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Search results for: surface engineering
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Visible light photoactivity of TiO2loaded with monometallic(Au or Pt) and bimetallic (Au/Pt) nanoparticles
PublicationTiO2modified with monometallic (Au or Pt) and bimetallic (Au/Pt) nanoparticles have been preparedusing a water-in-oil microemulsion system (water/AOT/cyclohexane) followed by calcination step. Theeffect of metal ratio, reducing agent type (NaBH4or N2H4), TiO2matrix type (P-25, ST-01, TiO-5, TiO2nano-tubes or TiO2obtained by TIP hydrolysis) as well as calcination temperature (from 350 to 650◦C) weresystematically investigated. Obtained...
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Spray pyrolysis of doped-ceria barrier layers for solid oxide fuel cells
PublicationGadolinium doped ceria (Ce0.8Gd0.2O2 − x-CGO) layer fabricated by spray pyrolysis is investigated as the diffusion barrier for solid oxide fuel cell. It is deposited between the La0.6Sr0.4FeO3 − δ cathode and the yttria stabilized zirconia electrolyte to mitigate harmful interdiffusion of elements. The parameters of the fabrication process are linked to the measured area specific resistances of the symmetrical cells and the efficiency...
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Nanostructuring of thin Au films deposited on ordered Ti templates for applications in SERS
PublicationIn this work the results on thermal nanostructuring of the Au films on Ti templates as well as morphology and optical properties of the obtained structures are reported. The bimetal nanostructures are fabricated in a multi-step process. First, the titania nanotubes are produced on the surface of Ti foil by anodization in an ethylene glycol-water solution containing fluoride ions. This is followed by chemical etching in oxalic acid...
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Binder-induced surface structure evolution effects on Li-ion battery performance
PublicationA comparative investigation on binder induced chemical and morphological evolution of Li4Ti5O12 electrodes was performed via X-ray photoemission spectroscopy, scanning electron microscopy, and electrochemical measurements. Composite electrodes were obtained using three different binders (PAA, PVdF, and CMC) with 80:10:10 ratio of active material:carbon:binder. The electrochemical performances of the electrodes, were found to be...
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Salt melt synthesis of curved nitrogen-doped carbon nanostructures: ORR kinetics boost
PublicationImplementing metal-free electrocatalysts for the oxygen reduction reaction (ORR) and revealing crucial chemical or topographical parameters driving their activity are vital for the development of power cells. The carbon-based catalysts are very often synthesized through carbonization of biopolymers, in particular, those one containing nitrogen groups such as chitosan. Unfortunately, the resulting carbonaceous materials usually...
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Towards high quality ITO coatings: the impact of nitrogen admixture in HiPIMS discharges
PublicationThe paper reports controlled deposition of optically transparent and electrically conductive ITO films prepared by a combination of rf (13.56 MHz) and High Power Impulse Magnetron Sputtering (HiPIMS) systems without any post deposition thermal treatment/annealing. It is shown that (i) reactive admixture of N2 gas to the process and (ii) pressure in the deposition chamber enable to optimize optical properties of ITO films. Furthermore,...
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Studies on novel BiyXz-TiO2/SrTiO3 composites: Surface properties and visible light-driven photoactivity
PublicationA series of novel BiyXz-TiO2/SrTiO3 composites were prepared by multistep synthesis route. The asprepared photocatalysts were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), Fourier transform infrared (FT-IR), Raman spectra and BET analysis. The photocatalytic activity test was performed in aqueous solution of phenol under...
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Fabrication of anti-corrosion nitrogen doped graphene oxide coatings by electrophoretic deposition
PublicationThis work assesses anti-corrosion properties of graphene and N-doped graphene coatings deposited on copper by an electrophoretic method. Graphene oxide (GO) precursor was synthesized by an improved Hummers' method, whereas N-doping was performed hydrothermally in the presence of ammonia. After nitrogenation, doped graphene oxide samples (NGO) contained a reduced amount of oxygen and about 9% w/w nitrogen as pyridinic, pyrrole,...
