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The cyclic voltammogram recorded in the potential range between 0 V and 800 mV with scan rate of 100 mV s −1 was used to determine the measure of antioxidants content (antioxidant capacity) present in Sambucus nigra L. extract. The antioxidant capacity of the extract was 4.06 mg GAE g −1 fw (mg of gallic acid equivalents per gram of fresh weight of the extract). The corrosion inhibition efficiency of Sambucus nigra L. extract on aluminium, copper, and bronze in 3 % NaCl solution was studied by potentiodynamic polarization and electrochemical impedance spectroscopy. Polarization data showed that extract acted as a mixed-type inhibitor, that the corrosion inhibition process was spontaneous physical adsorption (Δ G ≈ –16 kJ mol –1 ) of the extract molecules on metals surfaces and followed Freundlich isotherm. Impedance spectroscopy studies revealed that increasing the concentration of extract reduced the double-layer capacitance and increased the charge transfer resistance. The highest inhibition efficiencies (Cu: ~ 57 %, CuSn14: ~74 % and Al: ~58 %) were achieved for an extract concentration of 1.0 g L –1 .

G. Zlatić, Ivana Martinović, Z. Pilić, Andrea Paut, Ivana Mitar, A. Prkić, Dušan Čulum

Plant extracts are increasingly being examined in the corrosion inhibition of metal and alloys in various environments due to their potent antioxidant properties. The use of Artemisia annua L. aqueous extract (AAE) as an aluminium alloy 5083 (ALA) corrosion inhibitor in artificial seawater (ASW) was investigated using electrochemical tests and spectroscopy tools, while the active biocompounds found in AAE were analyzed using high-performance liquid chromatography (HPLC). Electrochemical results showed that AAE acts as an anodic inhibitor through the physisorption (ΔG ≈ –16.33 kJ mol−1) of extract molecules on the ALA surface, thus reducing the active sites for the dissolution of the alloy in ASW. Fourier-transform infrared spectra confirmed that phenolic acids found in AAE formed the surface layer that protects ALA against the corrosive marine environment, while HPLC analysis confirmed that the main phytoconstituents of AAE were chlorogenic acid and caffeic acid. The inhibition action of phenolic acids and their derivatives found in the AAE was based on the physisorption of caffeic acid on the ALA surface, which improved physicochemical properties of the barrier film and/or conversion of Al3+ to elemental aluminium by phenolic acids as reducens, which slowed down the diffusion rate of Al3+ to or from the ALA surfaces. The protective effect of the surface layer formed in the presence of AAE against ASW was also confirmed by inductively coupled plasma–optical emission spectrometry (ICP-OES) whereby the measured concentration of Al ions after 1 h of immersion of ALA in the pure ASW was 15.30 μg L−1 cm−2, while after the addition of 1 g L−1 AAE, the concentration was 3.09 μg L−1 cm−2.

Chih-Wei Hsu, Ivana Martinović, R. Magnusson, B. Bakhit, J. Palisaitis, P. Persson, P. Rouf, H. Pedersen

InxGa1−x N is a strategically important material for electronic devices given its tunable bandgap, modulated by the In/Ga ratio. However, current applications are hindered by defects caused by strain relaxation and phase separation in the material. Here, we demonstrate growth of homogeneous InxGa1−x N films with 0.3 < x < 0.8 up to ∼30 nm using atomic layer deposition (ALD) with a supercycle approach, switching between InN and GaN deposition. The composition is uniform along and across the films, without signs of In segregation. The InxGa1−x N films show higher In-content than the value predicted by the supercycle model. A more pronounced reduction of GPCInN than GPCGaN during the growth processes of InN and GaN bilayers is concluded based on our analysis. The intermixing between InN and GaN bilayers is suggested to explain the enhanced overall In-content. Our results show the advantage of ALD to prepare high-quality InxGa1−x N films, particularly with high In-content, which is difficult to achieve with other growth methods.

