Eija Kenttä

Hydrophobization of cellophane and cellulose nano-fibrils films by supercritical state carbon dioxide impregnation with walnut oil

Bio-based films are typically sensitive towards moisture which limits the industrial applicability. In this study the cellulosic films produced from cellulose nanofibrils and cellophane were treated using supercritical state carbon dioxide impregnation with hydrophobic polyunsaturated oil mixture (walnut oil). The effects on surface hydrophobicity with cellophane films were clear and indisputable. Water contact angles of non-treated cellophane, walnut oil impregnated and further 1,6-hexanediol dimethacrylate crosslinked films were 62, 82 and 91°, respectively. Also the moisture absorption and water vapour transmission rate as well as oxygen transmission rate at 80% relative humidity decreased as a result of supercritical state carbon dioxide impregnation. Water vapour transmission rate of walnut oil impregnated cellulose nanofibrils film decreased by 30% as compared to non-treated film. Based on the FTIR analysis and surface roughness measurements the walnut oil penetrated better into the structure of cellophane as compared to CNF film. The developed hydrophobization method can be exploited in strengthening the position of cellulosic films in high performance film applications.

Molecular Layer Deposition Using Ring-Opening Reactions: Molecular Modeling of the Film Growth and the Effects of Hydrogen Peroxide

Novel coating materials are constantly needed for current and future applications in the area of microelectronics, biocompatible materials, and energy-related devices. Molecular layer deposition (MLD) is answering this cry and is an increasingly important coating method for organic and hybrid organic–inorganic thin films. In this study, we have focused on hybrid inorganic–organic coatings, based on trimethylaluminum, monofunctional aromatic precursors, and ring-opening reactions with ozone. We present the MLD processes, where the films are produced with trimethylaluminum, one of the three aromatic precursors (phenol, 3-(trifluoromethyl)phenol, and 2-fluoro-4-(trifluoromethyl)benzaldehyde), ozone, and the fourth precursor, hydrogen peroxide. According to the in situ Fourier-transform infrared spectroscopy measurements, the hydrogen peroxide reacts with the surface carboxylic acid group, forming a peroxyacid structure (C(O)–O–OH), in the case of all three processes. In addition, molecular modeling for the processes with three different aromatic precursors was carried out. When combining these modeling results with the experimental research data, new interesting aspects of the film growth, reactions, and properties are exploited.

Low-temperature Molecular Layer Deposition Using Monofunctional Aromatic Precursors and Ozone-based Ring Opening Reactions

Molecular layer deposition (MLD) is an increasingly used deposition technique for producing thin coatings consisting of purely organic or hybrid inorganic-organic materials. When organic materials are prepared, low deposition temperatures are often required to avoid decomposition, thus causing problems with low vapor pressure precursors. Monofunctional compounds have higher vapor pressures than traditional bi- or trifunctional MLD precursors, but do not offer the required functional groups for continuing the MLD growth in subsequent deposition cycles. In this study, we have used high vapor pressure monofunctional aromatic precursors in combination with ozone-triggered ring-opening reactions to achieve sustained sequential growth. MLD depositions were carried out by using three different aromatic precursors in an ABC sequence, namely with TMA + phenol + O3, TMA + 3-(trifluoromethyl)phenol + O3, and TMA + 2-fluoro-4-(trifluoromethyl)benzaldehyde + O3. Furthermore, the effect of hydrogen peroxide as a fourth step was evaluated for all studied processes resulting in a four-precursor ABCD sequence. According to the characterization results by ellipsometry, infrared spectroscopy, and X-ray reflectivity, self-limiting MLD processes could be obtained between 75 and 150 °C with each of the three aromatic precursors. In all cases, the GPC (growth per cycle) decreased with increasing temperature. In situ infrared spectroscopy indicated that ring-opening reactions occurred in each ABC sequence. Compositional analysis using time-of-flight elastic recoil detection indicated that fluorine could be incorporated into the film when 3-(trifluoromethyl)phenol and 2-fluoro-4-(trifluoromethyl)benzaldehyde were used as precursors.