28) (entfernen)
The movement of the macroscopic magnetic moment in ferromagnetic systems can be described by the Landau-Lifshitz (LL) or Landau-Lifshitz-Gilbert (LLG) equation. These equations are strictly valid only at absolute zero temperature. To include temperature effects a stochastic version of the LL or LLG equation for a spin density of one per unit cell can be used instead. To apply the stochastic LL to micromagnetic simulations, where the spin density per unit cell is generally higher, a conversion regarding simulation cell size and temperature has to be established. Based on energetic considerations, a conversion for ferromagnetic bulk and thin film systems is proposed. The conversion is tested in micromagnetic simulations which are performed with the Object Oriented Micromagnetic Framework (OOMMF). The Curie temperatures of bulk Nickel, Cobalt and Iron systems as well as Nickel thin-film systems with thicknesses between 6.3 mono layer (ML) and 31ML are determined from micromagnetic simulations. The results show a good agreement with experimentally determined Curie temperatures of bulk and thin film systems when temperature scaling is performed according to the presented model.
Dose enhancement by gold nanoparticles (AuNP) was shown to increase the biological effectiveness of radiation damage in biomolecules and tissue. Most of the current studies focus on external beam therapy on combination with AuNP. Here we present a Monte-Carlo study (Geant4) to characterise radioactive AuNP. Radioactive ¹⁹⁸Au emits beta and gamma rays and is considered for applications with solid tumours. To effectively apply ¹⁹⁸AuNP their energy deposit characteristics have to be determined in terms of intrinsic and extrinsic properties e.g. AuNP diameter, AuNP density, and their clustering behaviour. After each decay process, the energy deposit, inelastic scattering events, kinetic energy spectrum of secondary particles within the AuNP themselves and in a spherical target volume of water up to 1 μm radius were determined. Simulations were performed for AuNP radii ranging from 2.5 nm to 20 nm radius, different cluster sizes and densities. The results show an increase of the energy deposit in the vicinity of the AuNP up to 150 nm. This effect nearly vanishes for distances up to one micron. For the case of AuNP clusters and the same activity, the enhancement of the energy deposit increases with the relative gold mass percentage and therefore can be adjusted by changing AuNP radius or clustering behaviour.
In this study, a method for the determination of tire and road wear particle (TRWP) contents in particulate samples from road Environment was developed. Zn was identified as the most suitable elemental marker for TRWP, due to its high concentration in tire tread and the possibility of separation from other Zn sources. The mean concentration of 21 tire samples was 8.7 ± 2.0 mg Zn/g. Before quantification in samples from road environment, TRWP were separated from the particulate matrix by density separation. Method development was conducted using shredded tread particles (TP) as a surrogate for TRWP.
Recovery of TP from spiked sediment was 95 ± 17% in a concentration range of 2 - 200 mg TP/g. TP determination was not affected by other Zn containing solids or spiked Zn-salts. By adjusting the density of the separation solution to 1.9 g/cm3, more than 90% of total TRWP were separated from the sample matrix. TRWP concentrations in particulate matter collected in two road runoff treatment Systems ranged from 0.38 to 150 mg TRWP/g. Differences in quantified TRWP contents of the two Systems indicate changes in particle dynamics due to ageing and aggregation processes. The developed method allows TRWP determination in road runoff and in environments that are influenced by road traffic. The validated separation procedure can also be applied for TRWP characterization in future studies.
Based on the three-phase model of semi-crystalline polymers, we determined all phase fractions of the NiAl-LDH/PLLA nanocomposites in dependence on the concentration of the nanofiller. Moreover, the rigid amorphous fraction (RAF) was separated into the RAFcrystal and the RAFfiller unbiasedly. A detailed comparison to the related nanocomposite system MgAl-LDH/PLLA was made considering that Mg and Ni have different atomic weights. As a first result is was found that NiAl-LDH/PLLA displays a higher crystallization rate compared to MgAl-LDH/PLLA, which is related to the different morphologies of the two nanocomposite systems. For both systems RAFcrystal increases with increasing concentration of the nanofiller. This means in the case of the nanocomposite not each crystal produces the same amount of RAF, as often assumed. Also, RAFfiller increases with the concentration for both systems but in a different way. This is discussed considering again the different morphologies of both nanocomposites.
