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Search results for: molybdenum sulfide
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A Convenient Way to Methylated 2-Imidazolines. Syntheses of Fluorene and Triazine Cyclic Diamidines
PublicationOne N-methyl- and 4-substituted 2-imidazolines are described. Fluorene bisimidazolines were obtained in good yield (64-92%), starting from 2,7-dicyanofluorene and ammonium sulfide. In a two-step procedure the crude bisthioamide was reacted with excess diaminoalkane-ethanol (1:1 mixt.) in an oil bath. This new procedure is superior over std. methods. For the sake of comparison, a new triazine bisimidazoline (I) was prepd. by...
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Mass transfer in Spinning Fluids Reactor — Measurement and prediction
PublicationSpecific mass transfer area (a) and overall volumetric mass transfer coefficient (kLa) are mass transfer parameters commonly used in the description and comparison of various chemical reactors’ constructions. Determination of these was performed for Spinning Fluids Reactor (SFR). Sodium sulfite oxidation in the presence of cobalt ion catalyst was used for the determination of a and kLa. The a and kLa were successful predicted....
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Alkanethiolates of Group 1,2, and 13-15 Metals
PublicationThis manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of alkanethiolates of group 1, 2, and 13-15 metals. Alkanethiolates can be converted into S-alkyl thiocarboxylic acid esters, 1-thioglycosides, S-alkyl thiosulfinates, tetrahydro-1,4-thiazine-3-ones, sulfides, disulfides, sulfonium salts, dithioacetals and dithioketals, etc. These transformations are accomplished by...
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Seasonal changes of mercury speciation in the coastal sediments
PublicationPurpose Mercury speciation in sediments is linked to environmental conditions and processes. Domination of particular mercury species depends on its source, displays considerable seasonal behavior, and may be further modified due to oxygen levels, icing conditions, or the input of fresh organic matter. The purpose of this study was to examine the coastal area of the Gulf of Gdańsk in terms of mercury contamination and the influence...
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Photoinduced K+ Intercalation into MoO3/FTO Photoanode—the Impact on the Photoelectrochemical Performance
PublicationIn this work, thin layers of MoO3 were tested as potential photoanodes for water splitting. The influence of photointercalation of alkali metal cation (K+) into the MoO3 structure on the photoelectrochemical properties of the molybdenum trioxide films was investigated for the first time. MoO3 thin films were synthesized via thermal annealing of thin, metallic Mo films deposited onto the FTO substrate using a magnetron sputtering...
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Evaluation of the Impact of Different Types of Uncoupling on the Processing Capacity of Hump Yards
PublicationThe paper considers the issue of evaluating the impact of different types of uncoupling to increase the processing capacity of hump yards to ensure high technical-economic indicators in the conditions of limited capital funds. Moreover it describes the mathematical formulation of the sorting slide. For the mathematical formulation, the sorting slide is taken as a surface that is uniquely projected onto a horizontal plane. Based...
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Effect of Ion and Binding Site on the Conformation of Chosen Glycosaminoglycans at the Albumin Surface
PublicationAlbumin is one of the major components of synovial fluid. Due to its negative surface charge, it plays an essential role in many physiological processes, including the ability to form molecular complexes. In addition, glycosaminoglycans such as hyaluronic acid and chondroitin sulfate are crucial components of synovial fluid involved in the boundary lubrication regime. This study presents the influence of Na+, Mg2+ and Ca2+ ions...
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Modified Manganese Phosphate Conversion Coating on Low-Carbon Steel
PublicationConversion coatings are one of the primary types of galvanic coatings used to protect steel structures against corrosion. They are created through chemical reactions between the metal surface and the environment of the phosphating. This paper investigates the impact that the addition of new metal cations to the phosphating reaction environment has on the quality of the final coating. So far, standard phosphate coatings have contained...
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Antimicrobial Activity of Chimera Peptides Composed of Human Neutrophil Peptide 1 (HNP-1) Truncated Analogues and Bovine Lactoferrampin
PublicationThree chimera peptides composed of bovine lactoferrampin and the analogue of truncated human neutrophil peptide 1 were synthesized by the solid-phase method. In two compounds peptide chains were connected via isopeptide bond, whereas in the third one disulfide bridge served as a linker. All three chimeras displayed significantly higher antimicrobial activity than the constituent peptides as well as their equimolar mixtures. The...
