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Study of plasmachemical reduction of corrosive layers on brass
Řádková, Lucie ; Selucká, Alena (referee) ; Krčma, František (advisor)
The main topic of this bachelor thesis is plasmachemical treatment of archeological artifacts, especially plasma chemical treatment of brass corrosion layers. Low-pressure, low-temperature hydrogen plasma is used for this process. Nowadays, the technology is used mainly for iron or silver based materials but even for them the optimal conditions for the corrosion removal are not fully known yet. The knowledge about other metallic materials is fully missing. Two sets of brass samples were prepared in different corrosion atmospheres. The first atmosphere was prepared using saturated vapors of HCl. The samples were in this atmosphere during one month, and corrosion layers were orange-brown. The second set was prepared using ammonium solution, the samples were in this atmosphere for one day, corrosion layers were blue. The generation of capacitively coupled plasma in continuous mode by different supplied power was done. The experiments were carried out at 100 Pa with hydrogen gas flow of 50 sccm. Discharge power was varied in the interval 50 – 200 W and the treatment duration was 70 – 140 min. The optical emission spectroscopy of OH radical was used to find out all changes those have been resulting from plasmachemical reactions. The OH radical integral intensities were observed, they were used to monitoring plasma chemical reduction process. Spectral intensity of spectroscope was in the range 290 – 330 nm. After the plasmachemical treatment, it was very difficult to remove corrosion layers of HCl, but removing of NH3 corrosion layers was easy. It was caused by type of corrosion process (corrosion layers were influenced by time of corrosion process). This bachelor thesis is the start to find out conduct corrosion layers of brass in plasma treatment. In future, plasma treatment could be used to treatment of real archaeological artifacts.
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Low pressure plasma application for the surface cleaning of archaeological objects
Bubnová, Kateřina ; Grossmannová, Hana (referee) ; Krčma, František (advisor)
This diploma thesis builds on my bachelor thesis, which was focused on the application of low-pressure hydrogen plasma and argon-hydrogen plasma on layers of corrosion products. According to results of the experiments, an appropriate temperature for plasma chemical treatment of lead samples was detected. However, the process of corrosion removal through plasma chemical treatment needs to be further optimized to prevent potential damage to the original historical artefacts. Optimization of the treatment process is therefore the main subject of this work’s research. The model samples with artificial corrosion layers with dual composition were prepared. These samples were put to desiccator with sand and organic acid. The samples corroded in environment of acetic acid or formic acid with the aim of creating the corrosion, which would be at least partially simulated with corrosion on the original artefacts. The process of corrosion lasted for eleven months. After that, the samples were dried out under reduced pressure, put to the protecting foil with humid and oxygen absorbers. In contrast with my bachelor thesis where the continuous regime was chosen for the treatment, the pulse regime with three different condition settings is used. Process of experiment was monitored by OES, surface of samples was analyzed by SEM, EDX, XRD methods. Results from experiments with model samples were used for treatment of original artefacts with missing documentation, so their eventual damaging was acceptable.
