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Optimization of electrochemical sensor for detection in microvolume
Gajdoš, Libor ; Pekárek, Jan (referee) ; Prášek, Jan (advisor)
This thesis describes optimization and modification of standard thick-film electrochemical sensor to be able to be used for detection in microvolumes. In the theoretical part, the thick film technology is described. The work is then focused on the wettability of surfaces followed by introduction to electrochemistry and electro-analytical methods. In the experimental part, screen-printing of various types of thick film pastes on ceramic substrates for determination of their wettability and the following modification of the sensors with thick-film paste and with Parylene vaporization can be found, as well as the basic electrochemical measurements in microvolume using the modified sensor. Finally the results are summarized in conclusion.
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Mechanical and Electrical Properties of Thin Metal Films Deposited by Vacuum Evaporation
W. F. Yahya, Doaa ; Kolařík, Vladimír (referee) ; Štencl,, Jiří (referee) ; Šandera, Josef (advisor)
Thin layers are widely used in many fields of technology and today we can say that they are found in all modern technologies. Thin layers can be created in two ways, namely by chemical or physical means. This work focuses on the latter method, more particularly a technology of thermal evaporation of thin layers in a vacuum. The work focuses on the process principles during and after the evaporation. Much of the work focuses on the development and design of experiments. These experiments illustrate some of the phenomena that take place on thin films produced by the aforementioned technology. Work helps to better understand processes during formation of thin layers and properties that influence the quality and stability of thin films. In conclusion we describe results of experiments and new developments in the field of thin films deposition using evaporation under vakuum are summarized.
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Barier films based on polyparaxylylene and their properties
Horák, Jakub ; Mazánková, Věra (referee) ; Přikryl, Radek (advisor)
This diploma thesis is focused on preparation and characterization of parylene C barrier properties. The layers were prepared by chemical vapour deposition (CVD). The interest in characterization of those layers is huge mainly because of their possible use in museology for the protection of the museum archives against the corrosion. Chlorinated dimer of para-xylylene was used as a precursor. Polypropylene foils, metal sheets and silica wafers were used as tested substrates for thin film preparation. Polypropylene foils were used for oxygen transmission rate measurements, metal sheets were used for corrosion tests and silica wafers were used for Fourier transform infrared spectroscopy (FTIR), confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM) and stylus profilometry.
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Poly-para-xylylene films preparation and characterization of their properties
Menčík, Přemysl ; Salyk, Ota (referee) ; Přikryl, Radek (advisor)
Poly-p-xylylene is a basic polymer of parylene family. It was discovered in 50s of the 20th century. In practical applications, there are used several derivates. Most of them are discussed in this thesis. Poly-p-xylylene has many utility properties, like barrier, thermal and mechanical properties. It can be used for conservation and protection of electronic equipments, medical tools and devices or museum exhibits. The most important property of parylene is its low dielectric constant which enables parylene to have good insulating properties in form of very thin layer. The most common precursor used for parylene coatings by Chemical Vapor Deposition (CVD) is [2,2]paracyclophane. Special device invented for this process was described in this thesis, including every part and assembly. The main aim of this thesis was to test properties of thin parylene layers on metal samples. High degree of polymer crystallinity was confirmed by confocal laser microscopy and optical microscopy in the polarized light measurements. Problems in the conventional method of production of parylene layers were found during the measurement of thickness of layers. Purity of deposited films was determined using Infrared spectroscopy (IR). Parylene barrier properties were quantified by the measurement of Oxygen Transmission Rate through a layer deposited on the surface of PP foil. Because the research has been mainly focused on protection of museum exhibits, the corrosion resistance test is the most important. Metal samples with thin parylene film were compared to samples with conventional restoration coating. The samples with parylene protection were slowly corroded by point corrosion. In contrast to them, the samples conserved by conventional restoration method were almost destroyed by corrosion.