Copper has a strong bactericidal effect against multi-drug resistant pathogens and polyethers are known for their resistance to biofilm formation. Herein, we combined Cu nanoparticles (NPs) and a polyether Plasma polymer in the form of nanocomposite thin films and studied whether both effects can be coupled. Cu NPs were produced by magnetron sputtering via the aggregation in a cool buffer gas whereasolyether layers were synthesized by Plasma-Assisted Vapor Phase Deposition with poly(ethylene oxide) (PEO) used as a precursor. In situ specific heat spectroscopy and XPS analysis revealed the formation of a modified polymer layer around the NPs which propagates on the scale of a few nanometers from the Cu NP/polymer interface and then transforms into a bulk polymer phase. The chemical composition of the modified layer is found to be ether-deficient due to the catalytic influence of copper whereas the bulk polymer Phase exhibits the chemical composition close to the original PEO. Two cooperative glass transition phenomena are revealed that belong to the modified polymer layer and the bulk phase. The former is characterized by constrained mobility of polymer segments which manifests itself via a 30 K increase of dynamic glass transition temperature. Furthermore, the modified layer is characterized by the heterogeneous structure which results in higher fragility of this layer as compared to the bulk phase. The Cu NPs/polyether thin films exhibit reduced Protein adsorption; however, the constrained segmental dynamics leads to the Deterioration of the non-fouling properties for ultra-thin polyether coatings. The films are found to have a bactericidal effect against multi-drug resistant Gram-positive Methicillin-Resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa.
Polyether and -ester urethanes (PU) were exposed to artificial weathering at 40 °C and artificial UV radiation in a weathering chamber. In 3 parallel exposures, humidity was varied between dry, humid, and wet conditions. Material alteration was investigated by various analytical techniques like size exclusion chromatography
(SEC), liquid chromatography-infrared spectroscopy (LC-FTIR), thermal-desorption gas chromatography-mass spectrometry (TD-GC-MS), fluorescence mapping and dynamic mechanical analysis (DMA). Our results show that depending on the weathering conditions, different degradation effects can be observed. By means of SEC an initial strong decrease of the molar masses and a broadening of the mass distributions was found. After a material dependent time span this was followed by a plateau where molar mass changes were less significant. A minor moisture-dependent degradation effect was only found for polyester PU. Fluorescence measurements on two materials revealed an increase in the luminescence intensity upon weathering process reaching a saturation level after about 500 h. The changes in the optical properties observed after different exposure conditions and times were very similar. The TD-GC-MS data showed the fate of the stabilizers and antioxidant in the course of weathering. LC-FTIR measurements revealed a change in peak intensities and the ratio of urethane and carbonyl bands.
Nanoporous media exhibit structures significantly smaller than the wavelengths of visible light and can thus act as photonic metamaterials. Their optical functionality is not determined by the properties of the base materials, but rather by tailored, multiscale structures, in terms of precise pore shape, geometry, and orientation. Embedding liquid crystals in pore space provides additional opportunities to control light–matter interactions at the single-pore, meta-atomic scale. Here, we present temperature-dependent 3D reciprocal space mapping using synchrotron-based X-ray diffraction in combination with high-Resolution birefringence experiments on disk-like mesogens (HAT6) imbibed in self-ordered arrays of parallel cylindrical pores 17 to 160 nm across in monolithic anodic aluminium oxide (AAO). In agreement with Monte Carlo computer simulations we observe a remarkably rich self-assembly behaviour, unknown from the bulk state. It encompasses transitions between the isotropic liquid state and discotic stacking in linear columns as well as circular concentric ring formation perpendicular and parallel to the pore axis. These textural transitions underpin an optical birefringence functionality, tuneable in magnitude and in sign from positive to negative via pore size, pore surface-grafting and temperature. Our study demonstrates that the advent of large-scale, self-organised nanoporosity in monolithic solids along with confinement-controllable phase behaviour of liquid-crystalline matter at the single-pore scale provides a reliable and accessible tool to design materials with adjustable optical anisotropy, and thus offers versatile pathways to finetune polarisation-dependent light propagation speeds in materials. Such a tailorability is at the core of the emerging field of transformative optics, allowing, e.g., adjustable light absorbers and extremely thin metalenses.