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Brass Corrosion Layers Reduction by Low-Pressure Low-Temperature Plasma
Řádková, Lucie ; Slavíček,, Pavel (referee) ; Zahoran,, Miroslav (referee) ; Krčma, František (advisor)
This thesis presents results of the corrosion layers removal which could be found on the archaeological artefact surfaces. The low pressure low temperature plasma reduction was used for this purpose. Brass samples were chosen for this study. Two different ways have been used to form model corrosion layers. Several sets of corrosion layers were prepared in laboratory in two different corrosion atmospheres, namely ammonia atmosphere and atmosphere of hydrochloric acid. These samples were placed into desiccator. Small quantities of sand were added to some sets of samples so samples with sandy incrustation were prepared. The corrosion layers had been usually formed during four weeks. The second way, which was used to prepare model corrosion layer, was the natural corrosion in soil or compost. In this case, the corrosion layers had been formed approximately 2 years. The samples were treated in the low pressure (150 Pa) cylindrical Quartz reactor (90 cm long and 9.5 cm in diameter) with a pair of external copper electrodes connected via the matching network to a radiofrequency generator (13.56 MHz). The flows of working gases were set by independent mass flow controllers. Whole system was continuously pumped by the rotary oil pump which was separated from the discharge reactor by liquid nitrogen trap with aluminium chips eliminating dust and reactive species from the gas flow. Each sample was placed on a glass holder at the reactor center. Plasma was generated in pure hydrogen or in mixture of hydrogen and argon. Total flow of working gas was 50 sccm. Different ratios of gas mixture were tested, the ratio 30 sccm hydrogen and 20 sccm argon flows was the best. RF discharge was used in a continuous and pulsed regime. Pulsed mode was carried out with various duty cycle at the frequency of 1000 Hz. There were two ways of temperature monitoring. The sample temperature during the treatment was monitored by a K-type thermocouple installed inside the sample in the first case. Thermometer optical probe was connected to the sample surface by a small stainless plate and allowed continuous sample temperature monitoring in the second way. Safe object temperature for copper and copper alloys is 100–120 °C. To avoid exceeding this temperature, power control or the duty cycle in pulse mode were automatically controlled if thermometer optical probe was used. Plasma chemical treatment is based on generation of reactive atomic hydrogen in plasma discharge. The main reactions during reduction were reactions between oxygen and chloride contained in the corrosion layer and the hydrogen ions and neutral atoms generated in the plasma. These reactions create an unstable OH radical, which emits light in the region of 306–312 nm. This radiation was detected by the optical emission spectroscopy using Ocean Optics HR4000 spectrometer with 2400 gr/mm grating. Data obtained from this method were used to calculate rotational temperatures and integral intensity of OH radicals that were used for the process monitoring. Corrosion layer was not completely removed during the reduction, but due to the reactions which occur in the plasma corrosion layer became brittle and after plasma chemical treatment can be removed easily. The SEM-EDS material analyses were carried out before and after treatment of some samples. Some samples were analysed by XRD analysis. EDS analysis showed that amount of oxygen and chloride was decreased, mainly at 400 W pulse mode.
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Study of plasmachemical reduction of corrosive layers on copper
Šimšová, Tereza ; Selucká, Alena (referee) ; Krčma, František (advisor)
The present diploma thesis concerns the research of plasmachemical reduction of copper corrosion layers. The process was based on using low pressure hydrogen RF plasma in which copper samples are treated for several hours. Four series of copper corrosion layers were prepared in four different corrosion atmospheres. The first two were prepared using saturated vapors of HCl and ammonium acetate that affected copper samples for one week. The second two sets were prepared by samples dipping in HNO3 and H2SO4. EDX analysis confirms visual composition of corrosion layers – chlorides, nitrides and sulphate, respectively. The ammonium acetate produced no corrosion layers and thus this set of samples was omitted. The optical emission spectroscopy was used to find out reactions in a hydrogen RF discharge. At the first, a character of plasma without samples was taken by measuring in continuous and pulsed regime. The integral spectrum intensity (300-700 nm) and intensities of hydrogen atomic lines were observed in the dependences on hydrogen flow, power and duty cycle. After that copper samples were treaded under various conditions in continual and pulse regime, typically at pressure of 170 Pa, 200 W power and hydrogen flow rate of 10.2 ml/min. The integral OH radical spectral intensity in the range of 305 – 330 nm was used as a monitor of plasma treatment process. The experimental results showed that intensities of OH radical depended strongly on the corrosion layer kind as well as on the RF discharge mode. Reduction of corrosion layers treated in the pulsed regime was not so satisfactory then in the continuous regime probably due to lower temperature of sample during the treatment. The total supplied energy into the system was also lower in this case. The sample sputtering was observed during the reduction in continuous regime. It means the corrosion was successfully removed but the process was not stopped at that moment, so it is necessary to propose another additional monitoring process besides observing OH radicals. Our experimental results are the first step in the spread research of plasmachemical treatment of copper made archaeological artifacts.
