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Poly(acrylonitrile-co-butadiene) as polymeric crosslinking accelerator for sulphur network formation

2020, Hait, Sakrit, Valentín, Juan López, Jiménez, Antonio González, Ortega, Pilar Bernal, Ghosh, Anik Kumar, Stöckelhuber, Klaus Werner, Wießner, Sven, Heinrich, Gert, Das, Amit

The major controlling factors that determine the various mechanical properties of an elastomer system are type of chemical crosslinking and crosslink density of the polymer network. In this study, a catalytic amount of acrylonitrile butadiene copolymer (NBR) was used as a co-accelerator for the curing of polybutadiene (BR) elastomer. After the addition of this copolymer along with other conventional sulphur ingredients in polybutadiene compounds, a clear and distinct effect on the curing and other physical characteristics was noticed. The crosslinking density of BR was increased, as evidenced by rheometric properties, solid-state NMR and swelling studies. The vulcanization kinetics study revealed a substantial lowering of the activation energy of the sulphur crosslinking process when acrylonitrile butadiene copolymer was used in the formulation. The compounds were also prepared in the presence of carbon black and silica, and it was found that in the carbon black filled system the catalytic effect of the NBR was eminent. The effect was not only reflected in the mechanical performance but also the low-temperature crystallization behavior of BR systems was altered. © 2020 The AuthorsMaterials science; Materials chemistry; Crosslinking accelerator; Sulphur network; Solid state NMR; Curing kinetics; Activation energy; Acrylonitrile butadiene; Polybutadiene; Low-temperature; Crystallization. © 2020 The Authors

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Precursor-surface interactions revealed during plasma-enhanced atomic layer deposition of metal oxide thin films by in-situ spectroscopic ellipsometry

2020, Kilic, Ufuk, Mock, Alyssa, Sekora, Derek, Gilbert, Simeon, Valloppilly, Shah, Melendez, Giselle, Ianno, Natale, Langell, Marjorie, Schubert, Eva, Schubert, Mathias

We find that a five-phase (substrate, mixed native oxide and roughness interface layer, metal oxide thin film layer, surface ligand layer, ambient) model with two-dynamic (metal oxide thin film layer thickness and surface ligand layer void fraction) parameters (dynamic dual box model) is sufficient to explain in-situ spectroscopic ellipsometry data measured within and across multiple cycles during plasma-enhanced atomic layer deposition of metal oxide thin films. We demonstrate our dynamic dual box model for analysis of in-situ spectroscopic ellipsometry data in the photon energy range of 0.7–3.4 eV measured with time resolution of few seconds over large numbers of cycles during the growth of titanium oxide (TiO2) and tungsten oxide (WO3) thin films, as examples. We observe cyclic surface roughening with fast kinetics and subsequent roughness reduction with slow kinetics, upon cyclic exposure to precursor materials, leading to oscillations of the metal thin film thickness with small but positive growth per cycle. We explain the cyclic surface roughening by precursor-surface interactions leading to defect creation, and subsequent surface restructuring. Atomic force microscopic images before and after growth, x-ray photoelectron spectroscopy, and x-ray diffraction investigations confirm structural and chemical properties of our thin films. Our proposed dynamic dual box model may be generally applicable to monitor and control metal oxide growth in atomic layer deposition, and we include data for SiO2 and Al2O3 as further examples.