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Nickel-nanodiamond coatings electrodeposited from tartrate electrolyte at ambient temperature
PublicationIn this study, nanocrystalline Ni and Ni-diamond coatings were obtained by electrodeposition from tartrate electrolyte at ambient temperature aiming at improving corrosion and wear properties of the material. The created surfaces were investigated with regard to microhardness, adhesion, wear- and corrosion-resistance. The various methods such as atomic force microscopy, scanning electron microscopy, electrochemical impedance spectroscopy...
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The role of electrolysis and enzymatic hydrolysis treatment in the enhancement of the electrochemical properties of 3D-printed carbon black/poly(lactic acid) structures
PublicationAdditive manufacturing, also known as 3D printing, is beginning to play an unprecedented role in developing many applications for industrial or personalized products. The conductive composite structures require additional treatment to achieve an electroactive surface useful for electrochemical devices. In this paper, the surfaces of carbon black/poly(lactic acid) CB-PLA printouts were activated by electrolysis or enzymatic digestion...
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Efficiency of exciton splitting in organic photovoltaic cells within EQE spectrum
PublicationThe paper presents a procedure of estimating the efficiency of exciton splitting at ED/EA interface. The procedure consists in evaluation of splitting of excitons into electron-hole pairs on the basis of the external quantum efficiency spectra of planar cells and spectra of absorbance of active organic layers. The fitting parameters are the exciton splitting probabilities at ED/EA interface. The presented procedure was applied...
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The influence of ILs on TiO2 microspheres activity towards 5-FU removal under artificial sunlight irradiation
PublicationIn this work, the effect of various ionic liquids (ILs), namely, choline chloride [Chol][Cl], hexadecylpyridynium chloride [HDPy][Cl], and tributylmethylammonium chloride [TBMA][Cl], on the morphology, surface compo-sition in relation to photocatalytic oxidation of 5-fluorouracil (5-FU) and phenol in the presence of TiO2 pho-tocatalysts under artificial sunlight conditions was investigated. The highest photoactivity towards cytostatic...
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Experimental tuning of AuAg nanoalloy plasmon resonances assisted by machine learning method
PublicationPlasmonic nanostructures based on AuAg nanoalloys were fabricated by thermal annealing of metallic films in an argon atmosphere. The nanoalloys were chosen because they can extend the wavelength range in which plasmon resonance occurs and thus allow the design of plasmonic platforms with the desired parameters. The influence of initial fabrication parameters and experimental conditions on the formation of nanostructures was investigated....
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Novel two-step synthesis method of thin film heterojunction of BiOBr/Bi2WO6 with improved visible-light-driven photocatalytic activity
PublicationA novel two-step ionic liquid assisted procedure was applied for a controllable synthesis of BiOBr/Bi2WO6 heterojunction thin films. The preparation route involved an anodic oxidation of tungsten foil and hydrothermal transformation of as-anodized oxide in the presence of bismuth precursor and ionic liquid, N-butylpyridinium bromide [BPy][Br]. The BiOBr plates with irregular shapes adhered to the surface of flower-like Bi2WO6 and...
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Lead-free bismuth-based perovskites coupled with g–C3N4: A machine learning based novel approach for visible light induced degradation of pollutants
PublicationThe use of metal halide perovskites in photocatalytic processes has been attempted because of their unique optical properties. In this work, for the first time, Pb-free Bi-based perovskites of the Cs3Bi2X9 type (X = Cl, Br, I, Cl/Br, Cl/I, Br/I) were synthesized and subjected to comprehensive morphological, structural, and surface analyses, and photocatalytic properties in the phenol degradation reaction were examined. Furthermore,...
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Insightful studies of AuCu nanostructures deposited on Ti platform: Effect of rapid thermal annealing on photoelectrochemical activity supported by synchrotron radiation studies
PublicationIn this work, we present the influence of annealing atmospheres during rapid thermal annealing (40◦C/s) on nanostructured Ti platforms modified by 10 nm layer of AuCu alloy obtained via magnetron sputtering. The AuCu/Ti platform annealed under hydrogen atmosphere exhibits the best photoelectrochemical activity under visible light, i.e. 27 times higher photocurrent than for pure Ti dimpled platform, and the lowest reflectance with minimum...
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Toughness augmentation by fibrillation and yielding in nanostructured blends with recycled polyurethane as a modifier
PublicationIn the present paper, we have carefully investigated the morphology and fracture mechanism of the recycled polyurethane (RPU) /epoxy blend system. The second phase (RPU) added to the epoxy resin has a positive effect on the overall mechanical properties. Interestingly, the recycled polymer has a remarkable effect on the fracture toughness of epoxy resin. The mechanism behind the fracture toughness improvement up on the addition...