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Reduction of bronze corrosion layers using hydrogen plasma
Miková, Petra ; Selucká, Alena (referee) ; Krčma, František (advisor)
This diploma thesis is focused to the plasma chemical reduction of model corrosion layers prepared on bronze samples. Bronze was the main material for production of the subjects in Bronze Age. First, it was very rare, and therefore was used only for making jewellery and other decorative subjects. Later, the objects of daily use and weapons were produced of bronze. These objects are found and it is necessary to restore him and preserve the cultural heritage for future generations. The research and the optimalization of plasmochemical reduction of model corrosion layers on bronze samples contributes to this. A metallographic grinder was used to create a defined surface, first with the sandpaper P 280 and then after sample 90 degree rotation with the sandpaper P 600. This ensured uniform surface at all bronze samples that is necessary to provide the same corrosion conditions. The grinded samples were washed by ethanol and dried by hot air stream. To prevent contact with the surrounding atmosphere and successive initiation of corrosion, the samples were stored in lockable polyethylene bags. This step was followed by the preparation of model corrosion layers. Hydrochloric and sulfuric acids were chosen as corrosive environments. Petri dish containing 20 ml of the selected acid was placed at the bottom of the desiccator. Samples were placed to the ceramic grate, over the dish, and they were corroded (in vapours of hydrochloric acid for 34 days and in vapours of sulfuric acid for 27 days). The corroded samples were treated using low-pressure hydrogen plasma excited by RF generator. Treatment of samples was carried out in quartz cylindrical reactor (length of 90 cm, inner diameter 9.5 cm) with copper electrodes placed outside. The pressure in the reactor was ranged around 160 Pa at hydrogen flow rate of 50 sccm during the experiments. The continuous and pulse modes (duty cycle of 25%, 50% or 75%) at peak power of 50–300 watts were used for the treatment of 90 minutes duration. The plasma treatment was monitored by optical emission spectroscopy of OH radical using compact Ocean Optics HR4000 spectrometer. Its integral intensity is proportional to the corrosion layer removal. The rotational temperatures of plasma were calculated using selected OH rotational lines, too. The sample temperature during the treatment was measured by thermocouple installed inside the additional non-corroded samples. The reduction of corrosion layer is successful when the maximum of relative intensity of OH radicals is produced and follow gradual decline. The samples which corroded in vapours of sulphuric acid and were treated in pulse modes with duty cycle of 25 % or with delivered power of 50 W has produced no maximum. To the remain samples the maximum although were observed, but reduced corrosion products on the surface were very cohesive. The maximum of relative intensity of OH radicals was observed at all samples corroded in vapours of hydrochloric acid. But there is problem with temperature of sample during experiment. The samples which layer of corrosion product was after experiment incoherent produced the layer of deposit tin. This effect formation at a higher temperature of sample during experiment and therefore with greater deliver energy.
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Plasma cleaning of corroded plumb objects
Bubnová, Kateřina ; Grossmannová, Hana (referee) ; Krčma, František (advisor)
This bachelor thesis deals with the application of low-pressure hydrogen plasma to lead corrosion products. There are many historical objects and these objects require careful removal of corrosion layers. Therefore, it is necessary to optimize the treatment process in order not to destroy real historical artefacts in the future. This work is focused on lead, which has not been explored by this method yet. Model samples with corrosion were prepared for comparison and these samples corrode in vapors of concentrated acetic acid and formic acid. There were three working temperatures for plasma chemical treatment because of the low lead melting point and the atomic heating. Argon-hydrogen plasma and hydrogen plasma was applied to 12 corroded samples during the experiment. Process progress was monitored by optical emission spectrometry and surface analysis was performed by SEM, XRD and EDX analysis. The results of these analyzes showed that the most appropriate temperature for plasma chemical treatment was 130 ° C. Based on the obtained results many suggesstions and ideas were obtained for the future research like using of pulse mode and gas composition.
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Preparation and Plasmachemical Reduction of Model Corrosion Layers on Iron.
