Spectroscopic Study of Post-Discharges in Nitrogen and its Mixtures

Cílem disertační práce je studium kinetických procesů v dohasínajícím plazmatu dusíku s příměsí kyslíku a dusíku ve směsi s argonem. Výsledky měření předložené v této práci jsou získány z optické emisní spektroskopie dohasínajícího plazmatu. Ve všech měřeních byl dobře identifikovatelný jev tzv. pink afterlow (maximální intenzita vyzařování) a vliv příměsí na tento jev. Pro měření byl vzhledem k našim experimentálním možnostem zvolen stejnosměrný výboj v proudícím režimu, kdy je možno dosáhnout časového rozlišení v řádově ms, což je pro studované jevy dostatečné. Měření bylo provedeno v rozsahu vlnových délek 300-800 nm. V naměřených spektrech byly identifikovány první pozitivní, druhy pozitivní a první negativní spektrální systémy dusíku a systémy NO beta a NO gama.Experimenty byly provedeny ve dvou konfiguracích aparatury, pro měření dohasínajícího plazmatu dusíku s příměsí kyslíku a pro měření dohasínajícího plazmatu ve směsi dusíku s argonem. V případě měření dusíku s příměsí kyslíku (koncentrace kyslíku do 0,2 %) byly k dispozici dvě výbojové trubice z různých materiálů – sklo PYREX a sklo QUARTZ. Aby bylo možno posoudit vliv teploty na procesy probíhající během dohasínání, byly provedeny dva typy měření za různých teplotních podmínek. Pro obě trubice bylo měření provedeno pro laboratorní teplotu 300 K a pro chlazení tekutým dusíkem (77 K) v místě spektroskopického měření. Celkový tlak byl při těchto experimentech 1 000 Pa a proud 200 mA. V naměřených spektrálních systémech byly identifikovány jednotlivé spektrální přechody a byly sestrojeny závislosti jejich intenzit na čase dohasínání. Dále byly vypočteny relativní vibrační populace jednotlivých stavů v závislosti na koncentraci kyslíku. Z relativních populací byla sestrojena i vibrační rozdělení pro jednotlivé stavy dusíku. Z výsledků obecně vyplývá, že s rostoucí koncentrací kyslíku lze pozorovat mírný nárůst populací molekulárního dusíku, ale koncentrace molekulárního iontu dusíku rapidně klesá. Při snížené teplotě se posouvá do pozdějších časů dohasínání. V trubici za skla QUARTZ lze pozorovat vymizení jevu pink afterglow už při velmi nízkých koncentracích kyslíku. Naopak dochází k nárůstu populací v pozdějším čase dohasínání. V případě směsi dusík-argon bylo měření provedeno pouze ve výbojové trubici ze skla PYREX a za teploty stěny 300 K. Konstantní byl udržován celkový výkon aktivního výboje na hodnotě 290 kW. Byl ale měněn celkový tlak v rozmezí 500-5 000 Pa a koncentrace argonu (0%-83%). Při nízkém tlaku 500 Pa je jev pink afterglow poměrně úzký a s rostoucím tlakem se jeho trvání podstatně prodlužuje. Současně se i maximum vyzařování posouvá k pozdějším časům. V závislosti na tlaku se podstatně mění i celková intenzita emise záření během dohasínání. Časový posun maxima intenzity vyzařování je v podstatě nezávislý na tlaku a maximum se nachází v pozdějším čase než v čistém dusíku. Celková intenzita vyzařování během dohasínání je ve směsi obsahující převážně argon podstatně nižší než v případě dohasínání čistého dusíku. Z dlouhodobějšího hlediska pak bude zajímavé porovnání experimentálně získaných výsledků s výsledky numerického modelování, jímž se zabývají spolupracující pracoviště na univerzitách v Portugalsku.Presented thesis gives results obtained during the spectroscopic observations of post –discharges of the pure nitrogen plasma with small oxygen admixture and in the nitrogen – argon mixture and the effect of the pink afterglow in it. The DC discharge in the flowing regime has been used for the plasma generation. The decaying plasma was study by optical emission spectroscopy, mainly in the range of 300–800 nm. The first positive, second positive, first negative nitrogen spectral system and NO spectral systems were observed in measured spectra. The band head intensities of these bands have been studied in the dependencies on experimental conditions. Simultaneously, the relative vibrational populations on the given nitrogen states have been calculated. Two discharge tubes made from different materials (PYREX glass and QUARTZ glass) were used in the case of nitrogen plasma containing low oxygen traces (up to 0.2 %). These experiments have been carried out at two wall temperatures for the determination of the temperature effect on the post-discharge. The discharge tube around the observation point was kept at the ambient temperature (300 K) or it was cooled down to 77 K by liquid nitrogen vapor. The total gas pressure of 1 000 Pa and the discharge current of 200 mA were conserved for all these experiments. The relative populations of electronic states were calculated in the dependence on the post-discharge time. The dependencies on oxygen concentration were given, too. The results showed no simple dependence of vibrational populations on oxygen concentration. Generally, slight increase of neutral nitrogen states populations was observed with the increase of oxygen concentration. These observations were well visible due to the intensity of nitrogen pink afterglow effect that was well visible at all oxygen concentrations. The pink afterglow maximal intensity was reached at about 5–10 ms at the wall temperature of 300 K in the PYREX tube. The molecular ion emission was strongly quenched by the oxygen and as this was dominant process for the pink afterglow emission the pink afterglow effect disappears at oxygen concentration of about 2000 ppm. The temperature and wall material influences were observed, too. The post-discharge in nitrogen argon mixtures was studied only in the PYREX tube at the ambient wall temperature of 300 K. The power dissipated in an active discharge was constant of 290 kW. The experimental studies had two new parameters – total gas pressure (500 Pa – 5 000 Pa) and the argon concentrations that were varied in the range of 0–83 %. Also in this case the dependencies of relative intensities of the bands given above were obtained and further the relative populations of electronic states as a function of decay time, total gas pressure and on argon concentration were obtained. The pink afterglow effect was observed at all applied discharge powers and total gas pressures. At the highest argon concentrations, especially at lower pressure, the pink afterglow effect disappeared. The presented experimental work is one of the hugest sets of experiments in the nitrogen with oxygen traces and in nitrogen-argon mixtures. These data can be used as a very good fundament for the further studies using wide numeric modeling of the post-discharge kinetic processes.