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High temperature corrosion of evaporator tubes with thermal sprayed coatings
PublicationDegradation examinations of outer surface of low-emission steam boiler evaporator tubes are presented in the paper. Metallographic evaluation of scale morphology, its micro sites chemical composition analysis and distribution of elements on cross sections have been performed. Water-wall tubes were exposed in steam boiler for up to two years period. Common tubes made of 16Mo3 steel suffered sulphide and molten salts corrosions....
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Weakly Hydrated Solute of Mixed Hydrophobic–Hydrophilic Nature
PublicationInfrared (IR) spectroscopy is a commonly used and invaluable tool in studies of solvation phenomena in aqueous solutions. Concurrently, density functional theory calculations and ab initio molecular dynamics simulations deliver the solvation shell picture at the molecular detail level. The mentioned techniques allowed us to gain insights into the structure and energy of the hydrogen bonding network of water molecules around methylsulfonylmethane...
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Monitoring of odors emitted from stabilized dewatered sludge subjected to aging using proton transfer reaction–mass spectrometry
PublicationOne of the potential emission sources of odorous compounds from wastewater treatment plants is sludge processing. The odorous compounds released from dewatered sludge can result in odor nuisance. This study concerns the use of flux hood chamber combined with proton transfer reaction—time of flight—mass spectrometry (PTR-MS) technique for periodical monitoring of odorous compounds emitted from aged, stabilized dewatered sludge samples...
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Synthesis and structural characterization of new cyclic siloxane with functionalized organic substituents
PublicationOcta(2-pyridyloxy)cyclotetrasiloxane was isolated as the product of the reaction between silicon disulfide and 2-hydroxypyridine. The new compound has been characterised by single crystal X-ray analysis, revealing a planar eight-membered ring with functionalized organic substituents on the silicon atoms.
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Features extraction from the electrocatalytic gas sensor responses
PublicationOne of the types of gas sensors used for detection and identification of toxic-air pollutant is an electrocatalytic gas sensor. The electrocatalytic sensors are working in cyclic voltammetry mode, enable detection of various gases. Their response are in the form of I-V curves which contain information about the type and the concentration of measured volatile compound. However,...
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Study of Different Advanced Oxidation Processes for Wastewater Treatment from Petroleum Bitumen Production at Basic pH
PublicationEffluents from production of petroleum bitumens were submitted to treatment by three different AOPs at basic pH (i.e., O3, H2O2 and the combination of O3 and H2O2, a so-called peroxone). The paper presents studies on the identification and monitoring of the volatile organic compounds (VOCs) degradation present in the effluents and formation of byproducts, COD, BOD5, sulfide ions, biotoxicity, and biodegradability changes during...
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INFLUENCE OF SOLID PARTICLE CONTAMINATION ON THE WEAR PROCESS IN WATER LUBRICATED MARINE STRUT BEARINGS WITH NBR AND PTFE BUSHES
PublicationThis paper reports on a study of the influence of solid particle contamination on the wear process in water-lubricated slide bearings (steel-acrylonitrile-butadiene rubber (NBR) and steel- polytetrafluoroethylene (PTFE)). To compare the wear of the shaft journal and bushes (NBR and PTFE) when lubricated with fresh water and contaminated water, an experiment was carried out to identify key factors that influence the state of wear...
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Evaluation of Selected Heavy Metal Contaminants as Well as Nitrates and Nitrites in the Microgreens of Nigella (Nigella sativa L.), Safflower (Carthamus tinctorius L.), and Camelina (Camelina sativa L.) at Different Stages of Vegetation
PublicationMicrogreens are a new, rapidly growing group of foodstuffs. The decorative function of these is often accompanied by their use in traditional dishes. As microgreens are eaten at very early stages, when the development of the epidermis is at its minimum, the bioavailability of minerals will be found to be higher in microgreens then in mature vegetables. So, microgreens can be an excellent functional food, especially for mineral-deficient...
