Plasma deposited thin layers of amorphous hydrogenated carbon (a-C:H) on selected biodegradable polymer films - Layer thickness and substrate dependent carbon hybridisation and its effect on layer stability

  • The three biodegradable polymers polylactic acid (PLA), polyhydroxybutyrate (PHB) and polybutylene adipate terephthalate (PBAT) were coated with hydrogenated amorphous carbon layers (a-C:H) in the context of this thesis. A direct alignment of the sample surface to the source was chosen, resulting in the deposition of a robust, r-type a-C:H. At the same time, a partly covered silicon wafer was placed together with the polymers in the coating chamber and was coated. Silicon is a hard material and serves as a reference for the applied layers. Due to the hardness of the material, no mixed phase occurs between the substrate and the applied layer (no interlayer formation). In addition, the thickness of the applied layer can be estimated with the help of the silicon sample. The deposition of the layer was realized by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD). For the coating the samples were pre-treated with an oxygen plasma. Acetylene was used as precursor gas for the plasma coating. Coatings with increasing thickness in 50 nm steps from 0-500 nm were realised. The surface analysis was performed using several techniques: The morphology and layer stability were analyzed with scanning electron microscopy (SEM) measurements. The wettability was determined by contact angle technique. In addition, the contact angles provide macroscopic information about the bond types of the carbon atoms present on the surface. For microscopic analysis of the chemical composition of the sample and layer surfaces, diffuse reflectance Fourier transform infrared spectroscopy (DRIFT) as well as synchrotron based X-ray photon spectroscopy (XPS) and near edge X-ray absorption fine structure spectroscopy (NEXAFS) were used. All coated polymers showed several cases of layer failure due to internal stress in the layers. However, these were at different layer thicknesses, so there was a substrate effect. In addition, it is visible in the SEM images that the coatings of PLA and PHB can cause the applied layer to wave, the so-called cord buckling. This does not occur with polymer PBAT, which indicates a possible better bonding of the layer to the polymer. The chemical analyses of the layer surfaces show for each material a layer thickness dependent ratio of sp² to sp³ bonds of carbon, which alternately dominate the layer. In all polymers, the sp³ bond initially dominates, but the sp² to sp³ ratio changes at different intervals. Although the polymers were coated in the same plasma, i.e. the respective layer thicknesses (50 nm, 100 nm, ...) were applied in the same plasma process, the respective systems differed considerably from each other. A substrate effect is therefore demonstrably present. In addition, it was found that a change in the dominant bond from sp³ to sp² is an indication ofan upcoming layer failure of the a-C:H layer deposited on the polymer. In the case of PLA, this occurs immediately with change to sp² as the dominant bond; in the case of PHB and PBAT, this occurs with different delay to increased layer thicknesses (at PHB 100 nm, at PBAT approx. 200 nm. Overall, this thesis shows that there is a substrate effect in the coating of the biodegradable polymers PLA, PHB and PBAT, since despite the same coating there is a different chemical composition of the surface at the respective layer thicknesses. In addition, a layer failure can be predicted by analyzing the existing bond.

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Metadaten
Author:Torben Schlebrowski
URN:urn:nbn:de:kola-20795
Referee:Christian B. Fischer, Barbara Hahn
Advisor:Christian B. Fischer, Stefan Wehner
Document Type:Doctoral Thesis
Language:English
Date of completion:2020/07/01
Date of publication:2020/07/02
Publishing institution:Universität Koblenz-Landau, Universitätsbibliothek
Granting institution:Universität Koblenz-Landau, Campus Koblenz, Fachbereich 3
Date of final exam:2020/06/29
Release Date:2020/07/02
Tag:Kohlenstoffschichten
amorphous hydrogenated carbon layer; carbon hybridisation
GND Keyword:Beschichtung; Biopolymere; Oberflächenveredelung; Physik
Number of pages:getrennte Zählung
Institutes:Fachbereich 3 / Institut für Integrierte Naturwissenschaften / Institut für Integrierte Naturwissenschaften, Abt. Physik
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik
BKL-Classification:33 Physik / 33.68 Oberflächen, Dünne Schichten, Grenzflächen
Licence (German):License LogoEs gilt das deutsche Urheberrecht: § 53 UrhG