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Various types of semiconductor photocatalysts modified by CdTe QDs and Pt NPs for toluene photooxidation in the gas phase under visible light
PublicationA novel synthesis process was used to prepare TiO2 microspheres, TiO2 P-25, SrTiO3 and KTaO3 decorated by CdTe QDs and/or Pt NPs. The effect of semiconductor matrix, presence of CdTe QDs and/or Pt NPs on the semiconductor surface as well as deposition technique of Pt NPs (photodeposition or radiolysis) on the photocatalytic activity were investigated. The as-prepared samples were characterized by X-ray powder diffractometry (XRD),...
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Tailoring a low-energy ball milled MnCo2O4 spinel catalyst to boost oxygen evolution reaction performance
PublicationThe development of cost-efficient oxygen evolution reaction (OER) catalysts is one of the most important tasks facing modern techniques for hydrogen production. In this work, for the first time, a low-energy ball milling process of MnCo2O4 (MCO) spinel powders, with a mechanical modification time exceeding 1 day was used. After 6 days of ball-milling, the obtained overpotential of the electrocatalyst reached the value of 375 mV...
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M-BDC (M = Co and/ or Fe) MOFs as effective catalysts for hydrogen generation via hydrolysis of sodium borohydride
PublicationMono- (Co-BDC, Fe-BDC) and bimetallic FeCo-BDC Metal-Organic Frameworks are successfully synthesized by the solvothermal method in DMF at 150 °C within 15 h and tested as catalysts for sodium borohydride hydrolysis. The materials are characterized by FTIR, PXRD, TGA, ICP-OES, H2-TPR, BET model, and SEM-EDS. The catalytic activity of these materials is studied for dehydrogenation of sodium borohydride in water at various temperatures...
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Influence of hydrochloric acid concentration and type of nitrogen source on the electrochemical performance of TiO2/N-MoS2 for energy storage applications
PublicationIn this work, nitrogen-doped molybdenum sulfide was directly deposited on titanium dioxide nanotubes substrate (TiO2/N-MoS2) during hydrothermal synthesis. The study focuses on the influence of hydrochloric acid concentration used for the synthesis, with the results indicating its essential role in thioacetamide hydrolysis and thus in the effectiveness of the N-MoS2 deposition. The electrode material itself is characterized by...
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Poly(hydroxybutyrate-co-hydroxyvalerate) as a biodegradable binder in a negative electrode material for lithium-ion batteries
PublicationIn this work, graphite-based negative electrode for lithium-ion battery consisting a novel and biodegradable binder poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) is compared with standard graphite electrode with polyvinylidene fluoride (PVDF) as a binder. The rate and cycling performance of lithium ion insertion/extraction of electrodes with PHBV in a half-cell configuration are evaluated. Moreover, on the basis of the electrochemical...
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Ionic liquid as morphology-directing agent of two-dimensional Bi2WO6: New insight into photocatalytic and antibacterial activity
PublicationAn efficient and durable utilization of light to drive photocatalytic reactions still requires the overcoming of barriers. Herein, two-dimensional (2D) ultrathin IL_Bi2WO6 (IL_BWO) photocatalysts were prepared for the first time via ionic liquid-assisted hydrothermal route by adjusting the amount of tetrabutylammonium chloride [TBA][Cl], synthesis temperature and duration. IL played the role of morphology-directing agent given...
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Laser-assisted approach for improved performance of Au-Ti based glucose sensing electrodes
PublicationThis paper focuses on the synthesis route and electrochemical properties of electrocatalytic material based on gold nanoparticles (NPs) embedded in a structured titanium template obtained via optimized anodization, chemical etching and laser processing. SEM inspection reveals the presence of Au NPs (60–90 nm in diameter) sited in the titanium foil cavities. Performed electrochemical measurements enable nomination of the set of working...
