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The Localization Behavior of Different CNTs in PC/SAN Blends Containing a Reactive Component

2021-3-1, Gültner, Marén, Boldt, Regine, Formanek, Petr, Fischer, Dieter, Simon, Frank, Pötschke, Petra

Co-continuous blend systems of polycarbonate (PC), poly(styrene-co-acrylonitrile) (SAN), commercial non-functionalized multi-walled carbon nanotubes (MWCNTs) or various types of commercial and laboratory functionalized single-walled carbon nanotubes (SWCNTs), and a reactive component (RC, N-phenylmaleimide styrene maleic anhydride copolymer) were melt compounded in one step in a microcompounder. The blend system is immiscible, while the RC is miscible with SAN and contains maleic anhydride groups that have the potential to reactively couple with functional groups on the surface of the nanotubes. The influence of the RC on the localization of MWCNTs and SWCNTs (0.5 wt.%) was investigated by transmission electron microscopy (TEM) and energy-filtered TEM. In PC/SAN blends without RC, MWCNTs are localized in the PC component. In contrast, in PC/SAN-RC, the MWCNTs localize in the SAN-RC component, depending on the RC concentration. By adjusting the MWCNT/RC ratio, the localization of the MWCNTs can be tuned. The SWCNTs behave differently compared to the MWCNTs in PC/SAN-RC blends and their localization occurs either only in the PC or in both blend components, depending on the type of the SWCNTs. CNT defect concentration and surface functionalities seem to be responsible for the localization differences.

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Epitaxial stannate pyrochlore thin films: Limitations of cation stoichiometry and electron doping

2021, Hensling, Felix V. E., Dahliah, Diana, Dulal, Prabin, Singleton, Patrick, Sun, Jiaxin, Schubert, Jürgen, Paik, Hanjong, Subedi, Indra, Subedi, Biwas, Rignanese, Gian-Marco, Podraza, Nikolas J., Hautier, Geoffroy, Schlom, Darrell G.

We have studied the growth of epitaxial films of stannate pyrochlores with a general formula A2Sn2O7 (A = La and Y) and find that it is possible to incorporate ∼25% excess of the A-site constituent; in contrast, any tin excess is expelled. We unravel the defect chemistry, allowing for the incorporation of excess A-site species and the mechanism behind the tin expulsion. An A-site surplus is manifested by a shift in the film diffraction peaks, and the expulsion of tin is apparent from the surface morphology of the film. In an attempt to increase La2Sn2O7 conductivity through n-type doping, substantial quantities of tin have been substituted by antimony while maintaining good film quality. The sample remained insulating as explained by first-principles computations, showing that both the oxygen vacancy and antimony-on-tin substitutional defects are deep. Similar conclusions are drawn on Y2Sn2O7. An alternative n-type dopant, fluorine on oxygen, is shallow according to computations and more likely to lead to electrical conductivity. The bandgaps of stoichiometric La2Sn2O7 and Y2Sn2O7 films were determined by spectroscopic ellipsometry to be 4.2 eV and 4.48 eV, respectively. © 2021 Author(s).

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Blend Structure and n-Type Thermoelectric Performance of PA6/SAN and PA6/PMMA Blends Filled with Singlewalled Carbon Nanotubes

2021-4-28, Krause, Beate, Liguoro, Alice, Pötschke, Petra

The present study investigates how the formation of melt-mixed immiscible blends based on PA6/SAN and PA6/PMMA filled with single walled nanotubes (SWCNTs) affects the thermoelectric (TE) properties. In addition to the detailed investigation of the blend morphology with compositions between 100/0 wt.% and 50/50 wt.%, the thermoelectric properties are investigated on blends with different SWCNT concentrations (0.25–3.0 wt.%). Both PA6 and the blend composites with the used type of SWCNTs showed negative Seebeck coefficients. It was shown that the PA6 matrix polymer, in which the SWCNTs are localized, mainly influenced the thermoelectric properties of blends with high SWCNT contents. By varying the blend composition, an increase in the absolute Seebeck coefficient, power factor (PF), and figure of merit (ZT) was achieved compared to the PA6 composite which is mainly related to the selective localization and enrichment of SWCNTs in the PA6 matrix at constant SWCNT loading. The maximum PFs achieved were 0.22 µW/m·K2 for PA6/SAN/SWCNT 70/30/3 wt.% and 0.13 µW/m·K2 for PA6/PMMA/SWCNT 60/40/3 wt.% compared to 0.09 µW/m·K2 for PA6/3 wt.% SWCNT which represent increases to 244% and 144%, respectively. At higher PMMA or SAN concentration, the change from matrix-droplet to a co-continuous morphology started, which, despite higher SWCNT enrichment in the PA6 matrix, disturbed the electrical conductivity, resulting in reduced PFs with still increasing Seebeck coefficients. At SWCNT contents between 0.5 and 3 wt.% the increase in the absolute Seebeck coefficient was compensated by lower electrical conductivity resulting in lower PF and ZT as compared to the PA6 composites.

