2018-11-02, Tahir, Muhammad, Heinrich, Gert, Mahmood, Nasir, Boldt, Regine, Wießner, Sven, Stöckelhuber, Klaus Werner

Specific physical and reactive compatibilization strategies are applied to enhance the interfacial adhesion and mechanical properties of heterogeneous polymer blends. Another pertinent challenge is the need of energy-intensive blending methods to blend high-tech polymers such as the blending of a pre-made hard polyurethane (-urea) with rubbers. We developed and investigated a reactive blending method to prepare the outstanding blends based on polyurethane-urea and rubbers at a low blending temperature and without any interfacial compatibilizing agent. In this study, the polyurethane-urea (PUU) was synthesized via the methylene diphenyl diisocyanate end-capped prepolymer and m-phenylene diamine based precursor route during blending at 100 °C with polar (carboxylated nitrile rubber (XNBR) and chloroprene rubber (CR)) and non-polar (natural rubber (NR), styrene butadiene rubber (sSBR), and ethylene propylene butadiene rubber (EPDM)) rubbers. We found that the in situ PUU reinforces the tensile response at low strain region and the dynamic-mechanical response up to 150 °C in the case of all used rubbers. Scanning electron microscopy reveals a stronger rubber/PUU interface, which promotes an effective stress transfer between the blend phases. Furthermore, energy filtered transmission electron microscopy (EFTEM) based elemental carbon map identifies an interphase region along the interface between the nitrile rubber and in situ PUU phases of this exemplary blend type.

2018-01-19, Das, Amit, Sallat, Aladdin, Böhme, Frank, Sarlin, Essi, Vuorinen, Jyrki, Vennemann, Norbert, Heinrich, Gert, Stöckelhuber, Klaus Werner

In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR). By this melt mixing process, the reactive allylic bromine of bromo-butyl rubber was converted into imidazole bromide salt. The resulting development of an ionic character to the polymer backbone leads to an ionic association of the groups which ultimately results to the formation of a network structure of the rubber chains. The modified BIIR thus behaves like a robust crosslinked rubber and shows unusual self-healing properties. The non-covalent reversible network has been studied in detail with respect to stress relaxation experiments, scanning electron microscopic and X-ray scattering.

2018-8-18, Gonçalves, Jordana, Lima, Patrícia, Krause, Beate, Pötschke, Petra, Lafont, Ugo, Gomes, José R., Abreu, Cristiano S., Paiva, Maria C., Covas, José A.

The present work reports the production and characterization of polyetheretherketone (PEEK) nanocomposite filaments incorporating carbon nanotubes (CNT) and graphite nanoplates (GnP), electrically conductive and suitable for fused deposition modeling (FDM) processing. The nanocomposites were manufactured by melt mixing and those presenting electrical conductivity near 10 S/m were selected for the production of filaments for FDM. The extruded filaments were characterized for mechanical and thermal conductivity, polymer crystallinity, thermal relaxation, nanoparticle dispersion, thermoelectric effect, and coefficient of friction. They presented electrical conductivity in the range of 1.5 to 13.1 S/m, as well as good mechanical performance and higher thermal conductivity compared to PEEK. The addition of GnP improved the composites' melt processability, maintained the electrical conductivity at target level, and reduced the coefficient of friction by up to 60%. Finally, three-dimensional (3D) printed test specimens were produced, showing a Young's modulus and ultimate tensile strength comparable to those of the filaments, but a lower strain at break and electrical conductivity. This was attributed to the presence of large voids in the part, revealing the need for 3D printing parameter optimization. Finally, filament production was up-scaled to kilogram scale maintaining the properties of the research-scale filaments.