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Napawanie elementów wymiennika ciepła austenitycznym drutem proszkowym
PublicationNa potrzeby przemysłu energetycznego produkuje się wymienniki ciepła przeznaczone do eksploatacji w warunkach agresywnych chemicznie, np. w środowisku siarkowodoru. Z przyczyn ekonomicznych często stosuje się w takim przypadku materiały bimetaliczne wytwarzane procesami napawania. W artykule przedstawiono wyniki badań nieniszczących, pomiarów twardości, analizy składu chemicznego, pomiarów ferrytu delta oraz badań makro- i mikroskopowych...
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Cloning, Expression and Purification of Wild-Type Trehalose Synthase from Deinococcus geothermalis
PublicationThe aim of this study was isolation and cloning of trehalose synthase gene derived from extremophilic microorganism to the expression vectors in the Tabor-Studier system and its expression in Rosetta(DE3)pLysS Escherichia coli cells. The second phase of the study consisted of proteins purification using an initial denaturation of host proteins and salting-out proteins by ammonium sulfate.
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The impact of graphene on the electrochemical performance of BiMeVOx catalysts in water splitting
PublicationThe development of efficient catalysts for electrochemical water splitting has become a significant contemporary challenge. Transition metal oxides, due to their unique electrochemical properties, have emerged as promising candidates. Among these, a group of BiMeVOx-based compounds shows particular potential for practical applications in hydrogen and oxygen evolution reactions. However, improvement is still necessary to achieve...
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Efficiency of linear and non-linear classifiers for gas identification from electrocatalytic gas sensor
PublicationElectrocatalytic gas sensors belong to the family of electrochemical solid state sensors. Their responses are acquired in the form of I-V plots as a result of application of cyclic voltammetry technique. In order to obtain information about the type of measured gas the multivariate data analysis and pattern classification techniques can be employed. However, there is a lack of information in literature about application of such...
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Determination of toxic gases based on the responses of a single electrocatalytic sensor and pattern recognition techniques
PublicationA response from an electrocatalytic gas sensor contains fingerprint information about the type of gas and its concentration. As a result, a single gas sensor can be used for the determination of different gases. However, information about the type of gas and its concentration is hidden in the unique shape of the current–voltage response and it is quite difficult to explore. One of the ways to get precise information about the measured...
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The Syntheses and Crystal Structures of the First Disiloxane-1,3-dithiol and Its Cadmium Complex.
PublicationThe new silicon–sulfur compound: disiloxane-1,3-dithiol was obtained from silicon disulfide and 2,6-diisopropylphenol in a reaction catalyzed by imidazole or 4-(dimethylamino)pyridine (DMAP). Crystal structure of disiloxane–1,3-dithiol reveals a close-to-linear Si–O–Si angle and a mutual trans position of the two hydrosulfido groups. The compound forms a chelating mononuclear complex with cadmium ions.
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Fatigue resistance investigation of the IC engine MB11 bearings, working under conditions of dynamic unidirectional loadings
PublicationThe slide bearing material MB11 fatigue resistance has been investigated with the application of SMOK - test stand in which dynamic unidirectional loadings to the test bearing is generated. Slide bearing layer consists of the bronze MB11 ( Cu Pb22 Sn 3 ) sintered to the steel shell. Each of the tested bearing has been subject to the standard 20-hour test, under conditions of the full fluid lubrication. Methodology of the experiments,...
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Degradation kinetics and mechanism of pentoxifylline by ultraviolet activated peroxydisulfate
PublicationDegradation of pentoxifylline (PTX) by sodium peroxydisulfate (SPDS) assisted by UV irradiation has been investigated in deionized water. The treatment was more favorable over direct photolysis or peroxydisulfate oxidation alone. The effects of various parameters, including different dosage of oxidant agent, PTX concentration, initial solution pH levels, and the presence of inorganic ions like chloride, nitrate and carbonate have...
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The role of the combined nitrogen-sulfur-carbon cycles for efficient performance of anammox-based systems
PublicationThe combined anammox/mixotrophic denitrification process was conducted in two granular sequencing batch reactors (SBRs) during a 200-day operation. Both reactors were fed with synthetic medium, but SBR2 was enriched with additional sulfate (SO4 2 ) which influenced sulfate reduction ammonium oxidation (SRAO) and heterotrophic reduction of SO4 2 by sulfate reducing bacteria. It was hypothesized that the addition of SO4 2 could...