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Preparation and characterization of thin barrier layers
Blahová, Lucie ; Mráček, Aleš (referee) ; Buršíková, Vilma (referee) ; Krčma, František (advisor)
Combinations of different acrylic resins and microcrystalline waxes are most often used for the conservation and preservation of metallic archaeological artefacts these days. However, their properties are not sufficient and satisfactory in many ways. Therefore, the aim of this doctoral thesis is to develop a conservation system which will draw on the new knowledge gained in the field of advanced materials and technologies during last years. A conservation coating based on a thin barrier film appears the most promising. The conservation coating must fulfil particularly following rather contradictory requirements: good barrier function against oxygen, humidity and other corrosive agents; transparency because of colour appearance preservation; long term stability and easy removability; possibility to apply to more objects at the same time and reasonable financial requirements of a deposition process. Parylene C polymer was chosen as suitable material for this purpose. It was prepared via modified chemical vapour deposition. Parylene removability was ensured through the soluble interlayer made of Laksil silicone-acrylic lacquer which was applied between the protected metallic object and the parylene thin film. Initially, the deposition process of Laksil/parylene bilayer was optimized, then its physical and chemical characteristics were determined and eventually, they were compared with the conventional conservation coating composed of Paraloid B72 acrylic resin and Revax microcrystalline wax. Regarding to the demands of the conservation coating, we were interested especially in barrier properties, optical properties, surface morphology and removability of Laksil/parylene bilayer. The most useful method for description of coating barrier properties was corrosion testing in which coated metallic samples were exposed to highly corrosive environment of salt spray (made of 50 g•l–1 brine), 100% humidity and temperature of 35 °C (ISO 9227). The Laksil/parylene bilayer showed excellent barrier properties; samples treated this way sustained unchanged in the corrosion chamber for almost three months. The surface roughness measured by profilometry and surface morphology scanned by SEM illustrated the synergy between Laksil and parylene layer which leads to the exceptional barrier and anticorrosion function of bilayer. The Laksil layer is able to flatten out rough surface of a substrate. Furthermore, it can toughen the item surface which is, in case of a number of archaeological findings, created by corrosion product layers with variable mechanical strength. Thereon deposited parylene film becomes smooth and defect free and can act as a good diffusion barrier. The colouristic measurements confirmed that the Laksil/parylene bilayer does not almost change the appearance of protected item, in terms of colour. The caused colour difference (ISO 11664-4) ranged around 1 which value is defined as “perceivable only for experienced observers”. The Laksil/parylene bilayer is removable thanks to the Laksil solubility in xylene. It is necessary to carefully scratch the outer parylene film to enable access of xylene solvent to the lacquer. The successful removal of Laksil/parylene bilayer was first confirmed by the EDX on metallic iron samples. Afterwards, the possibility of bilayer complete removal even from a corroded surface of the original artefact was proved by TGA. Thus the conservation treatment can be considered fully reversible.
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Multilayer barrier coatings
Sedláček, Ondřej ; Mazánková, Věra (referee) ; Přikryl, Radek (advisor)
The theme of this work is the preparation and characterization of multilayer barrier coatings to polymer and metal substrates based on SiOx and organic molecules. It deals with the determination of their properties in terms of oxygen permeability and corrosion protection. The starting materials for the preparation of these layers are hexamethyldisiloxane, octafluorocyclobutane and 4,12-dichloro[2.2]paracyclophane. These layers have been prepared with regard to their use as barrier coatings for use in archeology, with the focus on corrosion protection of coated items and other specific requirements museums. For these samples was realized characteristic of both in terms of their physical properties – the ability to resist permeation of oxygen and in terms of their chemical composition. The fourier transformation infrared spectroscopy (FTIR), scanning elektron microscopy (SEM), oxygen transmission rate (OTR), contac angle measurement and corrosion testing were used for the above-mentioned characterisations.