Atmospheric pressure plasma polymerized oxazoline-based thin films: antibacterial properties and cytocompatibility performance

Polyoxazolines are a new promising class of polymers for biomedical applications. Antibiofouling polyoxazoline coatings can suppress bacterial colonization of medical devices, which can cause infections to patients. However, the creation of oxazoline-based films using conventional methods is difficult. This study presents a new way to produce plasma polymerized oxazoline-based films with antibiofouling properties and good biocompatibility. The films were created via plasma deposition from 2-methyl-2-oxazoline vapors in nitrogen atmospheric pressure dielectric barrier discharge. Diverse film properties were achieved by increasing the substrate temperature at the deposition. The physical and chemical properties of plasma polymerized polyoxazoline films were studied by SEM, EDX, FTIR, AFM, depth-sensing indentation technique, and surface energy measurement. After tuning of the deposition parameters, films with a capacity to resist bacterial biofilm formation were achieved. Deposited films also promote cell viability.Ministry of Education, Youth and Sports of the Czech RepublicMinistry of Education, Youth & Sports - Czech Republic [LO1411]; Czech Science FoundationGrant Agency of the Czech Republic [GACR 19-15240S]; Ministry of Defence of the Czech Republi

Comparison of plasma-polymerized thin films deposited from 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline: I film properties