G. Zlatić, Anamarija Arapović, Ivana Martinović, Anita Martinović Bevanda, P. Bošković, A. Prkić, Andrea Paut, Tina Vukusic

Considering the vast cultural and traditional heritage of the use of aromatic herbs and wildflowers for the treatment of light medical conditions in the Balkans, a comparison of the antioxidant capacity of wildflowers extracts from Herzegovina was studied using both cyclic voltammetry and spectrophotometry. The cyclic voltammograms taken in the potential range between 0 V and 800 mV and scan rate of 100 mV s−1 were used for the quantification of the electrochemical properties of polyphenols present in four aqueous plant extracts. Antioxidant capacity expressed as mmoL of gallic acid equivalents per gram of dried weight of the sample (mmoL GAE g−1 dw) was deduced from the area below the major anodic peaks (Q400 pH 6.0, Q500 pH 4.7, Q600 pH 3.6). The results of electrochemical measurements suggest that the major contributors of antioxidant properties of examined plants are polyphenolic compounds that contain ortho-dihydroxy-phenol or gallate groups. Using Ferric reducing-antioxidant power (FRAP) and 2,2′-azino-bis spectrophotometric methods (3-ethylbenzthiazoline-6-sulphonic acid) radical cation-scavenging activity (ABTS) additionally determined antioxidant capacity. The FRAP results ranged from 2.9702–9.9418 mmoL Fe/g dw, while the results for ABTS assays expressed as Trolox equivalents (TE) ranged from 14.1842–42.6217 mmoL TE/g dw. The Folin–Ciocalteu procedure was applied to determine the total phenolics content (TP). The TP content expressed as Gallic acid equivalents (GAE) ranged from 6.0343–9.472 mmoL GAE/g dw. The measurements of total flavonoid (TF) and total condensed tannin (TT) contents were also performed to obtain a broader polyphenolic profile of tested plant materials. Origanum vulgare L. scored the highest on each test, with the exception of TT content, followed by the Mentha × piperita L., Artemisia annua L., and Artemisia absinthium L., respectively. The highest TT content, expressed as mg of (−)catechin equivalents per gram of dried weight of sample (mg CE/g dw), was achieved with A. absinthium extract (119.230 mg CE/g dw) followed by O. vulgare (90.384 mg CE/g dw), A. annua (86.538 mg CE/g dw) and M. piperita (69.231 mg CE/g dw), respectively. In addition, a very good correlation between electrochemical and spectroscopic methods was achieved.

The corrosion behavior of copper, tin, and bronze CuSn14 is studied in simulated acid rain (pH 4.5) by electrochemical techniques, cyclic voltammetry and electrochemical impedance spectroscopy. The potentiodynamic formation of anodic oxide film on copper and tin is described in terms of high‐field model. Cyclic voltammetry shows that dissolution of bronze is higher than of pure copper metal in acid rain. Electrochemical impedance spectroscopy data reveal that oxide films formed on copper and tin have a higher resistance and suppressed diffusion process through the surface layer than the oxide film formed on bronze CuSn14 at the same conditions.

Extract of Alchemilla vulgaris L. was investigated as eco-friendly corrosion inhibitor for aluminium in 3 % NaCl using electrochemical techniques. According to the results, inhibition efficiency increases with the increase concentration of extract and the highest efficiency (~80 %) is recorded for the maximal concentration of extract (1.0 g L–1). The inhibition activity of extract occurs by the spontaneous physisorption (ΔG ≈ –16 kJ mol–1) on active sites of aluminium surface that follows Freundlich isotherm. Polarization curves showed that Alchemilla vulgaris L. extract act s a mixed-type inhibitor. The effect of temperature on the aluminium corrosion and inhibition action of extract was studied and the result showed that the corrosion rate increased and the inhibitor efficiency decreased with increase of temperature. The calculated values of the activation energy confirmed presence of inhibitive Alchemilla vulgaris L. extract on aluminium surface.