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Development of novel (BiO)2OHCl/BiOBr enriched with boron doped-carbon nanowalls for photocatalytic cytostatic drug degradation: Assessing photocatalytic process utilization in environmental condition
PublicationIn this work, a series of novel (BiO)2OHCl/BiOBr-x%B:DGNW (x = 0%, 1%, 1.5%, 2%) composites with different content of boron-doped diamond/graphene nanowalls (B:DGNW) were fabricated by simple solvothermal synthesis. A boron-doped diamond/graphene nanowalls (B:DGNW) were prepared by CVD method. A series of analyses: XRD, XPS, SEM, and TEM showed that the photocatalyst (BiO)2OHCl/BiOBr-x%B:DGNW with a “flower-like” morphology was...
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The pulsed laser ablation synthesis of colloidal iron oxide nanoparticles for the enhancement of TiO2 nanotubes photo-activity
PublicationThe rapid, only a few minutes long synthesis of FeO, Fe3O4, and Fe2O3nanoparticles mixture utilizing the pulsedlaser ablation using simply pure iron target and water was demonstrated. The size and crystal phase of Fe-basedNPs were characterized using DLS and HR-TEM techniques, respectively. The metastable suspension of FeO,Fe3O4, and Fe2O3nanoparticles was used to the decoration of anodized TiO2nanotubes (TiO2-NTs) by means ofthe...
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Experimental and DFT insights into an eco-friendly photocatalytic system toward environmental remediation and hydrogen generation based on AgInS2 quantum dots embedded on Bi2WO6
PublicationBismuth tungstate (Bi2WO6) can work as a photocatalyst but suffers from rapid recombination of photogenerated charge carriers. Herein, density functional theory (DFT) simulations revealed that the formation of a thermodynamically stable AgInS2(112)/Bi2WO6(010) heterojunction could promote charge separation and enhance the photoactivity of Bi2WO6. To confirm these theoretical predictions, a new type of photocatalysts in the form...
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Helium-assisted, solvent-free electro-activation of 3D printed conductive carbon-polylactide electrodes
PublicationFused filament fabrication is one of the most rapidly developing 3D printing techniques, with numerous applications, including in the field of applied electrochemistry. Here, the utilisation of conductive carbon black polylactic acid (CB-PLA) for 3D printouts is the most promising. To use CB-PLA as an electrode material, an activation process must be performed, removing the polymer matrix and uncovering the electrically conductive...
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Effect of double thermal and electrochemical oxidation on titanium alloys for medical applications
PublicationThe research focuses on the development and characterization of innovative thin hybrid oxide coatings obtained in subsequent processes of thermal (TO) and electrochemical (EO) oxidation. Four different surface modifications were investigated and the microstructure was determined, the mechanical, chemical and biological properties of the Ti-13Nb-13Zr alloy were assessed using scanning electron microscopy, X-ray dispersion analysis,...
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Low-power microwave-induced fabrication of functionalised few-layer black phosphorus electrodes: A novel route towards Haemophilus Influenzae pathogen biosensing devices
PublicationIn this paper, various passivation schemes were applied at few-layer black phosphorus (FLBP) to achieve covalent functionalisation with 4-azidobenzoic acid, improving its electrochemical response intended for analytical and biosensing applications. The thermal and microwave assisted modification procedures in toluene and dime-thylformamide resulted in high reversibility of reactions on functionalised FLBP using a ferricyanide/ferrocya-nide...
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Stannates, titanates and tantalates modified with carbon and graphene quantum dots for enhancement of visible-light photocatalytic activity
PublicationMost efforts in heterogeneous photocatalysis are focused on development of new and stable photoactive materials efficient in degradation of various pollutants under visible-light irradiation. In this regard, the wide-bandgap perovskite semiconductors, i.e., SrTiO3 (titanate), SrSnO3 (stannate) and AgTaO3 (tantalate), were prepared by a solvothermal method, and then modified with carbon quantum dots (CQDs) or graphene quantum dots...
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Laser-assisted modification of titanium dioxide nanotubes in a tilted mode as surface modification and patterning strategy
PublicationElectrochemical anodization is regarded as a facile and easily scalable fabrication method of titania nanotubes (TiO2NTs). However, due to the extended duration of calcination and further modifications, much faster alternatives are highly required. As a response to growing interest in laser modification of nanotube arrays, a comprehensive investigation of pulsed-laser irradiation and its effect onto TiO2NT properties has been carried out....