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Barriere layers for culture herritage objects preservation
Procházka, Michal ; Lehocký, Marián (referee) ; Zahoranová, Anna (referee) ; Krčma, František (advisor)
Every year, many archeological findings are discovered. It is necessary to document and conserve these items dug up from the ground. However, archeologists and conservators cannot handle such a big amount of newly found items. This work offers an alternative approach to standard conservation techniques, increasing the processing capacity and lowering the cost on items’ conservation. Studied alternative, mainly for protection of metallic artefacts, includes thin films based on parylene and organosilicons. Thin films were prepared on two experimental apparatuses. Parylene films were deposited by chemical vapour deposition (CVD). Final product was a thin film of parylene C. Organosilicon thin films were deposited via plasma enhanced chemical vapour deposition (PECVD). PECVD apparatus operates with capacitively coupled radiofrequently initiated plasma. Using hexamethyldisiloxane, thin films very similar to silicon dioxide were produced, thus called SiOx. Thin films were characterized by several methods and compared to standard treatment used by conservators – tannate layer, acrylic furnish Paraloid B72 and microcrystalline wax Revax 30. Parylene films showed excellent conformity and resistance to corrosion on iron substrate. First signs of corrosion were observed on layer of 5 µm thickness after 24 hours in salt fog. On samples coated by SiOx films, corrosion was spreading wide even during 1st hour of the corrosion test. Most probable cause was that SiOx film has thermal expansion coefficient different from iron substrate and due to this fact cracking occurs during cooling down of the treated substrate. On samples coated by standard treatment, corrosion occurred after 1-3 hours of the test. Oxygen transmission rate (OTR) measurements (performed on polypropylene substrate) confirmed good barrier properties of parylene C. Best parylene thin films had OTR approximately 170 cm3•m-2•atm-1•day-1. SiOx films reached good results with OTR 300 cm3•m-2•atm-1•day-1, compared to clean polypropylene substrate with OTR 1700 cm3•m-2•atm-1•day-1. Standard conservation layers could not be applied on polypropylene substrate, thus their OTR was not measured. We did not succeed in finding a substrate which is compatible for all types of treatments. Next, the study focused on combinations of thin films forming sandwich structures. All types let the corrosion attack the substrate during the 1st hour of the test. The cause was insufficient film thickness as well as crack ing of SiOx films due to different thermal expansion properties from the iron substrate. Although SiOx thin films were not deposited on substrate directly, they have excellent adhesion to parylenu and thus they could tear parylenu films due to thermal expansion. However, OTR measurements showed improvement in barrier properties. Multilayer parylene C–SiOx–parylene C–SiOx had OTR 5 cm3•m-2•atm-1•day-1. Final result is that parylene C thin films have better barrier properties than standard coatings and are suitable for conservation of metallic archaeological artefacts. SiOx films and multilayers showed poor anticorrosion protection of metallic substrates but they have good barrier and chemical properties in combination with other types of substrates. Mainly deposited on polymers, there is great potential for their application in many fields. Further research would be focused on new substrates for SiOx thin films and on the improvement of UV stability of parylene films.