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Highly Visible-Light-Photoactive Heterojunction Based on TiO2 Nanotubes Decorated by Pt Nanoparticles and Bi2S3 Quantum Dots
PublicationA heterojunction with excellent visible light response and stability based on titanium dioxide nanotubes (TiO2 NTs), bismuth sulfide quantum dots (Bi2S3 QDs), and platinum nanoparticles (Pt NPs) is proposed. Both Pt NPs (3.0 ± 0.2 nm) and Bi2S3 QDs (3.50 ± 0.20 nm) are well distributed on the (i) top parts, (ii) inner walls, and (iii) outer walls of the TiO2 NTs. Visible-light-induced photoreaction was initialized by excitation...
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Sorption properties of asphaltene stationary phases for gas chromatography separations
PublicationW pracy przedstawiono wyniki badań nad możliwością wykorzystania faz stacjonarnych na bazie frakcji asfaltenowych do rozdzielania mieszanin związków chemicznych z wykorzystaniem chromatografii gazowej oraz porównano selektywność faz przygotowanych z frakcji asfaltenowych wyizolowanych z różnych surowców. Na podstawie uzyskanych wyników obliczono wartości liniowych indeksów retencji oraz stałych Rohrschneidera McReynoldsa, za pomocą...
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The influence of image masks definition onsegmentation results of histopathological imagesusing convolutional neural network
PublicationAbstract—In the era of collecting large amounts of tissue materials, assisting the work of histopathologists with various electronic and information IT tools is an undeniable fact. The traditional interaction between a human pathologist and the glass slide is changing to interaction between an AI pathologist with a whole slide images. One of the important tasks is the segmentation of objects (e.g. cells) in such images. In this...
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Paenibacillus alvei MP1 as a Producer of the Proteinaceous Compound with Activity against Important Human Pathogens, Including Staphylococcus aureus and Listeria monocytogenes
PublicationAn emerging need for new classes of antibiotics is, on the one hand, evident as antimicrobial resistance continues to rise. On the other hand, the awareness of the pros and cons of chemically synthesized compounds’ extensive use leads to a search for new metabolites in already known reservoirs. Previous research showed that Paenibacillus strain (P. alvei MP1) recovered from a buckwheat honey sample presented a wide spectrum of...
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Ultrasound-assisted heterogeneous activation of persulfate and peroxymonosulfate by asphaltenes for the degradation of BTEX in water
PublicationThis study investigated – for the first time - the simultaneous degradation of benzene, toluene, ethylbenzene and o-xylene (BTEX) by persulfate (PS) and peroxymonosulfate (PMS) activated by asphaltenes (Asph) under ultrasound (US) irradiation. Advantageous properties such as high thermal stability, low production cost and extensive availability make asphaltenes as an appealing carbonaceous material for heterogeneous catalysis....
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Ranking of Heterogeneous Catalysts Metals by Their Greenness
PublicationCatalysis is very important process in industry and laboratory practice, especially from the point of green chemistry principles. However, eco-friendly character of heterogeneous catalysts, containing transition metal components has not been evaluated, yet. Therefore, we perform a comprehensive assessment of 18 heterogeneous metal catalysts (Pd, Pt, V, Co, Ni, Mo, Ru, Mn, Au, Cu, Cd, Zr, Fe, Rh, Ir, Sn, Zn, Ag) using multicriteria...
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Novel and Efficient Methods for the Synthesis of Symmetrical Trisulfides
PublicationWe have developed a convenient methods for the synthesis of symmetrical trisulfides under mild conditions in very good yields. The described methods are based on the straightforward preparation of 5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-disulfanyl derivatives from readily available 5,5-dimethyl-2-sulfanyl-2-thioxo-1,3,2-dioxaphosphorinane or bis(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) disulfide. The symmetrical...
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TBAF Promoted Formation of Symmetrical Trisulfides
PublicationWe have developed a new method for the synthesis of functionalized symmetrical trisulfides based on (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorin-2-yl)disulfanyl derivatives prepared from readily available 5,5-dimethyl-2-sul-fanyl-2-thioxo-1,3,2-dioxaphosphorinane or bis(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) disulfide. The symmetrical trisulfides can be obtained from aliphatic and aromatic thiols andL-cysteine derivatives...