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Optical and photocatalytic properties of rare earth metal-modified ZnO quantum dots
PublicationA series of novel ZnO quantum dots modified with rare earth metals was successfully prepared by a simple sol-gel approach. The effects of types (Eu, Er, Tb, Yb, Ho, La) and amounts (from 0.09 to 0.45 mmol) of lanthanides on the optical properties, structural characterization and photocatalytic activity of ZnO/RE QDs were systematically investigated. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform...
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The geometry of free-standing titania nanotubes as a critical factor controlling their optical and photoelectrochemical performance
PublicationTitanium dioxide nanotubes are regarded as one of the most important functional materials and due to their unique electronic properties, chemical stability and photocorrosion resistance, they find applications in, for example, highly efficient photocatalysis or perovskite solar cells. Nevertheless, modification of TiO2 nanotubes is required to overcome their main drawback, i.e. large energy bandgap (>3.2 eV) limiting their ability...
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Solvothermal growth of {0 0 1} exposed anatase nanosheets and their ability to mineralize organic pollutants. The effect of alcohol type and content on the nucleation and growth of TiO2 nanostructures
PublicationHerein, the series of {0 0 1} exposed anatase nanosheets from HF-assisted solvothermal growth synthesis were obtained. The two-dimensional TiO2 were characterized, including both bulk (XRD, DR-UV–Vis, Mott-Schottky) and surface characteristics (N2 sorption, XPS, SEM) with experimental results compiled with Density Functional Theory (DFT) calculations. The effect of alcohol amount and type was studied, demonstrating the crucial...
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The use of lightweight aggregate saturated with PCM as a temperature stabilizing material for road surfaces.
PublicationThis paper presents the possibility of adding lightweight building aggregates to increase the stability – mechanical as well as thermal - of constructions and road objects. This stability can be achieved through saturating the porous granules of aggregate with a phase-change material (PCM) that allows the accumulation of solar heat. Intense solar radiation, especially during the summer, can cause the asphalt on road surfaces, bridges...
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Scalability of surrogate-assisted multi-objective optimization of antenna structures exploiting variable-fidelity electromagnetic simulation models
PublicationMulti-objective optimization of antenna structures is a challenging task due to high-computational cost of evaluating the design objectives as well as large number of adjustable parameters. Design speedup can be achieved by means of surrogate-based optimization techniques. In particular, a combination of variable-fidelity electromagnetic (EM) simulations, design space reduction techniques, response surface approximation (RSA) models,...
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SORPTION OF SELECTED CHLORINATED SOLVENTS ON PLANT DEBRIS COLLECTED IN A CITY PARK
PublicationDebris from deciduous trees in the form of park green waste was investigated as a potential biosorbent for the removal of chlorinated solvents from water. The sorption properties of beech leaves and cupules, oak leaves and acorns, birch leaves and lime leaves (all tree species common for a moderate climate) in a non-modified form were investigated with regard to the removal of perchloroethylene, 1,1,2-trichloroethane and 1,1,1,2-tetrachlorothane....
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High Performance Tubular Heat Exchanger with Minijet Heat Transfer Enhancement
PublicationIn the paper, the original cylindrical heat exchanger with minijets (MJHE) was introduced. The systematic experimental analysis of the prototype heat exchanger was described with special attention paid to such parameters as the heat transfer effectiveness, heat transfer rates, overall heat transfer coefficients, and pressure drop. The heat transfer coefficients were determined based on Wilson plot method, the most suitable approach...
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Elctrochemical oxidation and corrosion resistance of the Ti13Nb13Zr alloy
PublicationThis paper presents the results of oxidation and corrosion tests carried out on titanium alloy Ti13Nb13Zr. The oxide film was prepared by electrochemical environment 2M H3PO4 for 30 min and 1 h, at a constant voltage 40V. The tests of corrosion resistance were performed by potentiostatic method in Ringer's solution at different pH values: 7, 5 and 3. The change in an appearance of surface and the increase in corrosion resistance...
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Dependence between Ionic Liquid Structure and Mechanism of Visible-Light-Induced Activity of TiO2 Obtained by Ionic-Liquid-Assisted Solvothermal Synthesis
PublicationBecause of the tremendous structural diversityof ionic liquids (ILs), simple transfer of observations performed for one IL used for IL-TiO2 preparation on different samples is not possible. Therefore, four ionic liquids, all containing distinct nitrogen-bearing organic cations (pyridinium, pyrrolidinium, ammonium, imidazolium), were used for the first time for the preparation of IL-TiO2 composites. The role of the individual IL...