2017, Szwed, Małgorzata, Pin´skwar, Iwona, Kundzewicz, Zbigniew W., Graczyk, Dariusz, Mezghani, Abdelkader

The present paper examines variability of characteristics of snow cover (snow cover depth, number of days with snow cover and dates of beginning and end of snow cover) in Poland. The study makes use of a set of 43 long time series of observation records from the stations in Poland, from 1952 to 2013. To describe temporal changes in snow cover characteristics, the intervals of 1952–1990 and of 1991–2013 are compared and trends in analysed data are sought (e.g., using the Mann–Kendall test). Observed behaviour of time series of snow-related variables is complex and not easy to interpret, for instance because of the location of the research area in the zone of transitional moderate climate, where strong variability of climate events is one of the main attributes. A statistical link between the North Atlantic Oscillation (NAO) index and the snow cover depth, as well as the number of snow cover days is found.

2018-12-21, Christ, Josef F., Aliheidari, Nahal, Pötschke, Petra, Ameli, Amir

Fabricating complex sensor platforms is still a challenge because conventional sensors are discrete, directional, and often not integrated within the system at the material level. Here, we report a facile method to fabricate bidirectional strain sensors through the integration of multiwalled carbon nanotubes (MWCNT) and multimaterial additive manufacturing. Thermoplastic polyurethane (TPU)/MWCNT filaments were first made using a two-step extrusion process. TPU as the platform and TPU/MWCNT as the conducting traces were then 3D printed in tandem using multimaterial fused filament fabrication to generate uniaxial and biaxial sensors with several conductive pattern designs. The sensors were subjected to a series of cyclic strain loads. The results revealed excellent piezoresistive responses with cyclic repeatability in both the axial and transverse directions and in response to strains as high as 50%. It was shown that the directional sensitivity could be tailored by the type of pattern design. A wearable glove, with built-in sensors, capable of measuring finger flexure was also successfully demonstrated where the sensors are an integral part of the system. These sensors have potential applications in wearable electronics, soft robotics, and prosthetics, where complex design, multi-directionality, embedding, and customizability are demanded.

2018, Sallat, Aladdin, Das, Amit, Schaber, Jana, Scheler, Ulrich, Bhagavatheswaran, Eshwaran S., Stöckelhuber, Klaus W., Heinrich, Gert, Voit, Brigitte, Böhme, Frank

Rubber composites were prepared by mixing bromobutyl rubber (BIIR) with silica particles in the presence of 1-butylimidazole. In addition to pristine (precipitated) silica, silanized particles with aliphatic or imidazolium functional groups, respectively, were used as filler. The silanization was carried out either separately or in situ during compounding. The silanized particles were characterized by TGA, 1H-29Si cross polarization (CP)/MAS NMR, and Zeta potential measurements. During compounding, the bromine groups of BIIR were converted with 1-butylimidazole to ionic imidazolium groups which formed a dynamic network by ionic association. Based on DMA temperature and strain sweep measurements as well as cyclic tensile tests and stress-strain measurements it could be concluded that interactions between the ionic groups and interactions with the functional groups of the silica particles strongly influence the mechanical and viscoelastic behavior of the composites. A particularly pronounced reinforcing effect was observed for the composite with pristine silica, which was attributed to acid-base interactions between the silanol and imidazolium groups. In composites with alkyl or imidazolium functionalized silica particles, the interactions between the filler and the rubber matrix form dynamic networks with pronounced self-healing behavior and excellent tensile strength values of up to 19 MPa. This new approach in utilizing filler-matrix interactions in the formation of dynamic networks opens up new avenues in designing new kinds of particle-reinforced self-healing elastomeric materials with high technological relevance.

2018, Piniewski, Mikołaj, Marcinkowski, Paweł, Kundzewicz, Zbigniew W.

