Alexsander Tressino de Carvalho

Hydrophobic plasma polymerized hexamethyldisilazane thin films: characterization and uses

Hexametildisilazane (HMDS) plasma polymerized thin films obtained using low frequency power supplies can be used to make adsorbent films and turn surfaces hydrophobic. The aim of this work was to verify the hydrophobicity and adsorption properties of HMDS thin films (with and without the addition of oxygen, resulting in double or single layer films) obtained using an inductive reactor powered with a 13.56 MHz power supply. Single and double layer thin films were deposited on silicon for film characterization, polypropylene (PP) for ultraviolet (UVA/UVC) resistance tests, piezoelectric quartz crystal for adsorption tests. The double layer (intermixing) of HMDS plasma polymerized films and HMDS plasma oxidized surfaces showed a non-continuous layer. The films showed good adhesion to all substrates. Infrared analysis showed the presence of CHn, SiCH3, SiNSi and SiCH2Si within the films. Contact angle measurements with water showed hydrophobic surfaces. UVA/UVC exposure of the films resulted in the presence of cross-linking on carbonic radicals and SiCH2Si formation, which resulted in a possible protection of PP against UVA/UVC for a duration of up to two weeks. Adsorption tests showed that all organic reactants were adsorbed but not water. Plasma etching (PE) using O2 showed that even after 15 minutes of exposure the films do not change their hydrophobic characteristic but were oxidized. The results point out that HMDS films can be used: for ultraviolet protection of flexible organic substrates, such as PP, for sensor and/or preconcentrator development, due to their adsorption properties, and in spatial applications due to resistance for O2 attack in hostile conditions, such as plasma etching.

USE OF THIN FILMS OBTAINED BY PLASMA POLYMERIZATION FOR GRAIN PROTECTION AND GERMINATION ENHANCEMENT

In this work, preliminary results of the use of hydrophobic thin films obtained by plasma deposition to protect grains and seeds are presented: grains coated by the films did not present biological degradation when stored in a saturated water vapor environment, but had their germination accelerated in the presence of water. A model that explains the difference of behavior of the films when exposed to water in vapor form or in liquid form, based on the formation of microchannels within the film that lead to water uptake in seeds, is presented. The model was successfully tested using quartz crystal measurements, which showed that the microchannels within the films can favor the adsorption and permeation of water when the films are immersed in water.

Use of Electroless Plating Copper Thin Films for Catalysis

Recently, it was demonstrated that copper thin films show good adsorption characteristics for organic polar and non-polar compounds. Also, these films when used in small cavities can favor preconcentration of these organic compounds. It is also known that copper oxide can provide catalysis of organic compounds. Therefore, the aim of this work is the study of copper thin film catalysis when used in small cavities. Copper thin films, 25 nm thick, were deposited on silicon and/or rough silicon. These films do not show oxide on the surface when analyzed by Rutherford backscattering. Also, Raman analysis of these films showed only silicon bands, due to the substrate, however infrared spectroscopy shows oxide bands for films exposed to organic compound aqueous solutions. Cavities with copper films deposited inside were tested with a continuous flow of n-hexane, acetone or 2-propanol admitted in the system. The effluent was analyzed by Quartz Crystal Microbalance. It was shown that n-hexane or acetone can be trapped. The system also shows good reproducibility. Tests of catalysis were carried out using Raman spectroscopy and heating the films up to 300°C during 3 minutes after exposure to n-hexane, 2- propanol and acetophenone – pure or saturated aqueous solution. After the exposure, Raman spectra present intense bands only for 2-propanol, indicating that adsorption easily occurs. However, after heating with all solutions it was not found only silicon bands. Raman microscopy after heating also showed copper oxide cluster formation and, eventually, graphite formation. Although the heating provides oxide copper formation, this reaction does not produce a high amount of residues, which means that catalysis is possible in this condition. Thus, a simple device using copper thin films can be useful as sample pretreatment on microTAS development.

Low cost microstructures for preconcentration of polar and non-polar organic compounds

Films produced by plasma polymerization of ethyl ether and methyl or ethyl acetate show good adsorption characteristic for polar and non-polar organic compounds. These films when used in microchannels machined in a 3D-structure present some preconcentration of organic compounds. Therefore, the aim of this work is to investigate the physical-chemical preconcentration mechanisms on this structure. The test molecules used were n-hexane and 2-propanol. Quartz crystal microbalance and mass spectrometry were used to measure preconcentration. Two different procedures for reactant injection on the structure were used: a continuous flow during several minutes or a small amount injected on a single pulse and in a few seconds. The microchannels were also modified by the introduction of small ceramic particles for enhancement of the flow dispersion. It was possible to notice for all films a similar kinetic of retention. The main removal mechanism is adsorption. Although all films can provide the removal of the adsorbents molecules, the most important characteristic for the adsorption and/or retention is the surface condition. Thus, the retention of polar compound can be troubled if a non-polar compound was used previously. The most promising films for retention are ethyl ether and ethyl acetate when n-hexane and 2-propanol are used as test molecules. The results using n-hexane or 2-propanol point out the use of low-cost microchannels for preconcentration development.

Plasma polymerized acetaldehyde thin films for retention of volatile organic compounds

The aim of this work is the production and characterization of plasma polymerized acetaldehyde thin films. These films show highly polar species, are hydrophilic, organophilic and easily adsorb organic reactants with CO radicals but only allow permeation of reactants with OH radicals. The good step coverage of films deposited on aluminum trenches is useful for sensor development. Films deposited on hydrophobic substrates may result in a discontinued layer, which allows the use of preconcentration in sample pretreatment. Deposition on microchannels showed the possibility of chromatographic columns and/or retention system production to selectively detect or remove organic compounds from gas flows.