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Morphology and Physico-Mechanical Threshold of α-Cellulose as Filler in an E-SBR Composite

2021, Chowdhury, Soumya Ghosh, Chanda, Jagannath, Ghosh, Sreedip, Pal, Abhijit, Ghosh, Prasenjit, Bhattacharyya, Sanjay Kumar, Mukhopadhyay, Rabindra, Banerjee, Shib Shankar, Das, Amit

In the current context of green mobility and sustainability, the use of new generation natural fillers, namely, α-cellulose, has gained significant recognition. The presence of hydroxyl groups on α-cellulose has generated immense eagerness to map its potency as filler in an elastomeric composite. In the present work, α-cellulose-emulsion-grade styrene butadiene rubber (E-SBR) composite is prepared by conventional rubber processing method by using variable proportions of α-cellulose (1 to 40 phr) to assess its reinforce ability. Rheological, physical, visco-elastic and dynamic-mechanical behavior have clearly established that 10 phr loading of α-cellulose can be considered as an optimized dosage in terms of performance parameters. Morphological characterization with the aid of scanning electron microscope (SEM) and transmission electron microscopy (TEM) also substantiated that composite with 10 phr loading of α-cellulose has achieved the morphological threshold. With this background, synthetic filler (silica) is substituted by green filler (α-cellulose) in an E-SBR-based composite. Characterization of the compound has clearly established the reinforcement ability of α-cellulose.

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Investigating the morphology of bulk heterojunctions by laser photoemission electron microscopy

2022, Niefind, Falk, Shivhare, Rishi, Mannsfeld, Stefan C.B., Abel, Bernd, Hambsch, Mike

The nanoscale morphology of bulk heterojunctions is highly important for the charge dissociation and transport in organic solar cells and ultimately defines the performance of the cell. The visualization of this nano-morphology in terms of domain size and polymer orientation in a fast and straightforward way is therefore of great interest to evaluate the suitability of a film for efficient solar cells. Here, we demonstrate that the morphology of different blends of poly(3-hexylthiophene-2,5-diyl) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) can be imaged and analyzed by employing photoemission electron microscopy.

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Controlling line defects in wrinkling: a pathway towards hierarchical wrinkling structures

2021, Knapp, André, Nebel, Lisa Julia, Nitschke, Mirko, Sander, Oliver, Fery, Andreas

We demonstrate a novel approach for controlling the line defect formation in microscopic wrinkling structures by patterned plasma treatment of elastomeric surfaces. Wrinkles were formed on polydimethylsiloxane (PDMS) surfaces exposed to low-pressure plasma under uniaxial stretching and subsequent relaxation. The wrinkling wavelength λ can be regulated via the treatment time and choice of plasma process gases (H2, N2). Sequential masking allows for changing these parameters on micron-scale dimensions. Thus, abrupt changes of the wrinkling wavelength become feasible and result in line defects located at the boundary zone between areas of different wavelengths. Wavelengths, morphology, and mechanical properties of the respective areas are investigated by Atomic Force Microscopy and agree quantitatively with predictions of analytical models for wrinkle formation. Notably, the approach allows for the first time the realization of a dramatic wavelength change up to a factor of 7 to control the location of the branching zone. This allows structures with a fixed but also with a strictly alternating branching behavior. The morphology inside the branching zone is compared with finite element methods and shows semi-quantitative agreement. Thus our finding opens new perspectives for “programming” hierarchical wrinkling patterns with potential applications in optics, tribology, and biomimetic structuring of surfaces.