The issue of trend detection in long time series of river flow records is of vast theoretical interest and considerable practical relevance. Water management is based on the assumption of stationarity; hence, it is crucial to check whether taking this assumption is justified. The objective of this study is to analyse long-term trends in selected river flow indices in small- and medium-sized catchments with relatively unmodified flow regime (semi-natural catchments) in Poland. The examined indices describe annual and seasonal average conditions as well as annual extreme conditions—low and high flows. The special focus is on the spatial analysis of trends, carried out on a comprehensive, representative data set of flow gauges. The present paper is timely, as no spatially comprehensive studies (i.e. covering the entire Poland or its large parts) on trend detection in time series of river flow have been done in the recent 15 years or so. The results suggest that there is a strong random component in the river flow process, the changes are weak and the spatial pattern is complex. Yet, the results of trend detection in different indices of river flow in Poland show that there exists a spatial divide that seems to hold quite generally for various indices (annual, seasonal, as well as low and high flow). Decreases of river flow dominate in the northern part of the country and increases usually in the southern part. Stations in the central part show mostly ‘no trend’ results. However, the spatial gradient is apparent only for the data for the period 1981–2016 rather than for 1956–2016. It seems also that the magnitude of increases of river flow is generally lower than that of decreases.

2017-5-18, Müller, Michael Thomas, Hilarius, Konrad, Liebscher, Marco, Lellinger, Dirk, Alig, Ingo, Pötschke, Petra

The influence of the morphology of industrial graphite nanoplate (GNP) materials on their dispersion in polycarbonate (PC) is studied. Three GNP morphology types were identified, namely lamellar, fragmented or compact structure. The dispersion evolution of all GNP types in PC is similar with varying melt temperature, screw speed, or mixing time during melt mixing. Increased shear stress reduces the size of GNP primary structures, whereby the GNP aspect ratio decreases. A significant GNP exfoliation to individual or few graphene layers could not be achieved under the selected melt mixing conditions. The resulting GNP macrodispersion depends on the individual GNP morphology, particle sizes and bulk density and is clearly reflected in the composite's electrical, thermal, mechanical, and gas barrier properties. Based on a comparison with carbon nanotubes (CNT) and carbon black (CB), CNT are recommended in regard to electrical conductivity, whereas, for thermal conductive or gas barrier application, GNP is preferred.

2019-12-7, Krause, Beate, Barbier, Carine, Levente, Juhasz, Klaus, Maxim, Pötschke, Petra

The aim of this study is to reveal the influences of carbon nanotube (CNT) and polymer type as well as CNT content on electrical conductivity, Seebeck coefficient (S), and the resulting power factor (PF) and figure of merit (ZT). Different commercially available and laboratory made CNTs were used to prepare melt-mixed composites on a small scale. CNTs typically lead to p-type composites with positive S-values. This was found for the two types of multi-walled CNTs (MWCNT) whereby higher Seebeck coefficient in the corresponding buckypapers resulted in higher values also in the composites. Nitrogen doped MWCNTs resulted in negative S-values in the buckypapers as well as in the polymer composites. When using single-walled CNTs (SWCNTs) with a positive S-value in the buckypapers, positive (polypropylene (PP), polycarbonate (PC), poly (vinylidene fluoride) (PVDF), and poly(butylene terephthalate) (PBT)) or negative (polyamide 66 (PA66), polyamide 6 (PA6), partially aromatic polyamide (PARA), acrylonitrile butadiene styrene (ABS)) S-values were obtained depending on the matrix polymer and SWCNT type. The study shows that the direct production of n-type melt-mixed polymer composites from p-type commercial SWCNTs with relatively high Seebeck coefficients is possible. The highest Seebeck coefficients obtained in this study were 66.4 µV/K (PBT/7 wt % SWCNT Tuball) and −57.1 µV/K (ABS/0.5 wt % SWCNT Tuball) for p-and n-type composites, respectively. The highest power factor and ZT of 0.28 µW/m·K2 and 3.1 × 10−4, respectively, were achieved in PBT with 4 wt % SWCNT Tuball.

2019, Joksch, M., Spannenberg, A., Beweries, T.

In the crystal structure of the isostructural title compounds, namely {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridopalladium(II), [Pd(C22H39O3P2)Cl], 1, and {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridoplatinum(II), [Pt(C22H39O3P2)Cl], 2, the metal centres are coordinated in a distorted square-planar fashion by the POCOP pincer fragment and the chloride ligand. Both complexes form strong hydrogen-bonded chain structures through an interaction of the OH group in the 4-position of the aromatic POCOP backbone with the halide ligand.