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The possibility of use keratin products in various branches of industry
PublicationBird's feather, the main by-product of the poultry industry, are not enough utilized and negatively influencing the environment. They contain large amount of keratin, the protein with high cystine content. The aim of our work was to obtain hydrolysates and isolates of keratin, which can be used in various areas of food, cosmetics, pharmaceutical industry and as animal feed. Keratin can be hydrolyzed and extracted from feather after...
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Process Control and Investigation of Oxidation Kinetics of Postoxidative Effluents Using Gas Chromatography with Pulsed Flame Photometric Detection (GC-PFPD)
PublicationThis article presents the results of investigations on the use of headspace analysis and gas chromatography with pulsed flame photometric detection (HSA-GC-PFPD) to evaluate the effectiveness of oxidation of postoxidative effluents from the production of bitumens. Samples of effluents from the bitumen oxidation unit were used in the experiments. In addition, the kinetics of effluent oxidation was also investigated. The content...
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Development of a simple biogas analyzer module (BAM) for real-time biogas production monitoring
PublicationAnaerobic digestion (AD) relies on the cooperation of specific microbial communities, making it susceptible to process disruptions that could impact biogas production. In this regard, this study presents a technological solution based on the Arduino platform, in the form of a simple online monitoring system that can track the produced biogas profile, named as biogas analyzer module (BAM). The applicability of the BAM focused on...
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MOŻLIWOŚCI IDENTYFIKACJI STANU TECHNICZNEGO WARSTW ŚLIZGOWYCH ŁOżYSK SILNIKÓW SPALINOWYCH O ZAPŁONIE SAMOCZYNNYM W PRZYPADKU WYKORZYSTANIA EMISji AKUSTYCZNEJ JAKO SYGNAŁU DIAGNOSTYCZNEGO
PublicationW artykule zaprezentowano wyniki badań wielowarstwowych panwi łożysk ślizgowych silników tłokowych. Scharakteryzowano własności obciążeń tego rodzaju panwi oraz ich zużycia szczególnie zmęczeniowego i ściernego. Wykazano przydatność emisji akustycznej jako sygnału diagnostycznego do ujawniania zużycia powłok ślizgowych i zaporowych. Przedstawiono wyniki pomiarów parametrów emisji akustycznej, wykonanych za pomocą 12- kanałowej...
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Maria Jolanta Milewska prof. dr hab. inż.
PeopleMaria Jolanta Milewska, po ukończeniu Technikum Chemiczno-Mechanicznego w Wąbrzeźnie (specjalizacja: przetwórstwo tworzyw sztucznych) kontynuowała naukę na Wydziale Chemicznym Politechniki Gdańskiej. W 1979 r. zdobywa tytuł mgr inżyniera na kierunku Chemia, o specjalizacji Lekka Synteza Organiczna. Studium Doktoranckie PG ukończyła w 1984 r. W 1983 r została zatrudniona na macierzystym wydziale w Katedrze Chemii Organicznej, początkowo...
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Iron(III)-selective materials based on a catechol-bearing amide for optical sensing
PublicationThe synthesis and ion-binding properties of a new amide L derived from 3,4-dihydroxybenzoic acid are described. Due to the presence of a catechol unit, the compound interacts selectively with iron(III) in organic solvent (dimethyl sulfoxide, DMSO) to produce a color change from pale yellow to green. The incorporation of the ligand L into polymeric matrices or its encapsulation into surfactant-based spheres enables analyte detection...
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A versatile and convenient preparation of unsymmetrical diaryl disulfides
PublicationWe have developed a convenient method for the synthesis of unsymmetrical diaryl disulfides under mild conditions in excellent yields. The described method is based on the straightforward preparation of 5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-sulfenyl bromide from readily available 5,5-dimethyl-2-thiolo-2-thioxo-1,3,2-dioxaphosphorinane or bis(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) disulfide. The unsymmetrical...
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Selected Problems of Experimental Testing Marine Stern Tube Bearings
PublicationThis paper presents typical methods for conducting experimental tests on main shaft slide bearings. There are described their possible testing capabilities, advantages, drawbacks and limitations. Various testing methods were analyzed to find a solution able of providing a wide range of possible investigations at possibly acceptable limitations.