Poly(2-oxazoline) is a promising new class of polymeric materials due to their antibiofouling properties and good biocompatibility. Poly(2-oxazoline) coatings can be deposited on different substrates via plasma polymerization, which can be more advantageous than other coating methods. The aim of this study is to deposit poly(2-oxazoline) coatings using a surface dielectric barrier discharge burning in nitrogen at atmospheric pressure using 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline vapours as monomers and compare the film properties. For the comparison, the antibacterial and cytocompatibility tests were peformed according to ISO norms. The antibacterial tests showed that all the deposited films were highly active against Staphylococcus aureus and Escherichia coli bacteria. The chemical composition of the films was studied using FTIR and XPS, and the film surface’s properties were studied using AFM and surface energy measurement. The cytocompatibility tests showed good cytocompatibility of all the deposited films. However, the films deposited from 2-methyl-2-oxazoline exhibit better cytocompatibility. This difference can be explained by the different chemical compositions and surface morphologies of the films deposited from different monomers.Ministerstvo Školství, Mládeže a Tělovýchovy, MŠMT, (DKRVO RP/CPS/2022/005, RP/CPS/2022/001, RP/CPS/2022/002); Ministerstvo Obrany České Republiky, MOČRMinistry of Defence of the Czech Republi

Antibacterial thin films deposited from propane-butane mixture in atmospheric pressure discharge

Antibacterial coatings on biomedical instruments are of great interest because they can suppress bacterial colonization on these instruments. In this study, antibacterial polymeric thin coatings were deposited on teflon substrates using atmospheric pressure plasma polymerization from a propane–butane mixture. The plasma polymerization was performed by means of surface dielectric barrier discharge burning in nitrogen at atmospheric pressure. The chemical composition of plasma polymerized propane–butane films was studied by energy-dispersive X-ray spectroscopy (EDX) and FTIR. The film surface properties were studied by SEM and by surface energy measurement. The EDX analysis showed that the films consisted of carbon, nitrogen and oxygen from ambient air. The FTIR analysis confirmed, in particular, the presence of alkyl, nitrile, acetylene, imide and amine groups. The deposited films were hydrophilic with a water contact angle in the range of 13–23°. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. On the other hand, the films were cytocompatible, reaching more than 80% of the cell viability threshold compared to reference polystyrene tissue. © 2023 by the authors.Ministerstvo Školství, Mládeže a Tělovýchovy, MŠMT: RP/CPS/2022/001, RP/CPS/2022/002; Ministerstvo Obrany České Republiky, MOČ

Atmospheric pressure plasma polymerized 2-ethyl-2-oxazoline based thin films for biomedical purposes

Polyoxazoline thin coatings were deposited on glass substrates using atmospheric pressure plasma polymerization from 2-ethyl-2-oxazoline vapours. The plasma polymerization was performed in dielectric barrier discharge burning in nitrogen at atmospheric pressure. The thin films stable in aqueous environments were obtained at the deposition with increased substrate temperature, which was changed from 20◦ C to 150◦ C. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. The chemical composition of polyoxazoline films was studied by FTIR and XPS, the mechanical properties of films were studied by depth sensing indentation technique and by scratch tests. The film surface properties were studied by AFM and by surface energy measurement. After tuning the deposition parameters (i.e., monomer flow rate and substrate temperature), stable films, which resist bacterial biofilm formation and have cell-repellent properties, were achieved. Such antibiofouling polyoxazoline thin films can have many potential biomedical applications. © MDPI AG. All rights reserved.Czech Science FoundationGrant Agency of the Czech Republic [GACR 19-15240S]; Ministry of Defence of the Czech Republi

The effect of the aging of liquid organic scintillators used for gamma-neutron separation

Since the beginning of using liquid scintillators for gamma-neutron separation, there have been many articles dealing with long-term degradation especially due to oxygen presented during scintillator encapsulation. The effect of aging of liquid organic scintillators namely EJ301, EJ309 (both Eljen Technology), and new custom-made cocktails based on 1-Phenyl-3-(2,4,6-trimethylphenyl)-2-pyrazoline and 2,5-Bis(5-tert-butyl-benzoxazol-2-yl)thiophene fluors were investigated for more than half a year. The research was focused on the Compton edge shifting of gamma particles since the position is proportional to the light yield of the selected scintillator. Furthermore, the gamma-neutron separation was observed and quantified using FOM (Figure Of Merit) for samples prepared and filled under normal and nitrogen atmosphere during the mentioned period. All stated parameters of liquid scintillator NE213 manufactured by Nuclear Enterprises Limited opened more than three decades ago were measured and used for comparison