Thin films (200-7nm) of the asymmetric polymer blend poly(vinyl methyl ether) (PVME)/polystyrene (PS) (25/75wt%) were investigated by broadband dielectric spectroscopy (BDS). Thicker samples ([Formula: see text]37 nm) were measured by crossed electrode capacitors (CEC), where the film is capped between Al-electrodes. For thinner films ([Formula: see text]37 nm) nanostructured capacitors (NSC) were employed, allowing one free surface in the film. The dielectric spectra of the thick films showed three relaxation processes ( [Formula: see text] -, [Formula: see text] - and [Formula: see text] -relaxation), like the bulk, related to PVME fluctuations in local spatial regions with different PS concentrations. The thickness dependence of the [Formula: see text] -process for films measured by CECs proved a spatially heterogeneous structure across the film with a PS-adsorption at the Al-electrodes. On the contrary, for the films measured by NSCs a PVME segregation at the free surface was found, resulting in faster dynamics, compared to the CECs. Moreover, for the thinnest films ([Formula: see text]26 nm) an additional relaxation process was detected. It was assigned to restricted fluctuations of PVME segments within the loosely bounded part of the adsorbed layer, proving that for NSCs a PVME enrichment takes place also at the polymer/substrate interface.
Nanocomposites based on MgAL layered double hydroxides (LDH) and an epoxy resin were prepared and investigated by a combination of complementary methods. As epoxy resin Bisphenol A diglycidyl ether (DGEBA) was used with Diethylenetriamine as curing agent. The LDH was modified with taurine, which acts as an additional crosslinking agent due to its amine groups. The epoxy resin was cured in a presence of the nanofiller, which was added to the system in various concentrations. X-ray scattering, by combination of SAXS and WAXS was used to characterize the morphology of the obtained nanocomposites. These investigations show that the filler is distributed in the matrix as small stacks of ca. 10 layers. The molecular dynamics of the system, as probe for structure, was investigated by broadband dielectric spectroscopy. In addition to the - and -relaxation (dynamic glass transition), characteristic for the unfilled materials, a further process was found which was assigned to localized fluctuations of segments physically adsorbed or chemically bonded to the nanoparticles. The dielectric -relaxation is shifted to higher temperatures for the nanocomposites in comparison to the pure material but depends weakly on the content of nanoparticles. Further, for the first time Flash DSC was employed to a thermosetting system to investigate the glass transition behavior of the nanocomposites. The heating rates were converted in to relaxation rates. For low concentrations of the nanofiller the thermal data overlap more or less with that of the pure epoxy. For higher concentrations the thermal data are shifted significantly to higher temperatures. This is discussed in terms the cooperativity approach to the glass transition.
The molecular mobility of the highly asymmetric miscible blend poly(vinyl methyl ether)/polystyrene was investigated by broadband dielectric (frequency range 10^-1 Hz – 10^9 Hz) and specific heat spectroscopy (frequency range 10^1 Hz – 10^4 Hz). The dielectric spectra revealed a complex molecular dynamic behavior, where three different relaxation processes were observed. At temperatures below the glass transition temperature an α´-relaxation was found, with an Arrhenius-like temperature dependence of its relaxation rates. It is assigned to localized fluctuations of the confined PVME segments within a frozen glassy matrix dominated by PS. Above the thermal glass transition temperature two processes with a VFT behavior of their relaxation rates were detected called α1- and α2-relaxation, both originating from PVME dipoles fluctuating in PS-rich environments, however with diverse PS concentrations. The relevant length scales for the processes are assumed to be different, corresponding to the Kuhn segment length for the former relaxation and to the CRR for the latter one. The observed multiple glassy dynamics result from spatial local compositional heterogeneities on a microscopic level. Additionally, SHS investigations were performed for the first time for this system, proving an existence of a fourth relaxation process (α3-relaxation) due to the cooperative fluctuations of both PS and PVME segments. The separation between the thermal α3- and dielectric α2-relaxation increases dramatically with increasing polystyrene concentration, proving that the thermal response is dominated by PS.