Sázavská, Věra ; Novák, Stanislav (referee) ; Zahoranová, Anna (referee) ; Krčma, František (advisor)
The plasmachemical removal process of corrosion layers is based on a reduction effect of RF hydrogen low-pressure plasma, and it is used for archaeological objects. Incrustation layers on artifact surface become brittle and porous due to plasma processing. The structure and composition of corrosion layers is changed. Therefore, it is much easier to recover the original surface of the plasma treated artifacts in contrary to those treated by conventional ways. Moreover, we can save time on invasive and thus dangerous mechanical removal of corrosion layers as for example sanding is. After plasma treatment, we can observe fine details of the original surface and memory of tools used during its manufacturing. These details are important information on the origin and manufacturing methods of the artifacts. The plasma reduction process leads to the removal of impurities from cavities as well, and a function of mechanical components of archaeological object can be restored. Moreover, chlorides can be easily removed from the corrosion layers and thus any significant post-corrosion is protected. Each archaeological object is original and it has its own “corrosion history”. First, the object had been exposed to the atmosphere for a long time. Then, it had been often placed in a tomb or grave or it otherwise got into the soil or sea. Thus, each archaeological object was exposed to different corrosion stress (humidity, composition of corrosive environment, etc.). Due to these facts, any universal way of a corroded object treatment is very difficult or even impossible to propose. In this work, the problem was solved using model samples of common metals which were treated at various plasma treatment conditions. Archaeological objects made of iron are the most common artifacts, and the typical corrosion products on iron are akaganeite, rokuhnite, and szomolnokite. These three corrosion products were created on the model samples in laboratory and then, the plasmachemical reduction was applied for their removal. The experiment was done in a Quartz cylindrical reactor with capacitive coupled RF plasma created using outer electrodes. We used discharge power from 100 W to 400 W in a continuous or pulsed regime (duty cycle of 75 %, 50 % and 25 %). Flowing plasma was created in pure hydrogen at pressure of 150200 Pa. Sample temperature was monitored by a thermocouple, and it did not exceed 200C during all these experiments. This temperature is regarded as a limit temperature for metallographic changes of archaeological iron. Higher temperature can cause destruction of archaeological iron objects. The optical emission spectroscopy of OH radical was used for the process monitoring. We focused on the monitoring of OH-radicals generated in the plasma, which are characteristic species formed by this process. Each corrosion product has a different time evaluation of generated OH-radicals, which is closely related to the degradation of a given corrosion product. Corrosion layers were analyzed before and after the plasmachemical reduction by SEM-EDX. We have found that the plasmachemical reduction is not very suitable for the szomolnokite corrosion product, which is degraded with difficulty and at high applied powers, only. However, very good removal efficiency was obtained for the rokuhnite and akaganeite corrosion.
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Low pressure plasma application for the surface cleaning of archaeological objects
Bubnová, Kateřina ; Grossmannová, Hana (referee) ; Krčma, František (advisor)
This diploma thesis builds on my bachelor thesis, which was focused on the application of low-pressure hydrogen plasma and argon-hydrogen plasma on layers of corrosion products. According to results of the experiments, an appropriate temperature for plasma chemical treatment of lead samples was detected. However, the process of corrosion removal through plasma chemical treatment needs to be further optimized to prevent potential damage to the original historical artefacts. Optimization of the treatment process is therefore the main subject of this work’s research. The model samples with artificial corrosion layers with dual composition were prepared. These samples were put to desiccator with sand and organic acid. The samples corroded in environment of acetic acid or formic acid with the aim of creating the corrosion, which would be at least partially simulated with corrosion on the original artefacts. The process of corrosion lasted for eleven months. After that, the samples were dried out under reduced pressure, put to the protecting foil with humid and oxygen absorbers. In contrast with my bachelor thesis where the continuous regime was chosen for the treatment, the pulse regime with three different condition settings is used. Process of experiment was monitored by OES, surface of samples was analyzed by SEM, EDX, XRD methods. Results from experiments with model samples were used for treatment of original artefacts with missing documentation, so their eventual damaging was acceptable.