Excitace atomů rtuti v dohasínajícím dusíkovém plazmatu

The work presents results obtained during spectroscopic observations of nitrogen DC flowing post-discharges at the total gas pressure of 1000 Pa and at the discharge current of 100 mA. Mercury traces were introduced into the system using auxiliary pure nitrogen flow enriched by mercury vapor. A very low mercury concentration of 3.7 ppb was introduced into the system before the active discharge. The strong quenching of nitrogen pink afterglow was observed but no mercury lines were recorded. Moreover, the vibrational distributions of nitrogen excited states were nearly unchanged. Based on these results, the new experimental set up was created. The introduction point of mercury vapor with higher concentration of 600 ppm was movable during the post discharge up to decay time of 40 ms. Besides three nitrogen spectral systems (first and second positive and first negative), NO-beta and NO-gamma bands, the mercury line at 254 nm was recorded at these conditions. Its intensity was dependent on the mercury vapor introduction position as well as on the mercury concentration. No other mercury lines were observed. The creation of mercury 3P1 state that is the upper state of the observed mercury spectral line is possible by the resonance excitation energy transfer form vibrationally excited nitrogen ground state N2 (X, v = 19). The observed results should form a background for the development of a new titration technique used for the highly vibrationally excited nitrogen ground state molecules determination.Práce prezentuje výsledky získané spektroskopickým pozorováním stejnosměrného dohasínajícího plazmatu v dusíku při celkovém tlaku 1000 Pa a výbojovém proudu 100 mA. Do systému byly přidávány stopy rtuti pomocí proudu čistého dusíku obohaceného o páry rtuti. Velmi nízké koncentrace rtuti (3,7 ppb) byly vpuštěny do systému před aktivním výbojem. Následně bylo pozorováno silné zhášení růžového dosvitu dusíku, ale nebyly zaznamenány žádné čáry rtuti. Navíc se vibrační rozdělení excitovaných stavů dusíku téměř nezměnilo. Na základě těchto výsledků byl vytvořen nový systém. Vstupní bod par rtuti s vyšší koncentrací (600 ppm) se tak mohl pohybovat kolem dohasínajícího výboje až do času 40 ms. Kromě tří spektrálních systémů dusíku (první a druhý pozitivní a první negativní) a pásů NO-beta a NOgamma byla za těchto podmínek zaznamenána i čára rtuti při 254 nm. Její intenzita byla závislá na místě vstupu par rtuti, jakožto i na koncentraci rtuti. Žádné další čáry rtuti nebyly zaznamenány. Tvorba 3P1 stavu rtuti, který je vyšším stavem pozorované spektrální čáry rtuti, je možná rezonančním přechodem excitované energie z vibračně vybuzeného základního stavu dusíku N2 (X, v = 19). Pozorované výsledky by měly tvořit základ pro rozvoj nové titrační techniky používané ke stanovení vysoce vibračně excitovaných základních stavů molekuly dusíku

Response to Mono-Energetic Neutrons and Light Output Function for Liquid Organic Scintillators PYR5/DIPN and THIO5/DIPN