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Barier Coatings based on Polyparaxylylene for the Space Research Applications
Horák, Jakub ; Zahoranová, Anna (referee) ; Mráček, Aleš (referee) ; Krčma, František (advisor)
Titan, a moon of the planet Saturn, is interesting to many researchers for its thick atmosphere, which, like its surface, is composed mainly of nitrogen (95%) and methane (5%) with various hydrocarbons, and thanks to the conditions that prevail on Titan, it is considered to be a model of Earth in the time before the origin of life. In order to be able to monitor the processes that take place on various space bodies, it is necessary to successfully transfer a space probe to them and thoroughly protect the electronics, which is affected by many adverse effects during takeoff, flight and landing, like thermal fluctuations, various radiation or the atmosphere of the space body to which the electronics may be exposed if the integrity of the probe shell is compromised (for example, in the case of landing modules). Parylene layers are already used in space research, and the aim of this work is a deeper understanding of the changes of their mechanical, chemical and physical properties after their exposure to the simulated atmosphere of Titan and UV radiation. Two thickness sets of parylene layers (2 and 6 µm) were prepared, which were subsequently exposed to the influence of a simulated atmosphere with a methane content of 1, 3 and 5% – at laboratory and reduced temperatures (cooling with liquid nitrogen). In each set, the samples were always duplicated, thanks to which we obtained two sets of samples – the first was affected only by the conditions used in the simulation of atmospheric events on Titan (reaction products and the used discharge) and the second set, which was additionally degraded using UV radiation (possible influence of photons). The effect of such treatments was characterized using FTIR and other analytical methods. It turns out that even when exposed to the conditions of the simulated atmosphere, photooxidation occurs for most of the samples exposed to the mixture with the highest methane content. For some samples, this led to a reduction of a subsequent effect of applied UV radiation, which is probably the result of the parylene layer cross-linking. AFM confirmed that the reactions taking place on the layers during the simulation of the atmosphere increase their roughness, and that after exposure to UV radiation, the layers exposed to Titan's atmosphere at laboratory and reduced temperatures exhibit strong surface degradation. This was also confirmed during nanoindentation, where the layers without the influence of secondary UV radiation did not show an increase in hardness or elastic modulus, while after UV irradiation the values were almost doubled, and their uncertainties also increased significantly. The strong degradation effect of the applied UV radiation was observed by SEM as well – these samples were almost impossible to measure due to the strong charging and visible in-situ deformation by the used electron beam. The work also included the synthesis of silver and copper nanoparticles for their later targeted incorporation into parylene layers. Nanoparticles were prepared by using electrical discharge in liquids. While the silver nanoparticles were metallic and spherical in shape, a nanowhiskers structure and significant agglomeration were observed for the copper-based particles; their surface was not metallic but formed of oxides/hydroxides. The direct application of nanoparticles into the parylene layers could not be implemented, yet.
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Preparation and characterization of thin barrier layers
Blahová, Lucie ; Mráček, Aleš (referee) ; Buršíková, Vilma (referee) ; Krčma, František (advisor)
Combinations of different acrylic resins and microcrystalline waxes are most often used for the conservation and preservation of metallic archaeological artefacts these days. However, their properties are not sufficient and satisfactory in many ways. Therefore, the aim of this doctoral thesis is to develop a conservation system which will draw on the new knowledge gained in the field of advanced materials and technologies during last years. A conservation coating based on a thin barrier film appears the most promising. The conservation coating must fulfil particularly following rather contradictory requirements: good barrier function against oxygen, humidity and other corrosive agents; transparency because of colour appearance preservation; long term stability and easy removability; possibility to apply to more objects at the same time and reasonable financial requirements of a deposition process. Parylene C polymer was chosen as suitable material for this purpose. It was prepared via modified chemical vapour deposition. Parylene removability was ensured through the soluble interlayer made of Laksil silicone-acrylic lacquer which was applied between the protected metallic object and the parylene thin film. Initially, the deposition process of Laksil/parylene bilayer was optimized, then its physical and chemical characteristics were determined and eventually, they were compared with the conventional conservation coating composed of Paraloid B72 acrylic resin and Revax microcrystalline wax. Regarding to the demands of the conservation coating, we were interested especially in barrier properties, optical properties, surface morphology and removability of Laksil/parylene bilayer. The most useful method for description of coating barrier properties was corrosion testing in which coated metallic samples were exposed to highly corrosive environment of salt spray (made of 50 g•l–1 brine), 100% humidity and temperature of 35 °C (ISO 9227). The Laksil/parylene bilayer showed excellent barrier properties; samples treated this way sustained unchanged in the corrosion chamber for almost three months. The surface roughness measured by profilometry and surface morphology scanned by SEM illustrated the synergy between Laksil and parylene layer which leads to the exceptional barrier and anticorrosion function of bilayer. The Laksil layer is able to flatten out rough surface of a substrate. Furthermore, it can toughen the item surface which is, in case of a number of archaeological findings, created by corrosion product layers with variable mechanical strength. Thereon deposited parylene film becomes smooth and defect free and can act as a good diffusion barrier. The colouristic measurements confirmed that the Laksil/parylene bilayer does not almost change the appearance of protected item, in terms of colour. The caused colour difference (ISO 11664-4) ranged around 1 which value is defined as “perceivable only for experienced observers”. The Laksil/parylene bilayer is removable thanks to the Laksil solubility in xylene. It is necessary to carefully scratch the outer parylene film to enable access of xylene solvent to the lacquer. The successful removal of Laksil/parylene bilayer was first confirmed by the EDX on metallic iron samples. Afterwards, the possibility of bilayer complete removal even from a corroded surface of the original artefact was proved by TGA. Thus the conservation treatment can be considered fully reversible.