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Plasma cleaning of corroded plumb objects
Bubnová, Kateřina ; Grossmannová, Hana (referee) ; Krčma, František (advisor)
This bachelor thesis deals with the application of low-pressure hydrogen plasma to lead corrosion products. There are many historical objects and these objects require careful removal of corrosion layers. Therefore, it is necessary to optimize the treatment process in order not to destroy real historical artefacts in the future. This work is focused on lead, which has not been explored by this method yet. Model samples with corrosion were prepared for comparison and these samples corrode in vapors of concentrated acetic acid and formic acid. There were three working temperatures for plasma chemical treatment because of the low lead melting point and the atomic heating. Argon-hydrogen plasma and hydrogen plasma was applied to 12 corroded samples during the experiment. Process progress was monitored by optical emission spectrometry and surface analysis was performed by SEM, XRD and EDX analysis. The results of these analyzes showed that the most appropriate temperature for plasma chemical treatment was 130 ° C. Based on the obtained results many suggesstions and ideas were obtained for the future research like using of pulse mode and gas composition.
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Brass Corrosion Layers Reduction by Low-Pressure Low-Temperature Plasma
Řádková, Lucie ; Slavíček,, Pavel (referee) ; Zahoran,, Miroslav (referee) ; Krčma, František (advisor)
This thesis presents results of the corrosion layers removal which could be found on the archaeological artefact surfaces. The low pressure low temperature plasma reduction was used for this purpose. Brass samples were chosen for this study. Two different ways have been used to form model corrosion layers. Several sets of corrosion layers were prepared in laboratory in two different corrosion atmospheres, namely ammonia atmosphere and atmosphere of hydrochloric acid. These samples were placed into desiccator. Small quantities of sand were added to some sets of samples so samples with sandy incrustation were prepared. The corrosion layers had been usually formed during four weeks. The second way, which was used to prepare model corrosion layer, was the natural corrosion in soil or compost. In this case, the corrosion layers had been formed approximately 2 years. The samples were treated in the low pressure (150 Pa) cylindrical Quartz reactor (90 cm long and 9.5 cm in diameter) with a pair of external copper electrodes connected via the matching network to a radiofrequency generator (13.56 MHz). The flows of working gases were set by independent mass flow controllers. Whole system was continuously pumped by the rotary oil pump which was separated from the discharge reactor by liquid nitrogen trap with aluminium chips eliminating dust and reactive species from the gas flow. Each sample was placed on a glass holder at the reactor center. Plasma was generated in pure hydrogen or in mixture of hydrogen and argon. Total flow of working gas was 50 sccm. Different ratios of gas mixture were tested, the ratio 30 sccm hydrogen and 20 sccm argon flows was the best. RF discharge was used in a continuous and pulsed regime. Pulsed mode was carried out with various duty cycle at the frequency of 1000 Hz. There were two ways of temperature monitoring. The sample temperature during the treatment was monitored by a K-type thermocouple installed inside the sample in the first case. Thermometer optical probe was connected to the sample surface by a small stainless plate and allowed continuous sample temperature monitoring in the second way. Safe object temperature for copper and copper alloys is 100–120 °C. To avoid exceeding this temperature, power control or the duty cycle in pulse mode were automatically controlled if thermometer optical probe was used. Plasma chemical treatment is based on generation of reactive atomic hydrogen in plasma discharge. The main reactions during reduction were reactions between oxygen and chloride contained in the corrosion layer and the hydrogen ions and neutral atoms generated in the plasma. These reactions create an unstable OH radical, which emits light in the region of 306–312 nm. This radiation was detected by the optical emission spectroscopy using Ocean Optics HR4000 spectrometer with 2400 gr/mm grating. Data obtained from this method were used to calculate rotational temperatures and integral intensity of OH radicals that were used for the process monitoring. Corrosion layer was not completely removed during the reduction, but due to the reactions which occur in the plasma corrosion layer became brittle and after plasma chemical treatment can be removed easily. The SEM-EDS material analyses were carried out before and after treatment of some samples. Some samples were analysed by XRD analysis. EDS analysis showed that amount of oxygen and chloride was decreased, mainly at 400 W pulse mode.
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