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Biological and mechanical properties of bone cement with nanoarticles - in vitro and in vivo research
PublicationDespite antibiotic preventive treatment both before and after implant implementation, the risks of infection are real. These infections develop at the implant surface a few months after inserting them into the body. To prevent the development of bacteria and reduce the risk of infection, implants coated with nanoparticles are used. The Mechanical Department of the Technical University of Gdansk carries out research into using bone...
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Preliminary studies of seamless flux cored wires stored in extreme conditions
PublicationIn the paper preliminary experimental studies of flux cored wires moisturized under controlled conditions are described. Three seamless wires of different grades have been placed in environmental chamber and moisturized in extremely adverse conditions (temperature T = 60° C, relative humidity H = 90%) for 240 hours. During this time measurements of weight gain and observations of surface of wires have been carried out. Also diffusible...
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Air journal bearing utilizing near-field acoustic levitation: stationary shaft case
PublicationResults of a study to examine a unique idea of self-levitating journal bearing are presented in this paper. the idea represents a radical departure from the current bearing technology. it utilisesacoustic levitation, which relies on the sound energy radiated by an object supporting a load. acoustic levitation has been demonstrated to support loads of up to 10 kg. in order to support a load theacoustic wave emitted by the radiating...
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Geotechnical Analysis and Stability Assessment of a Landslide Event in Gera Woreda, Ethiopia
PublicationThis study investigates the geotechnical factors influencing a recent landslide event in Gera Woreda, Ethiopia. The primary objective was to identify the soil properties contributing to landslide occurrence and understand the triggering mechanisms. Field investigations, soil sampling from both affected and unaffected areas, and subsequent laboratory characterization were conducted. The analysis revealed a dominance of fine-grained...
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M-integral for finite anti-plane shear of a nonlinear elastic matrix with rigid inclusions
PublicationThe path-independent M-integral plays an important role in analysis of solids with inhomogeneities. However, the available applications are almost limited to linear-elastic or physically non-linear power law type materials under the assumption of infinitesimal strains. In this paper we formulate the M-integral for a class of hyperelastic solids undergoing finite anti-plane shear deformation. As an application we consider the problem...
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SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF NIOBIUM-DOPED HYDROXYAPATITE CERAMICS
PublicationHydroxyapatite (HAp) ceramic materials are considered as one of the most promising implant materials in bone surgery and in dentistry. They exhibit unique biocompatibility, bioactivity, and osteoconductivity, which are the most desirable biomaterial features. However, HAp itself is brittle, has low strength, high degree of crystallinity and low solubility at physiological pH. Doping synthetic HAp with metal ions plays an important...
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Thermally activated natural chalcopyrite for Fenton-like degradation of Rhodamine B: Catalyst characterization, performance evaluation, and catalytic mechanism
PublicationIn this work, catalytic activity of natural chalcopyrite (CuFeS2) was improved by thermal activation. The modified chalcopyrite was used as efficient catalyst for degradation of organic dye Rhodamine B (RhB) through advanced oxidation process (AOP). Effects of catalyst dosage, H2O2 concentration, reaction temperature, solution pH, anions, and natural organic matter on the degradation efficiency of RhB were investigated. This study...
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Generative Process Planning with Reasoning based on Geometrical Product Specification
PublicationThe focus of this paper is on computer aided process planning for parts manufacture in systems of definite process capabilities, involving the use of multi-axis machining centers for parts shaping and grinding machines for finishing. It presents in particular a decision making scheme for setup determination as a part of generative process planning. The planning procedurę consists of two stages. The first stage is associated with...
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Multi-objective design optimization of antenna structures using sequential domain patching with automated patch size deter-mination
PublicationIn this paper, a simple yet efficient and reliable technique for fully automated multi-objective design optimization of antenna structures using sequential domain patching (SDP) is discussed. The optimization procedure according to SDP is a two-step process: (i) obtaining the initial set of Pareto-optimal designs representing the best possible trade-offs between considered conflicting objectives, and (ii) Pareto set refinement...