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Barriere layers for culture herritage objects preservation
Procházka, Michal ; Lehocký, Marián (referee) ; Zahoranová, Anna (referee) ; Krčma, František (advisor)
Every year, many archeological findings are discovered. It is necessary to document and conserve these items dug up from the ground. However, archeologists and conservators cannot handle such a big amount of newly found items. This work offers an alternative approach to standard conservation techniques, increasing the processing capacity and lowering the cost on items’ conservation. Studied alternative, mainly for protection of metallic artefacts, includes thin films based on parylene and organosilicons. Thin films were prepared on two experimental apparatuses. Parylene films were deposited by chemical vapour deposition (CVD). Final product was a thin film of parylene C. Organosilicon thin films were deposited via plasma enhanced chemical vapour deposition (PECVD). PECVD apparatus operates with capacitively coupled radiofrequently initiated plasma. Using hexamethyldisiloxane, thin films very similar to silicon dioxide were produced, thus called SiOx. Thin films were characterized by several methods and compared to standard treatment used by conservators – tannate layer, acrylic furnish Paraloid B72 and microcrystalline wax Revax 30. Parylene films showed excellent conformity and resistance to corrosion on iron substrate. First signs of corrosion were observed on layer of 5 µm thickness after 24 hours in salt fog. On samples coated by SiOx films, corrosion was spreading wide even during 1st hour of the corrosion test. Most probable cause was that SiOx film has thermal expansion coefficient different from iron substrate and due to this fact cracking occurs during cooling down of the treated substrate. On samples coated by standard treatment, corrosion occurred after 1-3 hours of the test. Oxygen transmission rate (OTR) measurements (performed on polypropylene substrate) confirmed good barrier properties of parylene C. Best parylene thin films had OTR approximately 170 cm3•m-2•atm-1•day-1. SiOx films reached good results with OTR 300 cm3•m-2•atm-1•day-1, compared to clean polypropylene substrate with OTR 1700 cm3•m-2•atm-1•day-1. Standard conservation layers could not be applied on polypropylene substrate, thus their OTR was not measured. We did not succeed in finding a substrate which is compatible for all types of treatments. Next, the study focused on combinations of thin films forming sandwich structures. All types let the corrosion attack the substrate during the 1st hour of the test. The cause was insufficient film thickness as well as crack ing of SiOx films due to different thermal expansion properties from the iron substrate. Although SiOx thin films were not deposited on substrate directly, they have excellent adhesion to parylenu and thus they could tear parylenu films due to thermal expansion. However, OTR measurements showed improvement in barrier properties. Multilayer parylene C–SiOx–parylene C–SiOx had OTR 5 cm3•m-2•atm-1•day-1. Final result is that parylene C thin films have better barrier properties than standard coatings and are suitable for conservation of metallic archaeological artefacts. SiOx films and multilayers showed poor anticorrosion protection of metallic substrates but they have good barrier and chemical properties in combination with other types of substrates. Mainly deposited on polymers, there is great potential for their application in many fields. Further research would be focused on new substrates for SiOx thin films and on the improvement of UV stability of parylene films.
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