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Fabrication of Durable Ordered Ta2O5 Nanotube Arrays Decorated with Bi2S3 Quantum Dots
PublicationOne of the most important challenges in the fabrication of ordered tantalum pentaoxide (Ta2O5) nanotube arrays (NTs) via the electrochemical method is the formation of nanotubes that adhere well to the Ta substrate. In this paper, we propose a new protocol that allows tight-fitting Ta2O5 nanotubes to be obtained through the anodic oxidation of tantalum foil. Moreover, to enhance their activity in the photocatalytic reaction, in...
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Effects of preheating on laser beam–welded NSSC 2120 lean duplex steel
PublicationDuplex stainless steels show sustainable alternative for the conventional austenitic grades, with higher strength, higher resistance against stress corrosion cracking, and lower purchase cost. Thus, duplex stainless steel gains more attention in construction, oil and gas, and chemical industries. Among duplex stainless steels, low nickel and low molybdenum alloyed lean duplex stainless steel are a cost-efective substitution of...
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Activated persulfate and peroxymonosulfate based advanced oxidation processes (AOPs) for antibiotics degradation – A review
PublicationSulfate radical AOPs (SR-AOP) were successfully utilized in degradation of antibiotics in water and wastewater treatment. The review discusses details on SR-AOPs mechanisms and applications for antibiotics degradation. The progress in this field was discussed, highlighting the most promising developments and remaining challenges. The applicability of SR-AOPs was summarized revealing the most susceptible and persistent to oxidation...
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Metal dusting in CCR platforming unit
PublicationPrzedstawiono mechanizm pylenia metalu w stali 9Cr-1Mo w instalacji platformingu CCR, na postawie badań rury podgrzewacza wsadu po 10 latach pracy, przy temperaturze metalu koło 600C. W badaniach wykorzystano techniki elektronowej mikroskopii skaningowej, dyfrakcji rentgenowskiej i mikroanalizy rentgenowskiej. Wykazano, że dyfuzji wegla w głąb stali toarzyszy odrdzeniowa dyfuzja pierwiastków węglikotwórczych - chromu i molibdenu....
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Metal dusting in CCR platforming unit
PublicationPrzedstawiono mechanizm pylenia metalu w stali 9Cr-1Mo w instalacji platformingu CCR, na postawie badań rury podgrzewacza wsadu po 10 latach pracy, przy temperaturze metalu koło 600C. W badaniach wykorzystano techniki elektronowej mikroskopii skaningowej, dyfrakcji rentgenowskiej i mikroanalizy rentgenowskiej. Wykazano, że dyfuzji wegla w głąb stali toarzyszy odrdzeniowa dyfuzja pierwiastków węglikotwórczych - chromu i molibdenu....
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Influence of laser processing of the low alloy medium carbon structural steel on the development of the fatigue crack
PublicationThe paper contains the results of the structural analysis, hardness tests and fatigue tests conducted for the medium carbon structural steel with low content of Cr and Ni after its processing with CO2 laser beam. Pre-cracks were made in the round compact tension (RCT) specimen used for fatigue test. Next, four paths, parallel to each other, were melted on both sides of the samples using a laser beam. The paths were perpendicular...
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Wpływ strat mechanicznych w siłowniku teleskopowym zespołu zagęszczającego w pojeździe do usuwania odpadów z pojemników na skuteczność prasowania odpadów
PublicationHydraulic telescopic cylinders are used to power the moving wall of rear loader garbage trucks equipped with the traditional "sweep and slide" system. As the garbage compression force is directly dependent on the resistance force of the moving wall, losses in the hydraulic telescopic cylinder influence the compaction process. Taking them into account in the control system may improve the operation of the compaction...
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Effect of Laminar Pulsatile Fluid Flow on Separation of Volatile Organic Compounds from Aqueous Solution by a Hollow Fiber Membrane-Based Process
PublicationIn this study, a laminar pulsatile fluid flow was used for the separation of benzene, toluene, ethylbenzene, and xylene isomers (BTEX) from aqueous solutions. Polyether sulfone hollow fiber membrane has been applied to this process. The effects of BTEX concentration, and feed and extraction flow rates were examined. It was found that the application of the pulsatile fluid flow with...