P. Rouf, Rouzbeh Samii, Karl Rönnby, B. Bakhit, S. Buttera, Ivana Martinović, L. Ojamäe, Chih-Wei Hsu et al.

Gallium nitride (GaN) is the main component of modern-day high electron mobility transistor electronic devices due to its favorable electronic properties. As electronic devices become smaller with more complex architecture, the ability to deposit high-quality GaN films at low temperature is required. Herein, we report a new highly volatile Ga(III) triazenide precursor and demonstrate its ability to deposit high-quality epitaxial GaN by atomic layer deposition (ALD). This new Ga(III) triazenide precursor, the first hexacoordinated M–N bonded Ga(III) precursor used in a vapor deposition process, was easily synthesized and purified by sublimation. Thermogravimetric analysis showed single step volatilization with an onset temperature of 150 °C and negligible residual mass. Three temperature intervals with self-limiting growth were observed when depositing GaN films. In the second growth interval, the films were found to be near stoichiometric with very low levels of impurities and epitaxial orientation on 4H-SiC without an AlN seed layer. The films grown at 350 °C were found to be smooth with a sharp interface between the substrate and film. The bandgap of these films was 3.41 eV with the Fermi level at 1.90 eV, showing that the GaN films were unintentionally n-type doped. This new triazenide precursor enables ALD of GaN for semiconductor applications and provides a new Ga(III) precursor for future deposition processes.

Chih-Wei Hsu, P. Deminskyi, Ivana Martinović, I. Ivanov, J. Palisaitis, H. Pedersen

Indium nitride (InN) is a highly promising material for high frequency electronics given itslow band gap and high electron mobility. The development of InN-based devices is hamperedby the limitations in depositing very thin InN films of high quality. We demonstrate growth ofhigh-structural-quality nanometer thin InN films on 4H-SiC by atomic layer deposition (ALD).High resolution X-ray diffraction and transmission electron microscopy show epitaxial growthand an atomically sharp interface between InN and 4H-SiC. The InN film is fully relaxed already after a few atomic layers and shows a very smooth morphology where the low surfaceroughness (0.14 nm) is found to reproduced sub-nanometer surface features of the substrate. Raman measurements show an asymmetric broadening caused by grains in the InN film. Our results show the potential of ALD to prepare high quality nanometer-thin InN films for subsequent formation of heterojunctions.

P. Rouf, N. O’Brien, S. Buttera, Ivana Martinović, B. Bakhit, Erik Martinsson, J. Palisaitis, Chih-Wei Hsu et al.

Low temperature deposition of high-quality epitaxial GaN is crucial for its integration inelectronic applications. Chemical vapor deposition at approximately 800 °C using SiC with anAlN buffer layer or nitridized sapphire as substrates is used to facilitate the GaN growth. Here,we present a low temperature atomic layer deposition (ALD) process usingtris(dimethylamido)gallium(III) with NH3 plasma. The ALD process shows self-limitingbehaviour between 130-250 °C with a growth rate of 1.4 Å/cycle. The GaN films produced werecrystalline on Si(100) at all deposition temperatures with a near stochiometric Ga/N ratio withlow carbon and oxygen impurities. When GaN was deposited on 4H-SiC, the films grewepitaxially without the need for an AlN buffer layer, which has never been reported before. The bandgap of the GaN films was measured to be ~3.42 eV and the fermi level showed that the GaN was unintentionally n-type doped. This study shows the potential of ALD for GaN-basedelectronic devices.

The inhibition of copper corrosion by Helichrysum italicum extract (HI) in simulated acid rain was investigated using electrochemical techniques. Results indicate an increase in corrosion inhibition efficiency with the HI extract concentration. The inhibitive process was assumed to occur via adsorption of the extract on the metal surface. The thermodynamic data indicated physical adsorption and followed the Freundlich isotherm. The effect of temperature on the copper corrosion was studied. The value of the activation energy confirmed physisorption of extract molecules on the copper surface. The concentration of Cu ions released into solution, measured by atomic absorption spectrometry, was in accordance with the electrochemical results.

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