Liquid organic scintillators are important devices for measurements of neutron radiation. Currently, large-scale liquid organic scintillators have capabilities of detecting neutrons, but the determination of the neutron energy spectra is a challenge. This work aims to measure the responses of two liquid two-component scintillators to mono-energetic neutron radiation and to determine their light output function, which is necessary for proper neutron energy spectra determination. Both scintillators are composed of the solvent di-iso-propyl-naphthalene (DIPN) mixed isomers. The first scintillator, labeled PYR5/DIPN, contains the luminophore 1-phenyl-3-(2,4,6-trimethyl-phenyl)-2-pyrazoline with a concentration of 5 g/L. The second scintillator labeled THIO5/DIPN contains the luminophore 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene also with a concentration of 5 g/L. The responses to neutron energies of 1.5 MeV, 2.5 MeV, and 19 MeV are measured at PTB in Braunschweig. The responses to neutron energies of 2.45 MeV and 14 MeV were measured at CTU in Prague using DD and DT reactions. The responses to a silicon filtered beam were measured at Research Centre Řež. The measurements were processed using a two-parameter spectrometric system NGA-01 to discriminate neutrons from gamma rays. The obtained responses are dominated by recoil protons from elastic collisions of neutrons with hydrogen atoms. The edge of the response of recoil protons gives information about the light output of neutrons, compared to gamma rays for the same radiation energy. The light output function for protons in the PYR5/DIPN scintillator is L(Ep)=0.6294Ep−1.00(1−exp(−0.4933Ep0.95)). The light output function for protons in the THIO5/DIPN scintillator is L(Ep)=0.6323Ep−1.00(1−exp(−0.4986Ep0.9883)). The light output functions well resemble the standard shape, and they are quite similar to each other. That suggests a weak influence of the luminophore on the light output function. The light output functions are ready to be incorporated to the response matrix for the neutron energy spectra determination

Response to Mono-Energetic Neutrons and Light Output Function for Liquid Organic Scintillators PYR5/DIPN and THIO5/DIPN

Liquid organic scintillators are important devices for measurements of neutron radiation. Currently, large-scale liquid organic scintillators have capabilities of detecting neutrons, but the determination of the neutron energy spectra is a challenge. This work aims to measure the responses of two liquid two-component scintillators to mono-energetic neutron radiation and to determine their light output function, which is necessary for proper neutron energy spectra determination. Both scintillators are composed of the solvent di-iso-propyl-naphthalene (DIPN) mixed isomers. The first scintillator, labeled PYR5/DIPN, contains the luminophore 1-phenyl-3-(2,4,6-trimethyl-phenyl)-2-pyrazoline with a concentration of 5 g/L. The second scintillator labeled THIO5/DIPN contains the luminophore 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene also with a concentration of 5 g/L. The responses to neutron energies of 1.5 MeV, 2.5 MeV, and 19 MeV are measured at PTB in Braunschweig. The responses to neutron energies of 2.45 MeV and 14 MeV were measured at CTU in Prague using DD and DT reactions. The responses to a silicon filtered beam were measured at Research Centre Řež. The measurements were processed using a two-parameter spectrometric system NGA-01 to discriminate neutrons from gamma rays. The obtained responses are dominated by recoil protons from elastic collisions of neutrons with hydrogen atoms. The edge of the response of recoil protons gives information about the light output of neutrons, compared to gamma rays for the same radiation energy. The light output function for protons in the PYR5/DIPN scintillator is L(Ep)=0.6294Ep−1.00(1−exp(−0.4933Ep0.95)). The light output function for protons in the THIO5/DIPN scintillator is L(Ep)=0.6323Ep−1.00(1−exp(−0.4986Ep0.9883)). The light output functions well resemble the standard shape, and they are quite similar to each other. That suggests a weak influence of the luminophore on the light output function. The light output functions are ready to be incorporated to the response matrix for the neutron energy spectra determination

Antibacterial Thin Films Deposited from Propane–Butane Mixture in Atmospheric Pressure Discharge

Antibacterial coatings on biomedical instruments are of great interest because they can suppress bacterial colonization on these instruments. In this study, antibacterial polymeric thin coatings were deposited on teflon substrates using atmospheric pressure plasma polymerization from a propane–butane mixture. The plasma polymerization was performed by means of surface dielectric barrier discharge burning in nitrogen at atmospheric pressure. The chemical composition of plasma polymerized propane–butane films was studied by energy-dispersive X-ray spectroscopy (EDX) and FTIR. The film surface properties were studied by SEM and by surface energy measurement. The EDX analysis showed that the films consisted of carbon, nitrogen and oxygen from ambient air. The FTIR analysis confirmed, in particular, the presence of alkyl, nitrile, acetylene, imide and amine groups. The deposited films were hydrophilic with a water contact angle in the range of 13–23°. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. On the other hand, the films were cytocompatible, reaching more than 80% of the cell viability threshold compared to reference polystyrene tissue